Attrition Resistant Fischer-Tropsch Catalysts Based on FCC Supports

DOE Office of Scientific and Technical Information (OSTI.GOV)

Adeyiga, Adeyinka

2010-02-05

Commercial spent fluid catalytic cracking (FCC) catalysts provided by Engelhard and Albemarle were used as supports for Fe-based catalysts with the goal of improving the attrition resistance of typical F-T catalysts. Catalysts with the Ruhrchemie composition (100 Fe/5 Cu/4.2 K/25 spent FCC on mass basis) were prepared by wet impregnation. XRD and XANES analysis showed the presence of Fe{sub 2}O{sub 3} in calcined catalysts. FeC{sub x} and Fe{sub 3}O{sub 4} were present in the activated catalysts. The metal composition of the catalysts was analyzed by ICP-MS. F-T activity of the catalysts activated in situ in CO at the same conditionsmore » as used prior to the attrition tests was measured using a fixed bed reactor at T = 573 K, P = 1.38 MPa and H{sub 2}:CO ratio of 0.67. Cu and K promoted Fe supported over Engelhard provided spent FCC catalyst shows relatively good attrition resistance (8.2 wt% fines lost), high CO conversion (81%) and C{sub 5}+ hydrocarbons selectivity (18.3%).« less

Too much FCC catalyst activity can cut yields

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wichers, W.R.; Upson, L.

1984-03-19

For many people working in the field of catalytic cracking, high equilibrium catalyst activity is inherently good. It is surprising how many times this line of reasoning is accepted by the refiner. There also seems to be something psychologically satisfying in seeing an equilibrium catalyst report where the catalyst activity is reported as a high number. Generally, everyone is happy when the reported activity of equilibrium catalyst is increasing and unhappy when it is going down. In the past, increasing catalyst activity did result in improved operations. For units that operated with substantial amounts of bed cracking, higher activity catalystmore » allowed the amount of bed cracking to be reduced and the relative amount of cracking that occurred in the riser to be increased. The switch from bed to riser cracking decreased catalytic coke make and gasoline overcracking, thus reducing regenerator temperature and improving gasoline yields.« less

High-throughput investigation of catalysts for JP-8 fuel cracking to liquefied petroleum gas.

PubMed

Bedenbaugh, John E; Kim, Sungtak; Sasmaz, Erdem; Lauterbach, Jochen

2013-09-09

Portable power technologies for military applications necessitate the production of fuels similar to LPG from existing feedstocks. Catalytic cracking of military jet fuel to form a mixture of C₂-C₄ hydrocarbons was investigated using high-throughput experimentation. Cracking experiments were performed in a gas-phase, 16-sample high-throughput reactor. Zeolite ZSM-5 catalysts with low Si/Al ratios (≤25) demonstrated the highest production of C₂-C₄ hydrocarbons at moderate reaction temperatures (623-823 K). ZSM-5 catalysts were optimized for JP-8 cracking activity to LPG through varying reaction temperature and framework Si/Al ratio. The reducing atmosphere required during catalytic cracking resulted in coking of the catalyst and a commensurate decrease in conversion rate. Rare earth metal promoters for ZSM-5 catalysts were screened to reduce coking deactivation rates, while noble metal promoters reduced onset temperatures for coke burnoff regeneration.

Making fired bricks with spent equilibrium catalyst-a technical feasibility study

USGS Publications Warehouse

Chou, M.-L.; Chen, L.-M.; Lai, Y.-C.; Chou, S.-F.

2009-01-01

Fluid catalytic cracking in an oil refinery uses a catalyst, such as an alumino-silicate zeolite, in the conversion of heavy hydrocarbons to light hydrocarbons. A small fraction of the catalyst is continually replaced with fresh catalyst to maintain activity. In North America, more than 400 tons of spent alumino-silicate equilibrium catalyst (spent e-cat), and worldwide, more than 1,100 tons, are generated daily, most of which is disposed of in landfills (municipal and on-site facilities). In this study, three spent e-cat samples were tested in a value-added application that would utilize this waste in the manufacturing of fired bricks. The results of this study indicate that spent e-cat is a technically feasible raw material substitute for the clay and shale commonly used in fired brick production. Fired bricks produced with up to 30 wt% of spent e-cat showed good physical appearance and their water absorption properties met the ASTM C 62 specifications for building bricks of either the moderate-or severe-weathering grade.

Assessment of the Pozzolanic Activity of a Spent Catalyst by Conductivity Measurement of Aqueous Suspensions with Calcium Hydroxide

PubMed Central

Velázquez, Sergio; Monzó, José M.; Borrachero, María V.; Payá, Jordi

2014-01-01

The pozzolanic activity of the spent catalyst produced by fluid catalytic cracking (FCC) has been studied by various methods in recent years. However, no quick and easy method has been reported for this activity based on the associated studies. In this work, the pozzolanic activity of a spent catalyst was investigated by measuring its electrical conductivity in aqueous suspensions of pozzolan/calcium hydroxide. The behavior of the FCC catalyst residue was compared to that of reactive and inert materials of similar chemical compositions. Further, the influence of temperature on the suspension was studied, and also, a new method was proposed in which the pozzolan/calcium hydroxide ratio was varied (with the initial presence of solid Ca(OH)2 in the system). It was concluded that the method is effective, fast and simple for evaluating the high reactivity of the catalyst. Therefore, this method is an alternative for the evaluation of the reactivity of pozzolanic materials. PMID:28788583

Rapid starting methanol reactor system

DOEpatents

Chludzinski, Paul J.; Dantowitz, Philip; McElroy, James F.

1984-01-01

The invention relates to a methanol-to-hydrogen cracking reactor for use with a fuel cell vehicular power plant. The system is particularly designed for rapid start-up of the catalytic methanol cracking reactor after an extended shut-down period, i.e., after the vehicular fuel cell power plant has been inoperative overnight. Rapid system start-up is accomplished by a combination of direct and indirect heating of the cracking catalyst. Initially, liquid methanol is burned with a stoichiometric or slightly lean air mixture in the combustion chamber of the reactor assembly. The hot combustion gas travels down a flue gas chamber in heat exchange relationship with the catalytic cracking chamber transferring heat across the catalyst chamber wall to heat the catalyst indirectly. The combustion gas is then diverted back through the catalyst bed to heat the catalyst pellets directly. When the cracking reactor temperature reaches operating temperature, methanol combustion is stopped and a hot gas valve is switched to route the flue gas overboard, with methanol being fed directly to the catalytic cracking reactor. Thereafter, the burner operates on excess hydrogen from the fuel cells.

High-performance Fuel Cell with Stretched Catalyst-Coated Membrane: One-step Formation of Cracked Electrode.

PubMed

Kim, Sang Moon; Ahn, Chi-Yeong; Cho, Yong-Hun; Kim, Sungjun; Hwang, Wonchan; Jang, Segeun; Shin, Sungsoo; Lee, Gunhee; Sung, Yung-Eun; Choi, Mansoo

2016-05-23

We have achieved performance enhancement of polymer electrolyte membrane fuel cell (PEMFC) though crack generation on its electrodes. It is the first attempt to enhance the performance of PEMFC by using cracks which are generally considered as defects. The pre-defined, cracked electrode was generated by stretching a catalyst-coated Nafion membrane. With the strain-stress property of the membrane that is unique in the aspect of plastic deformation, membrane electrolyte assembly (MEA) was successfully incorporated into the fuel cell. Cracked electrodes with the variation of strain were investigated and electrochemically evaluated. Remarkably, mechanical stretching of catalyst-coated Nafion membrane led to a decrease in membrane resistance and an improvement in mass transport, which resulted in enhanced device performance.

Development Of Simulation Model For Fluid Catalytic Cracking

NASA Astrophysics Data System (ADS)

Ghosh, Sobhan

2010-10-01

Fluid Catalytic Cracking (FCC) is the most widely used secondary conversion process in the refining industry, for producing gasoline, olefins, and middle distillate from heavier petroleum fractions. There are more than 500 units in the world with a total processing capacity of about 17 to 20% of the crude capacity. FCC catalyst is the highest consumed catalyst in the process industry. On one hand, FCC is quite flexible with respect to it's ability to process wide variety of crudes with a flexible product yield pattern, and on the other hand, the interdependence of the major operating parameters makes the process extremely complex. An operating unit is self balancing and some fluctuations in the independent parameters are automatically adjusted by changing the temperatures and flow rates at different sections. However, a good simulation model is very useful to the refiner to get the best out of the process, in terms of selection of the best catalyst, to cope up with the day to day changing of the feed quality and the demands of different products from FCC unit. In addition, a good model is of great help in designing the process units and peripherals. A simple empirical model is often adequate to monitor the day to day operations, but they are not of any use in handling the other problems such as, catalyst selection or, design / modification of the plant. For this, a kinetic based rigorous model is required. Considering the complexity of the process, large number of chemical species undergoing "n" number of parallel and consecutive reactions, it is virtually impossible to develop a simulation model based on the kinetic parameters. The most common approach is to settle for a semi empirical model. We shall take up the key issues for developing a FCC model and the contribution of such models in the optimum operation of the plant.

Attrition of fluid cracking catalyst in fluidized beds

DOE Office of Scientific and Technical Information (OSTI.GOV)

Boerefijn, R.; Ghadiri, M.

1996-12-31

Particle attrition in fluid catalytic cracking units causes loss of catalyst, which could amount to a few tonnes per day! The dependence of attrition on the process conditions and catalyst properties is therefore of great industrial interest, but it is however not well established at present. The process of attrition in the jetting area of fluidised beds is addressed and the attrition test method of Forsythe & Hertwig is analysed in this paper. This method is used commonly to assess the attrition propensity of FCC powder, whereby the attrition rate in a single jet at very high orifice velocity (300more » m s{sup -1}) is measured. There has been some concern on the relevance of this method to attrition in FCC units. Therefore, a previously-developed model of attrition in the jetting region is employed in an attempt to establish a solid basis of interpretation of the Forsythe & Hertwig test and its application as an industrial standard test. The model consists of two parts. The first part predicts the solids flow patterns in the jet region, simulating numerically the Forsythe & Hertwig test. The second part models the breakage of single particles upon impact. Combining these two models, thus linking single particle mechanical properties to macroscopic flow phenomena, results in the modelling of the attrition rate of particles entrained into a single high speed jet. High speed video recordings are made of a single jet in a two-dimensional fluidised bed, at up to 40500 frames per second, in order to quantify some of the model parameters. Digital analysis of the video images yields values for particle velocities and entrainment rates in the jet, which can be compared to model predictions. 15 refs., 8 figs.« less

Mapping Metals Incorporation of a Whole Single Catalyst Particle Using Element Specific X-ray Nanotomography

DOE PAGES

Meirer, Florian; Morris, Darius T.; Kalirai, Sam; ...

2015-01-02

Full-field transmission X-ray microscopy has been used to determine the 3D structure of a whole individual fluid catalytic cracking (FCC) particle at high spatial resolution and in a fast, noninvasive manner, maintaining the full integrity of the particle. Using X-ray absorption mosaic imaging to combine multiple fields of view, computed tomography was performed to visualize the macropore structure of the catalyst and its availability for mass transport. We mapped the relative spatial distributions of Ni and Fe using multiple-energy tomography at the respective X-ray absorption K-edges and correlated these distributions with porosity and permeability of an equilibrated catalyst (E-cat) particle.more » Both metals were found to accumulate in outer layers of the particle, effectively decreasing porosity by clogging of pores and eventually restricting access into the FCC particle.« less

Effect of catalyst additives on the production of biofuels from palm oil cracking in a transport riser reactor.

PubMed

Chew, Thiam Leng; Bhatia, Subhash

2009-05-01

Catalytic cracking of crude palm oil (CPO) and used palm oil (UPO) were studied in a transport riser reactor for the production of biofuels at a reaction temperature of 450 degrees C, with residence time of 20s and catalyst-to-oil ratio (CTO) of 5 gg(-1). The effect of HZSM-5 (different Si/Al ratios), beta zeolite, SBA-15 and AlSBA-15 were studied as physically mixed additives with cracking catalyst Rare earth-Y (REY). REY catalyst alone gave 75.8 wt% conversion with 34.5 wt% of gasoline fraction yield using CPO, whereas with UPO, the conversion was 70.9 wt% with gasoline fraction yield of 33.0 wt%. HZSM-5, beta zeolite, SBA-15 and AlSBA-15 as additives with REY increased the conversion and the yield of organic liquid product. The transport riser reactor can be used for the continuous production of biofuels from cracking of CPO and UPO over REY catalyst.

High-resolution single-molecule fluorescence imaging of zeolite aggregates within real-life fluid catalytic cracking particles.

PubMed

Ristanović, Zoran; Kerssens, Marleen M; Kubarev, Alexey V; Hendriks, Frank C; Dedecker, Peter; Hofkens, Johan; Roeffaers, Maarten B J; Weckhuysen, Bert M

2015-02-02

Fluid catalytic cracking (FCC) is a major process in oil refineries to produce gasoline and base chemicals from crude oil fractions. The spatial distribution and acidity of zeolite aggregates embedded within the 50-150 μm-sized FCC spheres heavily influence their catalytic performance. Single-molecule fluorescence-based imaging methods, namely nanometer accuracy by stochastic chemical reactions (NASCA) and super-resolution optical fluctuation imaging (SOFI) were used to study the catalytic activity of sub-micrometer zeolite ZSM-5 domains within real-life FCC catalyst particles. The formation of fluorescent product molecules taking place at Brønsted acid sites was monitored with single turnover sensitivity and high spatiotemporal resolution, providing detailed insight in dispersion and catalytic activity of zeolite ZSM-5 aggregates. The results point towards substantial differences in turnover frequencies between the zeolite aggregates, revealing significant intraparticle heterogeneities in Brønsted reactivity. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

High-performance Fuel Cell with Stretched Catalyst-Coated Membrane: One-step Formation of Cracked Electrode

PubMed Central

Kim, Sang Moon; Ahn, Chi-Yeong; Cho, Yong-Hun; Kim, Sungjun; Hwang, Wonchan; Jang, Segeun; Shin, Sungsoo; Lee, Gunhee; Sung, Yung-Eun; Choi, Mansoo

2016-01-01

We have achieved performance enhancement of polymer electrolyte membrane fuel cell (PEMFC) though crack generation on its electrodes. It is the first attempt to enhance the performance of PEMFC by using cracks which are generally considered as defects. The pre-defined, cracked electrode was generated by stretching a catalyst-coated Nafion membrane. With the strain-stress property of the membrane that is unique in the aspect of plastic deformation, membrane electrolyte assembly (MEA) was successfully incorporated into the fuel cell. Cracked electrodes with the variation of strain were investigated and electrochemically evaluated. Remarkably, mechanical stretching of catalyst-coated Nafion membrane led to a decrease in membrane resistance and an improvement in mass transport, which resulted in enhanced device performance. PMID:27210793

Process for magnetic beneficiating petroleum cracking catalyst

DOEpatents

Doctor, R.D.

1993-10-05

A process is described for beneficiating a particulate zeolite petroleum cracking catalyst having metal values in excess of 1000 ppm nickel equivalents. The particulate catalyst is passed through a magnetic field in the range of from about 2 Tesla to about 5 Tesla generated by a superconducting quadrupole open-gradient magnetic system for a time sufficient to effect separation of said catalyst into a plurality of zones having different nickel equivalent concentrations. A first zone has nickel equivalents of about 6,000 ppm and greater, a second zone has nickel equivalents in the range of from about 2000 ppm to about 6000 ppm, and a third zone has nickel equivalents of about 2000 ppm and less. The zones of catalyst are separated and the second zone material is recycled to a fluidized bed of zeolite petroleum cracking catalyst. The low nickel equivalent zone is treated while the high nickel equivalent zone is discarded. 1 figures.

Process for magnetic beneficiating petroleum cracking catalyst

DOEpatents

Doctor, Richard D.

1993-01-01

A process for beneficiating a particulate zeolite petroleum cracking catalyst having metal values in excess of 1000 ppm nickel equivalents. The particulate catalyst is passed through a magnetic field in the range of from about 2 Tesla to about 5 Tesla generated by a superconducting quadrupole open-gradient magnetic system for a time sufficient to effect separation of said catalyst into a plurality of zones having different nickel equivalent concentrations. A first zone has nickel equivalents of about 6,000 ppm and greater, a second zone has nickel equivalents in the range of from about 2000 ppm to about 6000 ppm, and a third zone has nickel equivalents of about 2000 ppm and less. The zones of catalyst are separated and the second zone material is recycled to a fluidized bed of zeolite petroleum cracking catalyst. The low nickel equivalent zone is treated while the high nickel equivalent zone is discarded.

Catalyst Residence Time Distributions in Riser Reactors for Catalytic Fast Pyrolysis. Part 2: Pilot-Scale Simulations and Operational Parameter Study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Foust, Thomas D.; Ziegler, Jack L.; Pannala, Sreekanth

2017-02-21

Here, wsing the validated simulation model developed in part one of this study for biomass catalytic fast pyrolysis (CFP), we assess the functional utility of using this validated model to assist in the development of CFP processes in fluidized catalytic cracking (FCC) reactors to a commercially viable state. Specifically, we examine the effects of mass flow rates, boundary conditions (BCs), pyrolysis vapor molecular weight variation, and the impact of the chemical cracking kinetics on the catalyst residence times. The factors that had the largest impact on the catalyst residence time included the feed stock molecular weight and the degree ofmore » chemical cracking as controlled by the catalyst activity. Lastly, because FCC reactors have primarily been developed and utilized for petroleum cracking, we perform a comparison analysis of CFP with petroleum and show the operating regimes are fundamentally different.« less

Effect of Particle Size Upon Pt/SiO 2 Catalytic Cracking of n-Dodecane Under Supercritical Conditions: in situ SAXS and XANES Studies

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lee, Sungwon; Lee, Sungsik; Kumbhalkar, Mrunmayi

The endothermic cracking and dehydrogenation of n-dodecane is investigated over well-defined nanometer size platinum catalysts supported on SiO 2 to study the particle size effects in the catalytic cracking reaction, with simultaneous in situ monitoring of the particle size and oxidation state of the working catalysts by in situ SAXS (small angle X-ray scattering) and XAS (X-ray absorption spectroscopy). The selectivity toward olefins products was found dominant in the 1 nm size platinum catalysts, whereas paraffins are dominant in the 2 nm catalysts. This reveals a strong correlation between catalytic performance and catalyst size as well as the stability ofmore » the nanoparticles in supercritical condition of n-dodecane. The presented results suggest that controlling the size and geometric structure of platinum nanocatalysts could lead to a fundamentally new level of understanding of nanoscale materials by monitoring the catalysts in realistic reaction conditions.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dayton, David C; Kataria, Atish; Gupta, Rabhubir

The objective of the project is to develop and demonstrate a novel fluidized-bed process module called a Therminator to simultaneously destroy and/or remove tar, NH3 and H2S from raw syngas produced by a fluidized-bed biomass gasifier. The raw syngas contains as much as 10 g/m3 of tar, 4,000 ppmv of NH3 and 100 ppmv of H2S. The goal of the Therminator module would be to use promising regenerable catalysts developed for removing tar, ammonia, and H2S down to low levels (around 10 ppm). Tars are cracked to a non-condensable gas and coke that would deposit on the acid catalyst. Wemore » will deposit coke, much like a fluid catalytic cracker (FCC) in a petroleum refinery. The deposited coke fouls the catalyst, much like FCC, but the coke would be burned off in the regenerator and the regenerated catalyst would be returned to the cracker. The rapid circulation between the cracker and regenerator would ensure the availability of the required amount of regenerated catalyst to accomplish our goal. Also, by removing sulfur down to less than 10 ppmv, NH3 decomposition would also be possible in the cracker at 600-700°C. In the cracker, tar decomposes and lays down coke on the acid sites of the catalyst, NH3 is decomposed using a small amount of metal (e.g., nickel or iron) catalyst incorporated into the catalyst matrix, and H2S is removed by a small amount of a metal oxide (e.g. zinc oxide or zinc titanate) by the H2S-metal oxide reaction to form metal sulfide. After a tolerable decline in activity for these reactions, the catalyst particles (and additives) are transported to the regenerator where they are exposed to air to remove the coke and to regenerate the metal sulfide back to metal oxide. Sulfate formation is avoided by running the regeneration with slightly sub-stoichiometric quantity of oxygen. Following regeneration, the catalyst is transported back to the cracker and the cycling continues. Analogous to an FCC reactor system, rapid cycling will allow the use of very active cracking catalysts that lose activity due to coking within the order of several seconds.« less

Acid-catalyzed hydrogenation during kerosene hydrodewaxing over H/ZSM-5

DOE Office of Scientific and Technical Information (OSTI.GOV)

Longstaff, D.C.; Hanson, F.V.

1996-11-01

Hydrogen addition to the products derived from cracking kerosene over H/ZSM-5 was observed at hydrogen pressures between 4.1-8.7 MPa and at 373-390{degrees}C. At low pressures, kerosene cracking over H/ZSM-5 yielded typical cracked products: aromatics, as well as low molecular weight saturates and olefins. Endothermic reactor temperature profiles were also observed, indicative of cracking reactions. At high hydrogen partial pressures product selectivity was altered in that kerosene cracking gave high yields of low molecular weight paraffins and low yields of olefins and aromatics. Reactor temperature profiles were exothermic, indicative of hydrocracking reactions. A mechanism for acid catalyzed hydrogenation is suggested. Althoughmore » hydrogenation was not observed at lower hydrogen pressures, hydrogen proved beneficial in maintaining catalyst activity at a stable level. Lost catalyst activity was restored by maintaining the catalyst under static hydrogen at 1.4 MPa and 370{degrees}C for 16h. 36 refs., 14 figs., 3 tabs.« less

Crack-tips enriched platinum-copper superlattice nanoflakes as highly efficient anode electrocatalysts for direct methanol fuel cells.

PubMed

Zheng, Lijun; Yang, Dachi; Chang, Rong; Wang, Chengwen; Zhang, Gaixia; Sun, Shuhui

2017-07-06

We have developed "crack-tips" and "superlattice" enriched Pt-Cu nanoflakes (NFs), benefiting from the synergetic effects of "crack-tips" and "superlattice crystals"; the Pt-Cu NFs exhibit 4 times higher mass activity, 6 times higher specific activity and 6 times higher stability than those of the commercial Pt/C catalyst, respectively. Meanwhile, the Pt-Cu NFs show more enhanced CO tolerance than the commercial Pt/C catalyst.

Dynamic response of fluid inside a penny shaped crack

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hayashi, Kazuo; Seki, Hitoshi

1997-12-31

In order to discuss the method for estimating the geometric characteristics of geothermal reservoir cracks, a theoretical study is performed on the dynamic response of the fluid inside a reservoir crack in a rock mass subjected to a dynamic excitation due to propagation of an elastic wave. As representative models of reservoir cracks, a penny shaped crack and a two-dimensional crack which are connected to a borehole are considered. It is found that the resonance frequency of the fluid motion is dependent on the crack size, the fluid`s viscosity and the permeability of the formation. The intensity of the resonancemore » is dependent on the fluid`s viscosity when the size, the aperture and the permeability are fixed. It is also found that, at a value of the fluid`s viscosity, the resonance of fluid pressure becomes strongest. The optimum value of the fluid`s viscosity is found to be almost perfectly determined by the permeability of the formation. Furthermore, it is revealed that, if the fluid`s viscosity is fixed to be the optimum value, the resonance frequency is almost independent of the permeability and aperture, but is dependent on the size of crack. Inversely speaking, this implies that the size of the reservoir crack can be estimated from the resonance frequency, if the fluid with the above mentioned optimum value of viscosity is employed for hydraulic fracturing.« less

Method for reactivating catalysts and a method for recycling supercritical fluids used to reactivate the catalysts

DOEpatents

Ginosar, Daniel M.; Thompson, David N.; Anderson, Raymond P.

2008-08-05

A method of reactivating a catalyst, such as a solid catalyst or a liquid catalyst. The method comprises providing a catalyst that is at least partially deactivated by fouling agents. The catalyst is contacted with a fluid reactivating agent that is at or above a critical point of the fluid reactivating agent and is of sufficient density to dissolve impurities. The fluid reactivating agent reacts with at least one fouling agent, releasing the at least one fouling agent from the catalyst. The at least one fouling agent becomes dissolved in the fluid reactivating agent and is subsequently separated or removed from the fluid reactivating agent so that the fluid reactivating agent may be reused. A system for reactivating a catalyst is also disclosed.

40 CFR 60.105a - Monitoring of emissions and operations for fluid catalytic cracking units (FCCU) and fluid coking...

Code of Federal Regulations, 2011 CFR

2011-07-01

... for fluid catalytic cracking units (FCCU) and fluid coking units (FCU). 60.105a Section 60.105a... and operations for fluid catalytic cracking units (FCCU) and fluid coking units (FCU). (a) FCCU and... Emission Standards for Hazardous Air Pollutants for Petroleum Refineries: Catalytic Cracking Units...

40 CFR 60.105a - Monitoring of emissions and operations for fluid catalytic cracking units (FCCU) and fluid coking...

Code of Federal Regulations, 2010 CFR

2010-07-01

... for fluid catalytic cracking units (FCCU) and fluid coking units (FCU). 60.105a Section 60.105a... and operations for fluid catalytic cracking units (FCCU) and fluid coking units (FCU). (a) FCCU and... Emission Standards for Hazardous Air Pollutants for Petroleum Refineries: Catalytic Cracking Units...

Effect of Steam Deactivation Severity of ZSM-5 Additives on LPG Olefins Production in the FCC Process.

PubMed

Gusev, Andrey A; Psarras, Antonios C; Triantafyllidis, Konstantinos S; Lappas, Angelos A; Diddams, Paul A

2017-10-21

ZSM-5-containing catalytic additives are widely used in oil refineries to boost light olefin production and improve gasoline octanes in the Fluid Catalytic Cracking (FCC) process. Under the hydrothermal conditions present in the FCC regenerator (typically >700 °C and >8% steam), FCC catalysts and additives are subject to deactivation. Zeolites (e.g., Rare Earth USY in the base catalyst and ZSM-5 in Olefins boosting additives) are prone to dealumination and partial structural collapse, thereby losing activity, micropore surface area, and undergoing changes in selectivity. Fresh catalyst and additives are added at appropriate respective levels to the FCC unit on a daily basis to maintain overall targeted steady-state (equilibrated) activity and selectivity. To mimic this process under accelerated laboratory conditions, a commercial P/ZSM-5 additive was hydrothermally equilibrated via a steaming process at two temperatures: 788 °C and 815 °C to simulate moderate and more severe equilibration industrial conditions, respectively. n -Dodecane was used as probe molecule and feed for micro-activity cracking testing at 560 °C to determine the activity and product selectivity of fresh and equilibrated P-doped ZSM-5 additives. The fresh/calcined P/ZSM-5 additive was very active in C 12 cracking while steaming limited its activity, i.e., at catalyst-to-feed (C/F) ratio of 1, about 70% and 30% conversion was obtained with the fresh and steamed additives, respectively. A greater activity drop was observed upon increasing the hydrothermal deactivation severity due to gradual decrease of total acidity and microporosity of the additives. However, this change in severity did not result in any selectivity changes for the LPG (liquefied petroleum gas) olefins as the nature (Brønsted-to-Lewis ratio) of the acid/active sites was not significantly altered upon steaming. Steam deactivation of ZSM-5 had also no significant effect on aromatics formation which was enhanced at higher conversion levels. Coke remained low with both fresh and steam-deactivated P/ZSM-5 additives.

System for reactivating catalysts

DOEpatents

Ginosar, Daniel M.; Thompson, David N.; Anderson, Raymond P.

2010-03-02

A method of reactivating a catalyst, such as a solid catalyst or a liquid catalyst is provided. The method comprises providing a catalyst that is at least partially deactivated by fouling agents. The catalyst is contacted with a fluid reactivating agent that is at or above a critical point of the fluid reactivating agent and is of sufficient density to dissolve impurities. The fluid reactivating agent reacts with at least one fouling agent, releasing the at least one fouling agent from the catalyst. The at least one fouling agent becomes dissolved in the fluid reactivating agent and is subsequently separated or removed from the fluid reactivating agent so that the fluid reactivating agent may be reused. A system for reactivating a catalyst is also disclosed.

Corrosion Behavior of Steel Reinforcement in Concrete with Recycled Aggregates, Fly Ash and Spent Cracking Catalyst.

PubMed

Gurdián, Hebé; García-Alcocel, Eva; Baeza-Brotons, Francisco; Garcés, Pedro; Zornoza, Emilio

2014-04-21

The main strategy to reduce the environmental impact of the concrete industry is to reuse the waste materials. This research has considered the combination of cement replacement by industrial by-products, and natural coarse aggregate substitution by recycled aggregate. The aim is to evaluate the behavior of concretes with a reduced impact on the environment by replacing a 50% of cement by industrial by-products (15% of spent fluid catalytic cracking catalyst and 35% of fly ash) and a 100% of natural coarse aggregate by recycled aggregate. The concretes prepared according to these considerations have been tested in terms of mechanical strengths and the protection offered against steel reinforcement corrosion under carbonation attack and chloride-contaminated environments. The proposed concrete combinations reduced the mechanical performance of concretes in terms of elastic modulus, compressive strength, and flexural strength. In addition, an increase in open porosity due to the presence of recycled aggregate was observed, which is coherent with the changes observed in mechanical tests. Regarding corrosion tests, no significant differences were observed in the case of the resistance of these types of concretes under a natural chloride attack. In the case of carbonation attack, although all concretes did not stand the highly aggressive conditions, those concretes with cement replacement behaved worse than Portland cement concretes.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kuehler, C.W.

This paper reports on the need for specialty fluid catalytic cracking (FCC) additives which is likely to increase, given the refining environment and the arrival of reformulated gasoline prompted by the most recent national environmental laws. C.W. Kuehler of Chevron Research and Technology Co., U.S.A. covered the participants in the field and the state of FCC additive technology this past June at Akzo Chemie's catalysts symposium in Scheveningen, The Netherlands. Other authors of the paper presented were A.S. Krishna, C.R. Hsieh, A.R.English, and T.A. Pecoraro, all with Chevron. The FCC process has undergone numerous changes in its 50-year history, Kuehlermore » pointed out. It shows the impressive continual growth of the process. One important aspect of additives is their ability to alter and control the nature of the FCC catalyst, thereby controlling the reactions carried out in the reactor and regenerator.« less

Motor fuels and chemicals from coal via the Sasol Synthol route

NASA Astrophysics Data System (ADS)

Hoogendoorn, J. C.

1981-03-01

The production of synthetic motor fuels and chemicals from coal by the Sasol procedures is discussed. This process is based on the Fischer-Tropsch reaction by passing hydrogen and carbon monoxide in a specific ratio over iron catalysts at elevated temperatures and pressures. Two parallel reactor systems are discussed. The smaller system employs fixed-bed reactors, using a precipitated iron catalyst and produces predominantly heavy hydrocarbons of an aliphatic nature with carbon chains up to 100. These straight-chain hydrocarbons yield excellent waxes and high quality diesel oil. The larger system uses a powdered iron catalyst in a circulating fluid-bed reactor, a concept developed from American catalytic cracker technology. This system has the advantage of high production capacity and scale-up potential, and produces light olefins which can be used either as petrochemical feedstock or refined and added to the motor fuel pool, and ethylene which is augmented by ethane cracking. Analysis of product selectivities and values shows that co-production of chemicals and motor fuels from coal is profitable and efficient.

Low-temperature superacid catalysis: Reactions of n - butane and propane catalyzed by iron- and manganese-promoted sulfated zirconia

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tsz-Keung, Cheung; d`Itri, J.L.; Lange, F.C.

1995-12-31

The primary goal of this project is to evaluate the potential value of solid superacid catalysts of the sulfated zirconia type for light hydrocarbon conversion. The key experiments catalytic testing of the performance of such catalysts in a flow reactor fed with streams containing, for example, n-butane or propane. Fe- and Mn-promoted sulfated zirconia was used to catalyze the conversion of n-butane at atmospheric pressure, 225-450{degrees}C, and n-butane partial pressures in the range of 0.0025-0.01 atm. At temperatures <225{degrees}C, these reactions were accompanied by cracking; at temperatures >350{degrees}C, cracking and isomerization occurred. Catalyst deactivation, resulting at least in part frommore » coke formation, was rapid. The primary cracking products were methane, ethane, ethylene, and propylene. The observation of these products along with an ethane/ethylene molar ratio of nearly 1 at 450{degrees}C is consistent with cracking occurring, at least in part, by the Haag-Dessau mechanism, whereby the strongly acidic catalyst protonates n-butane to give carbonium ions. The rate of methane formation from n-butane cracking catalyzed by Fe- and Mn-promoted sulfated zirconia at 450{degrees}C was about 3 x 10{sup -8} mol/(g of catalyst {center_dot}s). The observation of butanes, pentanes, and methane as products is consistent with Olah superacid chemistry, whereby propane is first protonated by a very strong acid to form a carbonium ion. The carbonium ion then decomposes into methane and an ethyl cation which undergoes oligocondensation reactions with propane to form higher molecular weight alkanes. The results are consistent with the identification of iron- and manganese-promoted sulfated zirconia as a superacid.« less

Elasticity-Driven Backflow of Fluid-Driven Cracks

NASA Astrophysics Data System (ADS)

Lai, Ching-Yao; Dressaire, Emilie; Ramon, Guy; Huppert, Herbert; Stone, Howard A.

2016-11-01

Fluid-driven cracks are generated by the injection of pressurized fluid into an elastic medium. Once the injection pressure is released, the crack closes up due to elasticity and the fluid in the crack drains out of the crack through an outlet, which we refer to as backflow. We experimentally study the effects of crack size, elasticity of the matrix, and fluid viscosity on the backflow dynamics. During backflow, the volume of liquid remaining in the crack as a function of time exhibits a transition from a fast decay at early times to a power law behavior at late times. Our results at late times can be explained by scaling arguments balancing elastic and viscous stresses in the crack. This work may relate to the environmental issue of flowback in hydraulic fracturing. This work is supported by National Science Foundation via Grant CBET-1509347 and partially supported by Andlinger Center for Energy and the Environment at Princeton University.

Effect of support on catalytic cracking of bio-oil over Ni/silica-alumina

NASA Astrophysics Data System (ADS)

Sunarno, Herman, Syamsu; Rochmadi, Mulyono, Panut; Budiman, Arief

2017-03-01

Depletion of petroleum and environmental problem have led to look for an alternative fuel sources In many ways, biomass is a potential renewable source. Among the many forms of biomass, oil palm empty fruit bunch (EFB) is a very attractive feedstock due to its abudance, low price and non-competitiveness with the food chain. EFB can be converted bio-oil by pyrolysis process. but this product can not be used directly as a transportation fuel, so it needs upgrading bio-oil through a catalytic cracking process. The catalyst plays an important role in the catalytic cracking process. The objective of this research is to study the effect of Ni concentrations (1,3,5 and 7 wt.%) on the characteristics of the catalyst Ni / Silica-Alumina and the performance test for the catalytic cracking of bio-oil. Preparation of the catalyst Ni / Silica-Alumina was done by impregnation at 80°C for 3 hours, then done to calcination and reduction at 500°C for 2 hours. The performance test was conducted on catalytic cracking temperature of 500°C. Results show that increasing concentration of Ni from 1 to 7 %, the pore diameter of the catalyst decreased from 35.71 to 32.70 A and surface area decreased from 209.78 to 188.53 m2/gram. With the increase of Ni concentration, the yield of oil reduced from 22.5 to 11.25 %, while the heating value of oil increased from 34.4 to 36.41MJ/kg.

Catalytic Decarboxylation of Fatty Acids to Aviation Fuels over Nickel Supported on Activated Carbon

PubMed Central

Wu, Jianghua; Shi, Juanjuan; Fu, Jie; Leidl, Jamie A.; Hou, Zhaoyin; Lu, Xiuyang

2016-01-01

Decarboxylation of fatty acids over non-noble metal catalysts without added hydrogen was studied. Ni/C catalysts were prepared and exhibited excellent activity and maintenance for decarboxylation. Thereafter, the effects of nickel loading, catalyst loading, temperature, and carbon number on the decarboxylation of fatty acids were investigated. The results indicate that the products of cracking increased with high nickel loading or catalyst loading. Temperature significantly impacted the conversion of stearic acid but did not influence the selectivity. The fatty acids with large carbon numbers tend to be cracked in this reaction system. Stearic acid can be completely converted at 370 °C for 5 h, and the selectivity to heptadecane was around 80%. PMID:27292280

Life extension of self-healing polymers with rapidly growing fatigue cracks.

PubMed

Jones, A S; Rule, J D; Moore, J S; Sottos, N R; White, S R

2007-04-22

Self-healing polymers, based on microencapsulated dicyclopentadiene and Grubbs' catalyst embedded in the polymer matrix, are capable of responding to propagating fatigue cracks by autonomic processes that lead to higher endurance limits and life extension, or even the complete arrest of the crack growth. The amount of fatigue-life extension depends on the relative magnitude of the mechanical kinetics of crack propagation and the chemical kinetics of healing. As the healing kinetics are accelerated, greater fatigue life extension is achieved. The use of wax-protected, recrystallized Grubbs' catalyst leads to a fourfold increase in the rate of polymerization of bulk dicyclopentadiene and extends the fatigue life of a polymer specimen over 30 times longer than a comparable non-healing specimen. The fatigue life of polymers under extremely fast fatigue crack growth can be extended through the incorporation of periodic rest periods, effectively training the self-healing polymeric material to achieve higher endurance limits.

Phenomenological modelling of self-healing polymers based on integrated healing agents

NASA Astrophysics Data System (ADS)

Mergheim, Julia; Steinmann, Paul

2013-09-01

The present contribution introduces a phenomenological model for self-healing polymers. Self-healing polymers are a promising class of materials which mimic nature by their capability to autonomously heal micro-cracks. This self-healing is accomplished by the integration of microcapsules containing a healing agent and a dispersed catalyst into the matrix material. Propagating microcracks may then break the capsules which releases the healing agent into the microcracks where it polymerizes with the catalyst, closes the crack and 'heals' the material. The present modelling approach treats these processes at the macroscopic scale, the microscopic details of crack propagation and healing are thus described by means of continuous damage and healing variables. The formulation of the healing model accounts for the fact that healing is directly associated with the curing process of healing agent and catalyst. The model is implemented and its capabilities are studied by means of numerical examples.

Catalytic removal of sulfur dioxide from dibenzothiophene sulfone over Mg-Al mixed oxides supported on mesoporous silica.

PubMed

You, Nansuk; Kim, Min Ji; Jeong, Kwang-Eun; Jeong, Soon-Yong; Park, Young-Kwon; Jeon, Jong-Ki

2010-05-01

Dibenzothiophene sulfone (DBTS), one of the products of the oxidative desulfurization of heavy oil, can be removed through extraction as well as by an adsorption process. It is necessary to utilize DBTS in conjunction with catalytic cracking. An object of the present study is to provide an Mg-Al-mesoporous silica catalyst for the removal of sulfur dioxide from DBTS. The characteristics of the Mg-Al-mesoporous silica catalyst were investigated through N2 adsorption, XRD, ICP, and XRF. An Mg-Al-mesoporous silica catalyst formulated in a direct incorporation method showed higher catalytic performance compared to pure MgO during the catalytic removal of sulfur dioxide from DBTS. The higher dispersion of Mg as well as the large surface area of the Mg-Al-mesoporous silica catalyst strongly influenced the catalyst basicity in DBTS cracking.

Pattern formation during healing of fluid-filled cracks: an analog experiment

DOE Office of Scientific and Technical Information (OSTI.GOV)

F. Renard; D. K. Dysthe; J. G. Feder

2009-11-01

The formation and subsequent healing of cracks and crack networks may control such diverse phenomena as the strengthening of fault zones between earthquakes, fluid migrations in the Earth's crust, or the transport of radioactive materials in nuclear waste disposal. An intriguing pattern-forming process can develop during healing of fluid-filled cracks, where pockets of fluid remain permanently trapped in the solid as the crack tip is displaced driven by surface energy. Here, we present the results of analog experiments in which a liquid was injected into a colloidal inorganic gel to obtain penny-shaped cracks that were subsequently allowed to close andmore » heal under the driving effect of interfacial tension. Depending on the properties of the gel and the injected liquid, two modes of healing were obtained. In the first mode, the crack healed completely through a continuous process. The second mode of healing was discontinuous and was characterized by a 'zipper-like' closure of a front that moved along the crack perimeter, trapping fluid that may eventually form inclusions trapped in the solid. This instability occurred only when the velocity of the crack tip decreased to zero. Our experiments provide a cheap and simple analog to reveal how aligned arrays of fluid inclusions may be captured along preexisting fracture planes and how small amounts of fluids can be permanently trapped in solids, modifying irreversibly their material properties.« less

Corrosion Behavior of Steel Reinforcement in Concrete with Recycled Aggregates, Fly Ash and Spent Cracking Catalyst

PubMed Central

Gurdián, Hebé; García-Alcocel, Eva; Baeza-Brotons, Francisco; Garcés, Pedro; Zornoza, Emilio

2014-01-01

The main strategy to reduce the environmental impact of the concrete industry is to reuse the waste materials. This research has considered the combination of cement replacement by industrial by-products, and natural coarse aggregate substitution by recycled aggregate. The aim is to evaluate the behavior of concretes with a reduced impact on the environment by replacing a 50% of cement by industrial by-products (15% of spent fluid catalytic cracking catalyst and 35% of fly ash) and a 100% of natural coarse aggregate by recycled aggregate. The concretes prepared according to these considerations have been tested in terms of mechanical strengths and the protection offered against steel reinforcement corrosion under carbonation attack and chloride-contaminated environments. The proposed concrete combinations reduced the mechanical performance of concretes in terms of elastic modulus, compressive strength, and flexural strength. In addition, an increase in open porosity due to the presence of recycled aggregate was observed, which is coherent with the changes observed in mechanical tests. Regarding corrosion tests, no significant differences were observed in the case of the resistance of these types of concretes under a natural chloride attack. In the case of carbonation attack, although all concretes did not stand the highly aggressive conditions, those concretes with cement replacement behaved worse than Portland cement concretes. PMID:28788613

Multiple use of waste catalysts with and without regeneration for waste polymer cracking.

PubMed

Salmiaton, A; Garforth, A A

2011-06-01

Waste plastics contain a substantial number of valuable chemicals. The wastes from post-consumer as well as from industrial production can be recycled to valuable chemical feedstock, which can be used in refineries and/or petrochemical industries. This chemical recycling process is an ideal approach in recycling the waste for a better environment. Polymer cracking using a laboratory fluidized bed reactor concentrated on the used highly contaminated catalyst, E-Cat 2. Even though E-Cat 2 had low activity due to fewer acid sites, the products yielded were similar with amorphous ASA and were far better than thermal cracking. The high levels of heavy metals, namely nickel and vanadium, deposited during their lifetime as an FCC catalyst, did not greatly affect on the catalyst activity. It was also shown that E-Cat 2 could be used with and without regeneration. Although there was more deactivation when there was no regeneration step, the yield of gases (C(2)-C(7)) remained fairly constant. For the first time, these results indicate that "waste" FCC catalyst (E-Cat) is a good candidate for future feedstock recycling of polymer waste. The major benefits of using E-Cat are a low market price, the ability to tolerate reuse and regeneration capacity. Copyright © 2011 Elsevier Ltd. All rights reserved.

Networks of channels for self-healing composite materials

NASA Astrophysics Data System (ADS)

Bejan, A.; Lorente, S.; Wang, K.-M.

2006-08-01

This is a fundamental study of how to vascularize a self-healing composite material so that healing fluid reaches all the crack sites that may occur randomly through the material. The network of channels is built into the material and is filled with pressurized healing fluid. When a crack forms, the pressure drops at the crack site and fluid flows from the network into the crack. The objective is to discover the network configuration that is capable of delivering fluid to all the cracks the fastest. The crack site dimension and the total volume of the channels are fixed. It is argued that the network must be configured as a grid and not as a tree. Two classes of grids are considered and optimized: (i) grids with one channel diameter and regular polygonal loops (square, triangle, hexagon) and (ii) grids with two channel sizes. The best architecture of type (i) is the grid with triangular loops. The best architecture of type (ii) has a particular (optimal) ratio of diameters that departs from 1 as the crack length scale becomes smaller than the global scale of the vascularized structure from which the crack draws its healing fluid. The optimization of the ratio of channel diameters cuts in half the time of fluid delivery to the crack.

Novel Fast Pyrolysis/Catalytic Technology for the Production of Stable Upgraded Liquids

DOE Office of Scientific and Technical Information (OSTI.GOV)

Oyama, Ted; Agblevor, Foster; Battaglia, Francine

The objective of the proposed research is the demonstration and development of a novel biomass pyrolysis technology for the production of a stable bio-oil. The approach is to carry out catalytic hydrodeoxygenation (HDO) and upgrading together with pyrolysis in a single fluidized bed reactor with a unique two-level design that permits the physical separation of the two processes. The hydrogen required for the HDO will be generated in the catalytic section by the water-gas shift reaction employing recycled CO produced from the pyrolysis reaction itself. Thus, the use of a reactive recycle stream is another innovation in this technology. Themore » catalysts will be designed in collaboration with BASF Catalysts LLC (formerly Engelhard Corporation), a leader in the manufacture of attrition-resistant cracking catalysts. The proposed work will include reactor modeling with state-of-the-art computational fluid dynamics in a supercomputer, and advanced kinetic analysis for optimization of bio-oil production. The stability of the bio-oil will be determined by viscosity, oxygen content, and acidity determinations in real and accelerated measurements. A multi-faceted team has been assembled to handle laboratory demonstration studies and computational analysis for optimization and scaleup.« less

Novel self-healing materials chemistries for targeted applications

NASA Astrophysics Data System (ADS)

Wilson, Gerald O.

Self-healing materials of the type developed by White and co-workers [1] were designed to autonomically heal themselves when damaged, thereby extending the lifetime of various applications in which such material systems are employed. The system was based on urea-formaldehyde microcapsules containing dicyclopentadiene (DCPD) and Grubbs' catalyst particles embedded together in an epoxy matrix. When a crack propagates through the material, it ruptures the microcapsules, releasing DCPD into the crack plane, where it comes in contact and reacts with the catalyst to initiate a ring opening metathesis polymerization (ROMP), bonding the crack and restoring structural continuity. The present work builds on this concept in several ways. Firstly, it expands the scope and versatility of the ROMP self-healing chemistry by incorporation into epoxy vinyl ester matrices. Major technical challenges in this application include protection of the catalyst from deactivation by aggressive curing agents, and optimization of the concentration of healing agents in the matrix. Secondly, new ruthenium catalysts are evaluated for application in ROMP-based self-healing materials. The use of alternative derivatives of Grubbs' catalyst gave rise to self-healing systems with improved healing efficiencies and thermal properties. Evaluation of the stability of these new catalysts to primary amine curing agents used in the curing of common epoxy matrices also led to the discovery and characterization of new ruthenium catalysts which exhibited ROMP initiation kinetics superior to those of first and second generation Grubbs' catalysts. Finally, free radical polymerization was evaluated for application in the development of bio-compatible self-healing materials. [1] White, S. R.; Sottos, N. R.; Geubelle, P. R.; Moore, J. S.; Kessler, M. R.; Sriram, S. R.; Brown, E. N.; Viswanathan, S. Nature 2001, 409, 794.

Roles of molecular hydrogen and a hydrogen donor solvent in the cracking of moal model compounds with dispersed catalysts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Suzuki, Toshimitsu; Ikenaga, Na-oki; Sakota, Takahiro

1994-12-31

It is of great importance to evaluate quantitative hydrogen transfer process by using coal model compounds with a hydrogen-donor solvent. Cronauer el al. showed that in the cracking of benzyl phenyl ether the hydrogen required to stabilize free radicals comes from a donor solvent or intramolecular rearrangement and not from gaseous hydrogen in the absence of a catalyst. Korobkov et al. and Schlosberg et al. showed that the thermolysis of benzyl phenyl ether and dibenzyl ether were accomplished by intramolecular rearrangements. Yokokawa et al. reported that tetralin retarded the catalyzed hydrocracking of coal model compounds containing C-C and C-O bonds.more » However, few studies dealt with quantitative discussion in the hydrogen transfer process from a hydrogen-donor solvent or molecular hydrogen to free radicals derived from a model compound except a series of studies by Nicole and co-workers. On the other hand, it is well known that the amount of naphthalene produced from tetralin decreases after the liquefaction of coal in tetralin with catalyst as compared to the liquefaction in the absence of catalysts. To account for this, two mechanisms are proposed. One is that the catalyst hydrogenates naphthalene produced from tetralin, and the other is that the catalyst promotes the direct hydrogen transfer from molecular hydrogen to free radicals. The purpose of this work is to elucidate the role of catalyst and tetralin by means of the quantitative treatment of the hydrogen transfer reaction stabilizing thermally decomposed free radicals. Cracking of benzyl phenyl ether (BPE), dibenzyl ether (DBE), 1,2-diphenylethane, and 1,3-diphenylpropane was studied in tetralin in the presence of highly disposed catalyst.« less

Decrepitation and crack healing of fluid inclusions in San Carlos olivine

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wanamaker, B.J.; Wong, Tengfong; Evans, B.

1990-09-10

Fluid inclusions break, or decrepitate, when the fluid pressure exceeds the least principal lithostatic stress by a critical amount. After decrepitation, excess fluid pressure is relaxed, resulting in crack arrest; subsequently, crack healing may occur. The authors developed a linear elastic fracture mechanics model to analyze new data on decrepitation and crack arrest in San Carlos Olivine, compared the model with previous fluid inclusion investigations, and used it to interpret some natural decrepitation microstructures. The common experimental observation that smaller inclusions may sustain higher internal fluid pressures without decrepitating may be rationalized by assuming that flaws associated with the inclusionmore » scale with the inclusion size. According to the model, the length of the crack formed by decrepitation depends on the lithostatic pressure at the initiation of cracking, the initial sizes of the flaw and the inclusion, and the critical stress intensity factor. Further experiments show that microcracks in San Carlos olivine heal within several days at 1,280 to 1,400{degree}C; healing rates depend on the crack geometry, temperature, and chemistry of the buffering gas. The regression distance of the crack tip during healing can be related to time through a power law with exponent n = 0.6. Chemical changes which become apparent after extremely long heat-treatments significantly affect the healing rates. Many of the inclusions in the San Carlos xenoliths stretched, decrepitated, and finally healed during uplift. The crack arrest model indicates that completely healed cracks had an initial fluid pressure of the order of 1 GPa. Using the crack arrest model and the healing kinetics, they estimate the ascent rate of these xenoliths to be between 0.001 and 0.1 m/s.« less

Getter materials for cracking ammonia

DOEpatents

Boffito, Claudio; Baker, John D.

1999-11-02

A method is provided for cracking ammonia to produce hydrogen. The method includes the steps of passing ammonia over an ammonia-cracking catalyst which is an alloy including (1) alloys having the general formula Zr.sub.1-x Ti.sub.x M.sub.1 M.sub.2, wherein M.sub.1 and M.sub.2 are selected independently from the group consisting of Cr, Mn, Fe, Co, and Ni, and x is between about 0.0 and about 1.0 inclusive; and between about 20% and about 50% Al by weight. In another aspect, the method of the invention is used to provide methods for operating hydrogen-fueled internal combustion engines and hydrogen fuel cells. In still another aspect, the present invention provides a hydrogen-fueled internal combustion engine and a hydrogen fuel cell including the above-described ammonia-cracking catalyst.

Dynamics of a fluid-driven crack in three dimensions by the finite difference method

NASA Astrophysics Data System (ADS)

Chouet, Bernard

1986-12-01

The finite difference method is applied to the study of the dynamics of a three-dimensional fluid-filled crack excited into resonance by the sudden failure of a small barrier of area ΔS on the crack surface. The impulse response of the crack is examined for various ratios of crack width to crack length and for several values of the crack stiffness C = (b/μ)(L/d), where b is the bulk modulus of the fluid, μ is the rigidity of the solid, and L and d are the crack length and crack thickness, respectively. The motion of the crack is characterized by distinct time scales representing the duration of brittle failure and the periods of acoustic resonance in the lateral and longitudinal dimensions of the source. The rupture has a duration proportional to the area of crack expansion and is the trigger responsible for the excitation of the crack into resonance; the resonant periods are proportional to the crack stiffness and to the width and length of the crack. The crack wave sustaining the resonance is analogous to the tube wave propagating in a fluid-filled borehole. It is dispersive, showing a phase velocity that decreases with increasing wavelength. Its wave speed is always lower than the acoustic velocity of the fluid and shows a strong dependence on the crack stiffness, decreasing as the stiffness increases. The initial motion of the crack surface is an opening, and the radiated far-field compressional wave starts with a strong but brief compression which has a duration proportional to the crack stiffness and size of the rupture area; the amplitude of this pulse increases with the area of rupture but decreases with increasing stiffness. Flow into the newly created cavity triggers a pressure drop in the fluid, which produces a partial collapse of the wall propagated over the crack surface at the speed of the crack wave. The collapse of the crack surface generates a weak long-period component of dilatation following the compressional first motion in the far-field P wave train; the dilatational component is clearer in the signal from stiffer cracks when seen in the direction of the rupture. The energy loss by radiation is stronger for high frequencies, resulting in a progressive enrichment of the crack response in lower frequencies over the duration of resonance. These source characteristics translate into a far-field signature that is marked by a high-frequency content near its onset and dominated by a longer-period component in its coda. The source duration shows a strong dependence on the fluid viscosity and associated viscous damping at the crack wall.

An Experimental Study of Penny-shaped Fluid-driven Cracks in an Elastic Matrix

NASA Astrophysics Data System (ADS)

Stone, Howard

2015-11-01

When a pressurized fluid is injected into an elastic matrix, the fluid generates a fracture that grows along a plane and forms a fluid-filled disc-like shape. For example, such problems occur in various natural and industrial applications involving the subsurface of Earth, such as hydraulic fracturing operations. We report a laboratory study of such a fluid-driven crack in a gelatin matrix, study the crack shape as a function of time, and investigate the influence of different experimental parameters such as the injection flow rate, Young's modulus of the matrix, and fluid viscosity. We find that the crack radius increases with time as a power law, which has been predicted both for the limit where viscous effects in the flow along the crack opening control the rate of crack propagation, as well as the limit where fracture toughness controls crack propagation. We vary experimental parameters to probe the physical limits and highlight that for our typical parameters both effects can be significant. Also, we measure the time evolution of crack shape, which has not been studied before. The rescaled crack shapes collapse at longer times, based on an appropriate scaling argument, and again we compare the scaling arguments in different physical limits. The gelatin system provides a useful laboratory model for further studies of fluid-driven cracks, some of which we will mention as they are inspired by the physics of hydraulic fracturing. This work is part of the PhD thesis of Ching-Yao Lai and is a collaboration with Drs. Zhong Zheng and Jason Wexler (Princeton University) and Professor Emilie Dressaire (NYU). Department of Mechanical and Aerospace Engineering.

Glass fabrics self-cracking catalytic growth of boron nitride nanotubes

NASA Astrophysics Data System (ADS)

Wang, Jilin; Peng, Daijang; Long, Fei; Wang, Weimin; Gu, Yunle; Mo, Shuyi; Zou, Zhengguang; Fu, Zhengyi

2017-02-01

Glass fabrics were used to fabricate boron nitride nanotubes (BNNTs) with a broad diameter range through a combined chemical vapor deposition and self-propagation high-temperature synthesis (CVD-SHS) method at different holding times (0min, 30min, 90min, 180min and 360min). SEM characterization has been employed to investigate the macro and micro structure/morphology changes of the glass fabrics and BNNTs in detail. SEM image analysis has provided direct experimental evidences for the rationality of the optimized self-cracking catalyst VLS growth mechanism, including the transformation situations of the glass fabrics and the BNNTs growth processes respectively. This paper was the further research and compensation for the theory and experiment deficiencies in the new preparation method of BNNTs reported in our previous work. In addition, it is likely that the distinctive self-cracking catalyst VLS growth mechanism could provide a new idea to preparation of other inorganic functional nano-materials using similar one-dimensional raw materials as growth templates and catalysts.

Cracking vegetable oil from Callophylluminnophyllum L. seeds to bio-gasoline by Ni-Mo/Al2O3 and Ni-Mo/Zeolite as micro-porous catalysts

NASA Astrophysics Data System (ADS)

Savitri, Effendi, R.; Tursiloadi, S.

2016-02-01

Natural minerals such as zeolite are local natural resources in the various regions in Indonesia. Studies on the application of natural mineral currently carried out by national research institutions, among others, as a filler, bleaching agent, or dehydration agent. However, not many studies that utilize these natural minerals as green catalysts material which has high performance for biomass conversion processes and ready to be applied directly by the bio-fuel industry. The trend movement of green and sustainable chemistry research that designing environmentally friendly chemical processes from renewable raw materials to produce innovative products derived biomass for bio-fuel. Callophylluminnophyllum L. seeds can be used as raw material for bio-energy because of its high oil content. Fatty acid and triglyceride compounds from this oil can be cracked into bio-gasoline, which does not contain oxygen in the hydrocarbon structure. Bio-gasoline commonly is referred to as drop-in biofuel because it can be directly used as a substitute fuel. This paper focused on the preparation and formulation of the catalyst NiMo/H-Zeolite and Ni-Mo/Al2O3 which were used in hydro-cracking process of oil from Callophylluminnophyllum L. seeds to produce bio-gasoline. The catalysts were analyzed using XRD, BET and IR-adsorbed pyridine method. The results of hydro-cracking products mostly were paraffin (C10-C19) straight chain, with 59.5 % peak area based on GC-MS analysis.

Method of producing pyrolysis gases from carbon-containing materials

DOEpatents

Mudge, Lyle K.; Brown, Michael D.; Wilcox, Wayne A.; Baker, Eddie G.

1989-01-01

A gasification process of improved efficiency is disclosed. A dual bed reactor system is used in which carbon-containing feedstock materials are first treated in a gasification reactor to form pyrolysis gases. The pyrolysis gases are then directed into a catalytic reactor for the destruction of residual tars/oils in the gases. Temperatures are maintained within the catalytic reactor at a level sufficient to crack the tars/oils in the gases, while avoiding thermal breakdown of the catalysts. In order to minimize problems associated with the deposition of carbon-containing materials on the catalysts during cracking, a gaseous oxidizing agent preferably consisting of air, oxygen, steam, and/or mixtures thereof is introduced into the catalytic reactor at a high flow rate in a direction perpendicular to the longitudinal axis of the reactor. This oxidizes any carbon deposits on the catalysts, which would normally cause catalyst deactivation.

Pyrolysis of triglyceride materials for the production of renewable fuels and chemicals.

PubMed

Maher, K D; Bressler, D C

2007-09-01

Conversion of vegetable oils and animal fats composed predominantly of triglycerides using pyrolysis type reactions represents a promising option for the production of renewable fuels and chemicals. The purpose of this article was to collect and review literature on the thermo-chemical conversion of triglyceride based materials. The literature was divided and discussed as (1) direct thermal cracking and (2) combination of thermal and catalytic cracking. Typically, four main catalyst types are used including transition metal catalysts, molecular sieve type catalysts, activated alumina, and sodium carbonate. Reaction products are heavily dependant on the catalyst type and reaction conditions and can range from diesel like fractions to gasoline like fractions. Research in this area is not as advanced as bio-oil and bio-diesel research and there is opportunity for further study in the areas of reaction optimization, detailed characterization of products and properties, and scale-up.

Growth rate of a penny-shaped crack in hydraulic fracturing of rocks

DOE Office of Scientific and Technical Information (OSTI.GOV)

Abe, H.; Keer, L.M.; Mura, T.

1976-01-01

The deformation and growth of a crack, fractured hydraulically, is investigated when fluid is injected from an inlet into the crack at a constant flow rate. The total flow rate at the inlet is divided as follows: flow rate extracted from an outlet hole; fluid loss rate from the crack surface; and total fluid mass change in the crack. Two cases are considered: (1) inlet flow rate is initially greater than the sum of the outlet flow and fluid loss rates; and (2) the reverse holds true. Ranges are shown for which the crack attains stationary states for given inletmore » flow rate and outlet pressure. For these two cases reasonable outlet flow rates are obtained when the outlet pressure is less than or equal to the difference between the tectonic stress and the fluid head at the inlet. Results are expected to be of use in considerations of heat extraction from hot, dry rock.« less

Co-Production of Electricity and Hydrogen Using a Novel Iron-based Catalyst

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hilaly, Ahmad; Georgas, Adam; Leboreiro, Jose

2011-09-30

The primary objective of this project was to develop a hydrogen production technology for gasification applications based on a circulating fluid-bed reactor and an attrition resistant iron catalyst. The work towards achieving this objective consisted of three key activities: Development of an iron-based catalyst suitable for a circulating fluid-bed reactor; Design, construction, and operation of a bench-scale circulating fluid-bed reactor system for hydrogen production; Techno-economic analysis of the steam-iron and the pressure swing adsorption hydrogen production processes. This report describes the work completed in each of these activities during this project. The catalyst development and testing program prepared and iron-basedmore » catalysts using different support and promoters to identify catalysts that had sufficient activity for cyclic reduction with syngas and steam oxidation and attrition resistance to enable use in a circulating fluid-bed reactor system. The best performing catalyst from this catalyst development program was produced by a commercial catalyst toll manufacturer to support the bench-scale testing activities. The reactor testing systems used during material development evaluated catalysts in a single fluid-bed reactor by cycling between reduction with syngas and oxidation with steam. The prototype SIP reactor system (PSRS) consisted of two circulating fluid-bed reactors with the iron catalyst being transferred between the two reactors. This design enabled demonstration of the technical feasibility of the combination of the circulating fluid-bed reactor system and the iron-based catalyst for commercial hydrogen production. The specific activities associated with this bench-scale circulating fluid-bed reactor systems that were completed in this project included design, construction, commissioning, and operation. The experimental portion of this project focused on technical demonstration of the performance of an iron-based catalyst and a circulating fluid-bed reactor system for hydrogen production. Although a technology can be technically feasible, successful commercial deployment also requires that a technology offer an economic advantage over existing commercial technologies. To effective estimate the economics of this steam-iron process, a techno-economic analysis of this steam iron process and a commercial pressure swing adsorption process were completed. The results from this analysis described in this report show the economic potential of the steam iron process for integration with a gasification plant for coproduction of hydrogen and electricity.« less

Cat cracking technology with reduced discharge of harmful substances to the atmosphere

DOE Office of Scientific and Technical Information (OSTI.GOV)

Elshin, A.I.; Aliev, R.R.; Solyar, B.Z.

1995-11-01

The operation of cat crackers creates a number of ecological problems involving pollution of the atmosphere. In the regeneration of coked catalyst, up to 10 tonnes/day of sulfur oxides are discharged to the atmosphere, along with catalyst dust in amounts up to 2 tonnes/day and carbon monoxide up to 120 tonnes/day. With increasingly severe requirements for environmental protection, the problem of reducing harmful discharges to the atmosphere has become more acute, necessitating either preliminary hydrotreating of the feed or scrubber cleanup of the stack gas to remove sulfur oxides. The high cost of these processes has provided the impetus formore » proposing various types of bifunctional cracking catalysts and effective catalyst additives to bind sulfur oxides directly in the regenerator. Basic oxides (of aluminum, magnesium, calcium, etc.) react with sulfur oxides to form stable sulfates that are then reduced to hydrogen sulfide in the reactor, while re-forming the basic oxide. Binding sulfur oxides in the regenerator is favored by the presence of an oxidizing agent or by the introduction of a promoter for afterburning carbon monoxide to dioxide. Compositions consisting mainly of aluminum oxide ({>=}90% by weight) have been patented as catalyst additives for binding sulfur oxides; other compositions that have been patented consist of Group II metal oxides and other oxides that have oxidizing properties. The additives are introduced into the catalyst charge in amounts of 5-10% by weight. On the basis of research, an aluminium oxide additive, PS-17, has been developed for binding sulfur oxides in the course of cracking.« less

Catalytic Upgrading of Biomass Pyrolysis Oxygenates with Vacuum Gas Oil Using a Davison Circulating Riser Reactor

DOE PAGES

Jarvis, Mark W.; Olstad, Jessica; Parent, Yves; ...

2018-01-02

We investigate and quantitate the changes in hydrocarbon product composition while evaluating the performance and operability of the National Renewable Energy Laboratory's Davison Circulating Riser (DCR) reactor system when biomass model compounds are cofed with traditional fluid catalyst cracking (FCC) feeds and catalyst: vacuum gas oil (VGO) and equilibrium zeolite catalyst (E-Cat). Three compounds (acetic acid, guaiacol, and sorbitan monooleate) were selected to represent the major classes of oxygenates present in biomass pyrolysis vapors. These vapors can contain 30-50% oxygen as oxygenates, which create conversion complications (increased reactivity and coking) when integrating biomass vapors and liquids into fuel and chemicalmore » processes long dominated by petroleum feedstocks. We used these model compounds to determine the appropriate conditions for coprocessing with petroleum and ultimately pure pyrolysis vapors only as compared with standard baseline conditions obtained with VGO and E-Cat only in the DCR. Model compound addition decreased the DCR catalyst circulation rate, which controls reactor temperature and measures reaction heat demand, while increasing catalyst coking rates. Liquid product analyses included 2-dimensional gas chromatography time-of-flight mass spectroscopy (2D GCxGC TOFS), simulated distillation (SIM DIST), 13C NMR, and carbonyl content. Aggregated results indicated that the model compounds were converted during reaction, and despite functional group differences, product distributions for each model compound were very similar. In addition, we determined that adding model compounds to the VGO feed did not significantly affect the DCR's operability or performance. Future work will assess catalytic upgrading of biomass pyrolysis vapor to fungible hydrocarbon products using upgrading catalysts currently being developed at NREL and at Johnson Matthey.« less

Catalytic Upgrading of Biomass Pyrolysis Oxygenates with Vacuum Gas Oil Using a Davison Circulating Riser Reactor

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jarvis, Mark W.; Olstad, Jessica; Parent, Yves

We investigate and quantitate the changes in hydrocarbon product composition while evaluating the performance and operability of the National Renewable Energy Laboratory's Davison Circulating Riser (DCR) reactor system when biomass model compounds are cofed with traditional fluid catalyst cracking (FCC) feeds and catalyst: vacuum gas oil (VGO) and equilibrium zeolite catalyst (E-Cat). Three compounds (acetic acid, guaiacol, and sorbitan monooleate) were selected to represent the major classes of oxygenates present in biomass pyrolysis vapors. These vapors can contain 30-50% oxygen as oxygenates, which create conversion complications (increased reactivity and coking) when integrating biomass vapors and liquids into fuel and chemicalmore » processes long dominated by petroleum feedstocks. We used these model compounds to determine the appropriate conditions for coprocessing with petroleum and ultimately pure pyrolysis vapors only as compared with standard baseline conditions obtained with VGO and E-Cat only in the DCR. Model compound addition decreased the DCR catalyst circulation rate, which controls reactor temperature and measures reaction heat demand, while increasing catalyst coking rates. Liquid product analyses included 2-dimensional gas chromatography time-of-flight mass spectroscopy (2D GCxGC TOFS), simulated distillation (SIM DIST), 13C NMR, and carbonyl content. Aggregated results indicated that the model compounds were converted during reaction, and despite functional group differences, product distributions for each model compound were very similar. In addition, we determined that adding model compounds to the VGO feed did not significantly affect the DCR's operability or performance. Future work will assess catalytic upgrading of biomass pyrolysis vapor to fungible hydrocarbon products using upgrading catalysts currently being developed at NREL and at Johnson Matthey.« less

Vibration analysis of partially cracked plate submerged in fluid

NASA Astrophysics Data System (ADS)

Soni, Shashank; Jain, N. K.; Joshi, P. V.

2018-01-01

The present work proposes an analytical model for vibration analysis of partially cracked rectangular plates coupled with fluid medium. The governing equation of motion for the isotropic plate based on the classical plate theory is modified to accommodate a part through continuous line crack according to simplified line spring model. The influence of surrounding fluid medium is incorporated in the governing equation in the form of inertia effects based on velocity potential function and Bernoulli's equations. Both partially and totally submerged plate configurations are considered. The governing equation also considers the in-plane stretching due to lateral deflection in the form of in-plane forces which introduces geometric non-linearity into the system. The fundamental frequencies are evaluated by expressing the lateral deflection in terms of modal functions. The assessment of the present results is carried out for intact submerged plate as to the best of the author's knowledge the literature lacks in analytical results for submerged cracked plates. New results for fundamental frequencies are presented as affected by crack length, fluid level, fluid density and immersed depth of plate. By employing the method of multiple scales, the frequency response and peak amplitude of the cracked structure is analyzed. The non-linear frequency response curves show the phenomenon of bending hardening or softening and the effect of fluid dynamic pressure on the response of the cracked plate.

Method For Reactivating Solid Catalysts Used For Alklation Reactions

DOEpatents

Ginosar, Daniel M.; Thompson, David N.; Coates, Kyle; Zalewski, David J.; Fox, Robert V.

2005-05-03

A method for reactivating a solid alkylation catalyst is provided which can be performed within a reactor that contains the alkylation catalyst or outside the reactor. Effective catalyst reactivation is achieved whether the catalyst is completely deactivated or partially deactivated. A fluid reactivating agent is employed to dissolve catalyst fouling agents and also to react with such agents and carry away the reaction products. The deactivated catalyst is contacted with the fluid reactivating agent under pressure and temperature conditions such that the fluid reactivating agent is dense enough to effectively dissolve the fouling agents and any reaction products of the fouling agents and the reactivating agent. Useful pressures and temperatures for reactivation include near-critical, critical, and supercritical pressures and temperatures for the reactivating agent. The fluid reactivating agent can include, for example, a branched paraffin containing at least one tertiary carbon atom, or a compound that can be isomerized to a molecule containing at least one tertiary carbon atom.

Method for reactivating solid catalysts used in alkylation reactions

DOEpatents

Ginosar, Daniel M.; Thompson, David N.; Coates, Kyle; Zalewski, David J.; Fox, Robert V.

2003-06-17

A method for reactivating a solid alkylation catalyst is provided which can be performed within a reactor that contains the alkylation catalyst or outside the reactor. Effective catalyst reactivation is achieved whether the catalyst is completely deactivated or partially deactivated. A fluid reactivating agent is employed to dissolve catalyst fouling agents and also to react with such agents and carry away the reaction products. The deactivated catalyst is contacted with the fluid reactivating agent under pressure and temperature conditions such that the fluid reactivating agent is dense enough to effectively dissolve the fouling agents and any reaction products of the fouling agents and the reactivating agent. Useful pressures and temperatures for reactivation include near-critical, critical, and supercritical pressures and temperatures for the reactivating agent. The fluid reactivating agent can include, for example, a branched paraffin containing at least one tertiary carbon atom, or a compound that can be isomerized to a molecule containing at least one tertiary carbon atom.

Long-Period Oscillations of Hydraulic Fractures: Attenuation, Scaling Relationships, and Flow Stability

NASA Astrophysics Data System (ADS)

Lipovsky, B.; Dunham, E. M.

2013-12-01

Long-period seismicity due to the excitation of hydraulic fracture normal modes is thought to occur in many geological systems, including volcanoes, glaciers and ice sheets, and hydrocarbon reservoirs. To better quantify the physical dimensions of fluid-filled cracks and properties of the fluid within them, we study wave motion along a thin hydraulic fracture waveguide. We present a linearized analysis that accounts for quasi-dynamic elasticity of the fracture wall, as well as fluid drag, inertia, and compressibility. We consider symmetric perturbations and neglect the effects of stratification and gravity. In the long-wavelength or thin-fracture limit, dispersive guided waves known as crack waves propagate with phase velocity cw=√(G*|k|w/ρ), where G* = G/(1-υ) for shear modulus G and Poisson ratio υ, w is the crack half-width, k is the wavenumber, and ρ is the fluid density. Restoring forces from elastic wall deformation drive wave motions. In the opposite, short-wavelength limit, guided waves are simply sound waves within the fluid and little seismic excitation occurs due to minimal fluid-solid coupling. We focus on long-wavelength crack waves, which, in the form of standing wave modes in finite-length cracks, are thought to be a common mechanism for long-period seismicity. The dispersive nature of crack waves implies several basic scaling relations that might be useful when interpreting statistics of long-period events. Seismic observations may constrain a characteristic frequency f0 and seismic moment M0~GδwR2, where δw is the change in crack width and R is the crack dimension. Resonant modes of a fluid-filled crack have associated frequencies f~cw/R. Linear elasticity provides a link between pressure changes δp in the crack and the induced opening δw: δp~G δw/R. Combining these, and assuming that pressure changes have no variation with crack dimension, leads to the scaling law relating seismic moment and oscillation frequency, M0~(Gwδp/ρ)f0-2. This contrasts with the well-known self-similar earthquake scaling M0∝f0-3. Attenuation of long-period crack waves is due to both drag within the fluid and radiative energy losses from excitation of seismic waves. Fluid drag may be characterized by either a turbulent or laminar viscous law. We present a thorough characterization of viscous damping that is valid at both low frequencies, where the flow is always fully developed, and at high frequencies, where fluid inertia becomes important. We have derived simple formulas for the quality factor due to viscous attenuation. Waves may become unstable for sufficiently fast background fluid velocity u0. This instability, first proposed by Julian (1994), was further investigated by Dunham and Ogden (2012), who determined the instability condition, u0>cw/2. We establish a more general result: that the stability condition is not only independent of viscosity, but also uninfluenced by fluid inertia, although both do alter growth rates. We also show that radiation damping (excitation of plane P waves normal to the crack walls) has only a stabilizing effect. This work suggests that under geologically relevant conditions, crack wave propagation is most likely stable, and the occurrence of long-period oscillations thus requires some additional excitation process.

A Linearized Model for Wave Propagation through Coupled Volcanic Conduit-crack Systems Filled with Multiphase Magma

NASA Astrophysics Data System (ADS)

Liang, C.; Dunham, E. M.; OReilly, O. J.; Karlstrom, L.

2015-12-01

Both the oscillation of magma in volcanic conduits and resonance of fluid-filled cracks (dikes and sills) are appealing explanations for very long period signals recorded at many active volcanoes. While these processes have been studied in isolation, real volcanic systems involve interconnected networks of conduits and cracks. The overall objective of our work is to develop a model of wave propagation and ultimately eruptive fluid dynamics through this coupled system. Here, we present a linearized model for wave propagation through a conduit with multiple cracks branching off of it. The fluid is compressible and viscous, and is comprised of a mixture of liquid melt and gas bubbles. Nonequilibrium bubble growth and resorption (BGR) is quantified by introducing a time scale for mass exchange between phases, following the treatment in Karlstrom and Dunham (2015). We start by deriving the dispersion relation for crack waves travelling along the multiphase-magma-filled crack embedded in an elastic solid. Dissipation arises from magma viscosity, nonequilibrium BGR, and radiation of seismic waves into the solid. We next introduce coupling conditions between the conduit and crack, expressing conservation of mass and the balance of forces across the junction. Waves in the conduit, like those in the crack, are influenced by nonequilibrium BGR, but the deformability of the surrounding solid is far less important than for cracks. Solution of the coupled system of equations provides the evolution of pressure and fluid velocity within the conduit-crack system. The system has various resonant modes that are sensitive to fluid properties and to the geometry of the conduit and cracks. Numerical modeling of seismic waves in the solid allows us to generate synthetic seismograms.

Aluminosilicate nanoparticles for catalytic hydrocarbon cracking.

PubMed

Liu, Yu; Pinnavaia, Thomas J

2003-03-05

Aluminosilicate nanoparticles containing 9.0-20 nm mesopores were prepared through the use of protozeolitic nanoclusters as the inorganic precursor and starch as a porogen. The calcined, porogen-free composition containing 2 mol % aluminum exhibited the porosity, hydrothermal stability, and acidity needed for the cracking of very large hydrocarbons. In fact, the hydrothermal stability of the nanoparticles to pure steam at 800 degrees C, along with the cumene cracking activity, surpassed the analogous performance properties of ultrastable Y zeolite, the main catalyst component of commercial cracking catalysts. The remarkable hydrothermal stability and catalytic reactivity of the new nanoparticles are attributable to a unique combination of two factors, the presence of protozeolitic nanoclusters in the pore walls and the unprecedented pore wall thickness (7-15 nm). In addition, the excellent catalytic longevity of the nanoparticles is most likely facilitated by the small domain size of the nanoparticles that greatly improves access to the acid sites on the pore walls and minimizes the diffusion length of coke precursors out of the pores.

An analytical formula for the longitudinal resonance frequencies of a fluid-filled crack

NASA Astrophysics Data System (ADS)

Maeda, Y.; Kumagai, H.

2013-12-01

The fluid-filled crack model (Chouet, 1986, JGR) simulates the resonances of a rectangular crack filled with an inviscid fluid embedded in a homogeneous isotropic elastic medium. The model demonstrates the existence of a slow wave, known as the crack wave, that propagates along the solid-fluid interfaces. The wave velocity depends on the crack stiffness. The model has been used to interpret the peak frequencies of long-period (LP) and very long period (VLP) seismic events at various volcanoes (Chouet and Matoza, 2013, JVGR). Up to now, crack model simulations have been performed using the finite difference (Chouet, 1986) and boundary integral (Yamamoto and Kawakatsu, 2008, GJI) methods. These methods require computationally extensive procedures to estimate the complex frequencies of crack resonance modes. Establishing an easier way to calculate the frequencies of crack resonances would help understanding of the observed frequencies. In this presentation, we propose a simple analytical formula for the longitudinal resonance frequencies of a fluid-filled crack. We first evaluated the analytical expression proposed by Kumagai (2009, Encyc. Complex. Sys. Sci.) through a comparison of the expression with the peak frequencies computed by a 2D version of the FDM code of Chouet (1986). Our comparison revealed that the equation of Kumagai (2009) shows discrepancies with the resonant frequencies computed by the FDM. We then modified the formula as fmL = (m-1)a/[2L(1+2ɛmLC)1/2], (1) where L is the crack length, a is the velocity of sound in the fluid, C is the crack stiffness, m is a positive integer defined such that the wavelength of the normal displacement on the crack surface is 2L/m, and ɛmL is a constant that depends on the longitudinal resonance modes. Excellent fits were obtained between the peak frequencies calculated by the FDM and by Eq. (1), suggesting that this equation is suitable for the resonant frequencies. We also performed 3D FDM computations of the longitudinal mode resonances. The peak frequencies computed by the FDM are well fitted by Eq. (1). The best-fit ɛmL values are different from those for 2D and depend on W/L, where W is the crack width. Eq. (1) shows that fmL is a simple analytical function of a/L and C given m and W/L. This enables simple and rapid interpretations of the source processes of LP events, including estimation of the fluid properties and crack geometries as well as identification of the resonance modes of the individual peak frequencies. LP events at volcanoes often exhibit peak frequency variations. In such cases, the frequency variations can be easily converted to variations in the fluid properties and crack geometries. We showed that Eq. (1) is consistent with the analytical solution for an infinite crack given by Ferrazzini and Aki (1987, JGR). Although a theoretical derivation of Eq. (1) was not obtained yet, Eq. (1) is consistent with the frequencies expected from the wavelengths of the fluid pressure variation.

Nitrogen Chemistry and Coke Transformation of FCC Coked Catalyst during the Regeneration Process

NASA Astrophysics Data System (ADS)

Shi, Junjun; Guan, Jianyu; Guo, Dawei; Zhang, Jiushun; France, Liam John; Wang, Lefu; Li, Xuehui

2016-06-01

Regeneration of the coked catalyst is an important process of fluid catalytic cracking (FCC) in petroleum refining, however, this process will emit environmentally harmful gases such as nitrogen and carbon oxides. Transformation of N and C containing compounds in industrial FCC coke under thermal decomposition was investigated via TPD and TPO to examine the evolved gaseous species and TGA, NMR and XPS to analyse the residual coke fraction. Two distinct regions of gas evolution are observed during TPD for the first time, and they arise from decomposition of aliphatic carbons and aromatic carbons. Three types of N species, pyrrolic N, pyridinic N and quaternary N are identified in the FCC coke, the former one is unstable and tends to be decomposed into pyridinic and quaternary N. Mechanisms of NO, CO and CO2 evolution during TPD are proposed and lattice oxygen is suggested to be an important oxygen resource. Regeneration process indicates that coke-C tends to preferentially oxidise compared with coke-N. Hence, new technology for promoting nitrogen-containing compounds conversion will benefit the in-situ reduction of NO by CO during FCC regeneration.

Investigation of problems of closing of geophysical cracks in thermoelastic media in the case of flow of fluids with impurities

NASA Astrophysics Data System (ADS)

Martirosyan, A. N.; Davtyan, A. V.; Dinunts, A. S.; Martirosyan, H. A.

2018-04-01

The purpose of this article is to investigate a problem of closing cracks by building up a layer of sediments on surfaces of a crack in an infinite thermoelastic medium in the presence of a flow of fluids with impurities. The statement of the problem of closing geophysical cracks in the presence of a fluid flow is presented with regard to the thermoelastic stress and the influence of the impurity deposition in the liquid on the crack surfaces due to thermal diffusion at the fracture closure. The Wiener–Hopf method yields an analytical solution in the special case without friction. Numerical calculations are performed in this case and the dependence of the crack closure time on the coordinate is plotted. A similar spatial problem is also solved. These results generalize the results of previous studies of geophysical cracks and debris in rocks, where the closure of a crack due to temperature effects is studied without taking the elastic stresses into account.

Self-Healing of biocompatible polymeric nanocomposities

NASA Astrophysics Data System (ADS)

Espino, Omar; Chipara, Dorina

2014-03-01

Polymers are vulnerable to damage in form of cracks deep within the structure, where detection is difficult and repair is near to impossible. These cracks lead to mechanical degradation of the polymer. A method has been created to solve this problem named polymeric self healing. Self healing capabilities implies the dispersion within the polymeric matrix of microcapsules filled with a monomer and of catalyst. Poly urea-formaldehyde microcapsules used in this method are filled with dicyclopentadiene that is liberated after being ruptured by the crack propagation in the material. Polymerization is assisted by a catalyst FGGC that ignites the self healing process. Nanocomposites, such as titanium oxide, will be used as an integration of these polymers that will be tested by rupturing mechanically slowly. In order to prove the self healing process, Raman spectroscopy, FTIR, and SEM are used.

Chemistry and catalysis of coal liquefaction catalytic and thermal upgrading of coal liquid and hydrogenation of CO to produce fuels. Quarterly progress report, July-September 1980

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wiser, W.H.

1981-02-01

Studies on the basic properties of supported sulfide catalysts showed that different supports have a profound influence on catalytic activities of CoMo catalysts. The three functions of hydrodesulfurization, hydrogenation and cracking were differently affected depending on the support used and the manner of preparation of the catalyst. Also, incorporation of additives to the support showed that the different catalytic functions can be selectively affected. A systematic study concerned with catalytic cracking of coal-derived liquids, viz., an SRC-II middle-heavy distillate and four hydrotreated SRC-II products was carried out in the range of 375 to 500/sup 0/C (LHSV, 0.2 to 3.9 h/supmore » -1/). Hydrotreatment, even to a limited extent, results in a remarkable improvement in the yield of gasoline-range products from the SRC-II distillate. This improvement is ascribed to: (a) hydrogenolysis reactions leading to lower molecular weight feedstock components and (b) limited hydrogenation of aromatic rings leading to polycyclic feed components with sufficient concentration of hydroaromatic rings needed for effective cracking. The results with model compounds and the data on hydrogen consumption during hydrotreatment of SRC-II liquids indicate that for tricyclic, tetracyclic, and pentacyclic coal-liquid components the optimal concentration of hydroaromatic rings for effective subsequent cracking is at least two rings per molecule.« less

Hydrocarbon liquid production via the bioCRACK process and catalytic hydroprocessing of the product oil

DOE PAGES

Schwaiger, Nickolaus; Elliott, Douglas C.; Ritzberger, Jurgen; ...

2015-01-01

Continuous hydroprocessing of liquid phase pyrolysis bio-oil, provided by BDI-BioEnergy International bioCRACK pilot plant at OMV Refinery in Schwechat/Vienna Austria was investigated. These hydroprocessing tests showed promising results using catalytic hydroprocessing strategies developed for unfractionated bio-oil. A sulfided base metal catalyst (CoMo on Al2O3) was evaluated. The bed of catalyst was operated at 400 °C in a continuous-flow reactor at a pressure of 12.1 MPa with flowing hydrogen. The condensed liquid products were analyzed and found that the hydrocarbon liquid was significantly hydrotreated so that nitrogen and sulfur were below the level of detection (<0.05), while the residual oxygen rangedmore » from 0.7 to 1.2%. The density of the products varied from 0.71 g/mL up to 0.79 g/mL with a correlated change of the hydrogen to carbon atomic ratio from 2.1 down to 1.9. The product quality remained high throughout the extended tests suggesting minimal loss of catalyst activity through the test. These tests provided the data needed to assess the quality of liquid fuel products obtained from the bioCRACK process as well as the activity of the catalyst for comparison with products obtained from hydrotreated fast pyrolysis bio-oils from fluidized-bed operation.« less

Acoustic properties of a crack containing magmatic or hydrothermal fluids

USGS Publications Warehouse

Kumagai, H.; Chouet, B.A.

2000-01-01

We estimate the acoustic properties of a crack containing maginatic or hydrothermal fluids to quantify the source properties of long-period (LP) events observed in volcanic areas assuming that a crack-like structure is the source of LP events. The tails of synthetic waveforms obtained from a model of a fluid-driven crack are analyzed by the Sompi method to determine the complex frequencies of one of the modes of crack resonance over a wide range of the model parameters ??/a and ??f/??s, where ?? is the P wave velocity of the rock matrix, a is the sound speed of the fluid, and ??f and ??s are the densities of the fluid and rock matrix, respectively. The quality factor due to radiation loss (Qr) for the selected mode almost monotonically increases with increasing ??/a, while the dimensionless frequency (??) of the mode decreases with increasing ??/a and ??f/??s. These results are used to estimate Q and ?? for a crack containing various types of fluids (gas-gas mixtures, liquid-gas mixtures, and dusty and misty gases) for values of a, ??f, and quality factor due to intrinsic losses (Qi) appropriate for these types of fluids, in which Q is given by Q-1 = Qr-1 + Qi-1. For a crack containing such fluids, we obtain Q ranging from almost unity to several hundred, which consistently explains the wide variety of quality factors measured in LP events observed at various volcanoes. We underscore the importance of dusty and misty gases containing small-size particles with radii around 1 ??m to explain long-lasting oscillations with Q significantly larger than 100. Our results may provide a basis for the interpretation of spatial and temporal variations in the observed complex frequencies of LP events in terms of fluid compositions beneath volcanoes. Copyright 2000 by the American Geophysical Union.

Localized fluid discharge in subduction zones: Insights from tension veins around an ancient megasplay fault (Nobeoka Thrust, SW Japan)

NASA Astrophysics Data System (ADS)

Otsubo, M.; Hardebeck, J.; Miyakawa, A.; Yamaguchi, A.; Kimura, G.

2017-12-01

Fluid-rock interactions along seismogenic faults are of great importance to understand fault mechanics. The fluid loss by the formation of mode I cracks (tension cracks) increases the fault strength and creates drainage asperities along the plate interface (Sibson, 2013, Tectonophysics). The Nobeoka Thrust, in southwestern Japan, is an on-land example of an ancient megasplay fault and provides an excellent record of deformation and fluid flow at seismogenic depths of a subduction zone (Kondo et al., 2005, Tectonics). We focus on (1) Pore fluid pressure loss, (2) Amount of fault strength recovery, and (3) Fluid circulation by the formation of mode I cracks in the post-seismic period around the fault zone of the Nobeoka Thrust. Many quartz veins that filled mode I crack at the coastal outcrops suggest a normal faulting stress regime after faulting of the Nobeoka Thrust (Otsubo et al., 2016, Island Arc). We estimated the decrease of the pore fluid pressure by the formation of the mode I cracks around the Nobeoka Thrust in the post-seismic period. When the pore fluid pressure exceeds σ3, veins filling mode I cracks are constructed (Jolly and Sanderson, 1997, Jour. Struct. Geol.). We call the pore fluid pressure that exceeds σ3 "pore fluid over pressure". The differential stress in the post-seismic period and the driving pore fluid pressure ratio P* (P* = (Pf - σ3) / (σ1 - σ3), Pf: pore fluid pressure) are parameters to estimate the pore fluid over pressure. In the case of the Nobeoka Thrust (P* = 0.4, Otsubo et al., 2016, Island Arc), the pore fluid over pressure is up to 20 MPa (assuming tensile strength = 10 MPa). 20 MPa is equivalent to <10% of the total pore fluid pressure around the Nobeoka Thrust (depth = 10 km, density = 2.7 kg/m3). When the pore fluid pressure decreases by 4%, the normalized pore pressure ratio λ* (λ* = (Pf - Ph) / (Pl - Ph), Pl: lithostatic pressure; Ph: hydrostatic pressure) changes from 0.95 to 0.86. In the case of the Nobeoka Thrust, the fault strength can increase by up to 10 MPa (assuming frictional coefficient = 0.6). 10 MPa is almost equivalent to the stress drop values in large trench type earthquakes. Hence, we suggest that the fluid loss caused by the formation of mode I cracks in the post-seismic period may play an important role by increasing frictional strength along the megasplay fault.

Phase field modeling of crack propagations in fluid-saturated porous media with anisotropic surface energy

NASA Astrophysics Data System (ADS)

Na, S.; Sun, W.; Yoon, H.; Choo, J.

2016-12-01

Directional mechanical properties of layered geomaterials such as shale are important on evaluating the onset and growth of fracture for engineering applications such as hydraulic fracturing, geologic carbon storage, and geothermal recovery. In this study, a continuum phase field modeling is conducted to demonstrate the initiation and pattern of cracks in fluid-saturated porous media. The discontinuity of sharp cracks is formulated using diffusive crack phase field modeling and the anisotropic surface energy is incorporated to account for the directional fracture toughness. In particular, the orientation of bedding in geomaterials with respect to the loading direction is represented by the directional critical energy release rate. Interactions between solid skeleton and fluid are also included to analyze the mechanical behavior of fluid-saturated geologic materials through the coupled hydro-mechanical model. Based on the linear elastic phase field modeling, we also addressed how the plasticity in crack phase field influences the crack patterns by adopting the elasto-plastic model with Drucker-Prager yield criterion. Numerical examples exhibit the features of anisotropic surface energy, the interactions between solid and fluid and the effects of plasticity on crack propagations.Sandia National Laboratories is a multi-program laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. Department of Energy's National Nuclear Security Administration under contract DE-AC04-94AL85000.

Application of microscopy technology in thermo-catalytic methane decomposition to hydrogen

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mei, Irene Lock Sow, E-mail: irene.sowmei@gmail.com; Lock, S. S. M., E-mail: serenelock168@gmail.com; Abdullah, Bawadi, E-mail: bawadi-abdullah@petronas.com.my

2015-07-22

Hydrogen production from the direct thermo-catalytic decomposition of methane is a promising alternative for clean fuel production because it produces pure hydrogen without any CO{sub x} emissions. However, thermal decomposition of methane can hardly be of any practical and empirical interest in the industry unless highly efficient and effective catalysts, in terms of both specific activity and operational lifetime have been developed. In this work, bimetallic Ni-Pd on gamma alumina support have been developed for methane cracking process by using co-precipitation and incipient wetness impregnation method. The calcined catalysts were characterized to determine their morphologies and physico-chemical properties by usingmore » Brunauer-Emmett-Teller method, Field Emission Scanning Electron Microscopy, Energy-dispersive X-ray spectroscopy and Thermogravimetric Analysis. The results suggested that that the catalyst which is prepared by the co-precipitation method exhibits homogeneous morphology, higher surface area, have uniform nickel and palladium dispersion and higher thermal stability as compared to the catalyst which is prepared by wet impregnation method. This characteristics are significant to avoid deactivation of the catalysts due to sintering and carbon deposition during methane cracking process.« less

Catalyst for cracking kerosene

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hsie, C. H.

1985-06-04

A catalyst capable of cracking kerosene under lower pressure and temperature comprising kerosene; metal powder mixture of chromium powder, copper powder, lead powder, zinc powder, nickel powder, manganese powder in an amount of 12 to 13 parts by weight per 100 parts by weight of said kerosene; sulfuric acid in an amount of 15 to 30 parts by weight per 100 parts by weight of said kerosene; inorganic powder mixture of aluminum oxide powder, serpentine powder, alum powder, magnesium oxide powder, limestone powder, slake lime powder, silica powder, and granite powder in an amount of 150 to 170 parts bymore » weight per 100 parts by weight of said kerosene.« less

Resonance of a fluid-driven crack: Radiation properties and implications for the source of long-period events and harmonic tremor

NASA Astrophysics Data System (ADS)

Chouet, Bernard

1988-05-01

A dynamic source model is presented, in which a three-dimensional crack containing a viscous compressible fluid is excited into resonance by an impulsive pressure transient applied over a small area ΔS of the crack surface. The crack excitation depends critically on two dimensionless parameters called the crack stiffness, C = (b/μ)(L/d), and viscous damping loss, F = (12ηL)/(ρƒd2α), where b is the bulk modulus, η is the viscosity, ρƒ is the density of the fluid, μ is the rigidity, α is the compressional velocity of the solid, L is the crack length, and d is the crack thickness. The first parameter characterizes the ability of the crack to vibrate and shapes the spectral signature of the source, and the second quantifies the effect of fluid viscosity on the duration of resonance. Resonance is sustained by a very slow wave trapped in the fluid-filled crack. This guided wave, called the crack wave, is similar to the tube wave propagating in a fluid-filled borehole; it is inversely dispersive, showing a phase velocity that decreases with increasing wavelength, and its wave speed is always lower than the acoustic velocity of the fluid, decreasing rapidly as the crack stiffness increases. The source spectrum shows many sharp peaks characterizing the individual modes of vibration of the crack; the variation of spectral shape, both in the number and width of peaks, is surprisingly complex, reflecting the interference between the lateral and longitudinal modes of resonance, as well as nodes for these modes. The far-field spectrum is marked by narrow-band dominant and subdominant peaks that reflect the interaction of the various source modes. The frequency of the dominant spectral peak radiated by the source is independent of the radiation direction. The frequency, bandwidth, and spacing of the resonant peaks are strongly dependent on the crack stiffness, larger values of the stiffness factor shifting these peaks to lower frequencies and decreasing their bandwidth. The excitation of a particular mode depends on the position of the trigger and on the extent of the crack surface affected by the pressure transient. Fluid viscosity decreases the amplitudes of the main spectral peaks, smears out the finer structure of the spectrum, and greatly reduces the duration of the radiated signal. The energy loss by radiation is stronger for high frequencies, producing a seismic signature that is marked by a high-frequency content near the onset of the signal and dominated by a longer-period component of much longer duration in the signal coda. Such signature is in harmony with those displayed by long-period events observed on active volcanoes and in hydrofracture experiments. The very low velocity which is possible in a crack with high stiffness (C ≥ 100) also provides an attractive explanation for very long period tremor, such as type 2 tremor at Aso volcano, Japan, without the requirement of an unrealistically large magma container. The standing wave pattern set up on the crack surface by the sustained resonance in the fluid is observable in the near field of the crack, suggesting that the location and extent of the source may be estimated from the mapping of the pattern of nodes and antinodes seen in its vicinity. According to the model, the long-period event and harmonic tremor share the same source but differ in the boundary conditions for fluid flow and in the triggering mechanism setting up the resonance of the source, the former being viewed as the impulse response of the tremor generating system and the latter representing the excitation due to more complex forcing functions.

The dependence of acoustic properties of a crack on the resonance mode and geometry

USGS Publications Warehouse

Kumagai, H.; Chouet, B.A.

2001-01-01

We examine the dependence of the acoustic properties of a crack containing magmatic or hydrothermal fluids on the resonance mode and geometry to quantify the source properties of long-period (LP) events observed in volcanic areas. Our results, based on spectral analyses of synthetic waveforms generated with a fluid-driven crack model, indicate that the basic features of the dimensionless frequency (??) and quality factor (Qr) for a crack containing various types of fluids are not strongly affected by the choice of mode, although the actual ranges of Q?? and ?? both depend on the mode. The dimensionless complex frequency systematically varies with changes in the crack geometry, showing increases in both Qr and ?? as the crack length to aperture ratio decreases. The present results may be useful for the interpretation of spatial and temporal variations in the observed complex frequencies of LP events.

Investigation of growth features in several hydraulic fractures

NASA Astrophysics Data System (ADS)

Bykov, Alexander; Galybin, Alexander; Evdokimov, Alexander; Zavialova, Natalia; Zavialov, Ivan; Negodiaev, Sergey; Perepechkin, Ilia

2017-04-01

In this paper we simulate the growth of three or more interacting hydraulic fractures in the horizontal well with a cross flow of fluid between them. Calculation of the dynamics of cracks is performed in three dimensional space. The computation of the movement of fracturing fluid with proppant is performed in the two-dimensional space (the flow was averaged along crack aperture). For determining the hydraulic pipe resistance coefficient we used a generalization of the Reynolds number for fluids with power rheology and a generalization of the von Karman equation made by Dodge and Meiner. The calculations showed that the first crack was developing faster than the rest in homogeneous medium. During the steady loading the outer cracks pinch the inner cracks and it was shown that only the first and last fracture develop in extreme case. It is also possible to simulate the parameters at which the two developing outer cracks pinch the central one in the horizontal direction. In this case, the central crack may grow in the vertical direction.

Resonance of a fluid-driven crack: radiation properties and implications for the source of long-period events and harmonic tremor.

USGS Publications Warehouse

Chouet, B.

1988-01-01

A dynamic source model is presented, in which a 3-D crack containing a viscous compressible fluid is excited into resonance by an impulsive pressure transient applied over a small area DELTA S of the crack surface. The crack excitation depends critically on two dimensionless parameters called the crack stiffness and viscous damping loss. According to the model, the long-period event and harmonic tremor share the same source but differ in the boundary conditions for fluid flow and in the triggering mechanism setting up the resonance of the source, the former being viewed as the impulse response of the tremor generating system and the later representing the excitation due to more complex forcing functions.-from Author

Corrosion of stainless steels in the riser during co-processing of bio-oils in a fluid catalytic cracking pilot plant

DOE PAGES

Brady, M. P.; Keiser, J. R.; Leonard, D. N.; ...

2017-01-31

Co-processing of bio-oils with conventional petroleum-based feedstocks is an attractive initial option to make use of renewable biomass as a fuel source while leveraging existing refinery infrastructures. But, bio-oils and their processing intermediates have high concentrations of organic oxygenates, which, among their other negative qualities, can result in increased corrosion issues. A range of stainless steel alloys (409, 410, 304L, 316L, 317L, and 201) was exposed at the base of the riser in a fluid catalytic cracking pilot plant while co-processing vacuum gas oil with pine-derived pyrolysis bio-oils that had been catalytically hydrodeoxygenated to ~ 2 to 28% oxygen. Wemore » studied the processing using a catalyst temperature of 704 °C, a reaction exit temperature of 520 °C, and total co-processing run times of 57–75 h. External oxide scaling 5–30 μm thick and internal attack 1–5 μm deep were observed in these short-duration exposures. The greatest extent of internal attack was observed for co-processing with the least stabilized bio-oil, and more so for types 409, 410, 304L, 316L, 317L stainless steel than for type 201. Finally, the internal attack involved porous Cr-rich oxide formation, associated with local Ni-metal enrichment and S-rich nanoparticles, primarily containing Cr or Mn. Implications for alloy selection and corrosion are discussed.« less

Corrosion of stainless steels in the riser during co-processing of bio-oils in a fluid catalytic cracking pilot plant

DOE Office of Scientific and Technical Information (OSTI.GOV)

Brady, M. P.; Keiser, J. R.; Leonard, D. N.

Co-processing of bio-oils with conventional petroleum-based feedstocks is an attractive initial option to make use of renewable biomass as a fuel source while leveraging existing refinery infrastructures. But, bio-oils and their processing intermediates have high concentrations of organic oxygenates, which, among their other negative qualities, can result in increased corrosion issues. A range of stainless steel alloys (409, 410, 304L, 316L, 317L, and 201) was exposed at the base of the riser in a fluid catalytic cracking pilot plant while co-processing vacuum gas oil with pine-derived pyrolysis bio-oils that had been catalytically hydrodeoxygenated to ~ 2 to 28% oxygen. Wemore » studied the processing using a catalyst temperature of 704 °C, a reaction exit temperature of 520 °C, and total co-processing run times of 57–75 h. External oxide scaling 5–30 μm thick and internal attack 1–5 μm deep were observed in these short-duration exposures. The greatest extent of internal attack was observed for co-processing with the least stabilized bio-oil, and more so for types 409, 410, 304L, 316L, 317L stainless steel than for type 201. Finally, the internal attack involved porous Cr-rich oxide formation, associated with local Ni-metal enrichment and S-rich nanoparticles, primarily containing Cr or Mn. Implications for alloy selection and corrosion are discussed.« less

76 FR 3566 - Airworthiness Directives; The Boeing Company Model 777-200 and -300 Series Airplanes Equipped...

Federal Register 2010, 2011, 2012, 2013, 2014

2011-01-20

... hydraulic fluid contamination, which can cause cracking of titanium parts in the system disconnect assembly, resulting in compromise of the engine firewall. A cracked firewall can allow fire in the engine area to enter the strut and can lead to an uncontained engine strut fire if flammable fluid is present. Cracking...

Growth rate of a penny-shaped crack in hydraulic fracturing of rocks

DOE Office of Scientific and Technical Information (OSTI.GOV)

Abe, H.; Mura, T.; Keer, L.M.

1976-10-10

The stable growth of a crack created by the hydraulic pressurizing of a penny-shaped crack in a dry rock mass is investigated. The rock mass is infinitely extended, homogeneous, and isotropic. It is verified on the basis of the equations of fluid dynamics that the fracturing fluid cannot penetrate the entire domain of a crack when the crack is moving. The effects of various terms in the basic equations also are studied. The solution of some typical examples is given, and the significant effect of the stress intensity factor of the rock on the crack propagation is shown. When themore » crack is expanding under a constant flow rate, the classical solution by Sack is found to be approx. valid for very large cracks, and nevertheless the crack is stable. (11 refs.)« less

Growth rate of a penny-shaped crack in hydraulic fracturing of rocks

DOE Office of Scientific and Technical Information (OSTI.GOV)

Abe, H.; Mura, T.; Keer, L.M.

1976-10-10

The stable growth of a crack created by the hydraulic pressurizing of a penny-shaped crack in a dry rock mass is investigated. The rock mass is infinitely extended, homogeneous, and isotropic. It is verified on the basis of the equations of fluid dynamics that the fracturing fluid cannot penetrate the entire domain of a crack when the crack is moving. The effects of various terms in the basic equations are also studied. The solution of some typical examples is given, and the significant effect of the stress intensity factor of the rock on the crack propagation is shown. When themore » crack is expanding under a constant flow rate, the classical solution by Sack is found to be approximately valid for very large cracks, and nevertheless the crack is stable.« less

Process for upgrading wax from Fischer-Tropsch synthesis

DOEpatents

Derr, Jr., W. Rodman; Garwood, William E.; Kuo, James C.; Leib, Tiberiu M.; Nace, Donald M.; Tabak, Samuel A.

1987-01-01

The waxy liquid phase of an oil suspension of Fischer-Tropsch catalyst containing dissolved wax is separated out and the wax is converted by hydrocracking, dewaxing or by catalytic cracking with a low activity catalyst to provide a highly olefinic product which may be further converted to premium quality gasoline and/or distillate fuel.

Refinery catalysts: Coping with performance anxiety

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shelley, S.

1994-04-01

Petroleum refiners worldwide are struggling to comply with environmental mandates that tightly dictate the composition of gasoline and diesel fuel. At the same time, many are trying to capitalize on cost advantages offered by heavy, dirty feedstocks. This is stimulating development in catalysts for resid cracking, isomerization, alkylation and hydrotreating. The paper briefly describes development efforts.

Trends in long-period seismicity related to magmatic fluid compositions

USGS Publications Warehouse

Morrissey, M.M.; Chouet, B.A.

2001-01-01

Sound speeds and densities are calculated for three different types of fluids: gas-gas mixture; ash-gas mixture; and bubbly liquid. These fluid properties are used to calculate the impedance contrast (Z) and crack stiffness (C) in the fluid-driven crack model (Chouet: J. Geophys. Res., 91 (1986) 13,967; 101 (1988) 4375; A seismic model for the source of long-period events and harmonic tremor. In: Gasparini, P., Scarpa, R., Aki, K. (Eds.), Volcanic Seismology, IAVCEI Proceedings in Volcanology, Springer, Berlin, 3133). The fluid-driven crack model describes the far-field spectra of long-period (LP) events as modes of resonance of the crack. Results from our calculations demonstrate that ash-laden gas mixtures have fluid to solid density ratios comparable to, and fluid to solid velocity ratios lower than bubbly liquids (gas-volume fractions 20% gas-volume fraction yields values of Q-1r similar to those for a rectangular crack. As with gas-gas and ash-gas mixtures, an increase in mass fraction narrows the bandwidth of the dominant mode and shifts the spectra to lower frequencies. Including energy losses due to dissipative processes in a bubbly liquid increases attenuation. Attenuation may also be higher in ash-gas mixtures and foams if the effects of momentum and mass transfer between the phases were considered in the calculations. ?? 2001 Elsevier Science B. V. All rights reserved.

Source process of a long-period event at Kilauea volcano, Hawaii

USGS Publications Warehouse

Kumagai, H.; Chouet, B.A.; Dawson, P.B.

2005-01-01

We analyse a long-period (LP) event observed by a dense seismic network temporarily operated at Kilauea volcano, Hawaii, in 1996. We systematically perform spectral analyses, waveform inversions and forward modeling of the LP event to quantify its source process. Spectral analyses identify two dominant spectral frequencies at 0.6 and 1.3 Hz with associated Q values in the range 10-20. Results from waveform inversions assuming six moment-tensor and three single-force components point to the resonance of a horizontal crack located at a depth of approximately 150 m near the northeastern rim of the Halemaumau pit crater. Waveform simulations based on a fluid-filled crack model suggest that the observed frequencies and Q values can be explained by a crack filled with a hydrothermal fluid in the form of either bubbly water or steam. The shallow hydrothermal crack located directly above the magma conduit may have been heated by volcanic gases leaking from the conduit. The enhanced flux of heat raised the overall pressure of the hydrothermal fluid in the crack and induced a rapid discharge of fluid from the crack, which triggered the acoustic vibrations of the resonator generating the LP waveform. The present study provides further support to the idea that LP events originate in the resonance of a crack. ?? 2005 RAS.

Effect of vanadium contamination on the framework and micropore structure of ultra stable Y-zeolite.

PubMed

Etim, U J; Xu, B; Ullah, Rooh; Yan, Z

2016-02-01

Y-zeolites are the main component of fluid catalytic cracking (FCC) catalyst for conversion of crude petroleum to products of high demand including transportation fuel. We investigated effects of vanadium which is present as one of the impurities in FCC feedstock on the framework and micropore structure of ultra-stable (US) Y-zeolite. The zeolite samples were prepared and characterized using standard techniques including: (1) X-ray diffraction, (2) N2 adsorption employing non local density functional theory method, NLDFT, (3) Transmittance and Pyridine FTIR, (4) Transmittance electron microscopy (TEM), and (5) (27)Al and (29)Si MAS-NMR. Results revealed that in the presence of steam, vanadium caused excessive evolution of non inter-crystalline mesopores and structural damage. The evolved mesopore size averaged about 25.0nm at 0.5wt.% vanadium loading, far larger than mesopore size in zeolitic materials with improved hydrothermal stability and performance for FCC catalyst. A mechanism of mesopore formation based on accelerated dealumination has been proposed and discussed. Vanadium immobilization experiments conducted to mitigate vanadium migration into the framework clearly showed vanadium is mobile at reaction conditions. From the results, interaction of vanadium with the passivator limits and decreases mobility and activity of vanadium into inner cavities of the zeolite capable of causing huge structure breakdown and acid sites destruction. This study therefore deepens insight into the causes of alteration in activity and selectivity of vanadium contaminated catalyst and hints on a possible mechanism of passivation in vanadium passivated FCC catalyst. Copyright © 2015 Elsevier Inc. All rights reserved.

Catalytic dehydrogenation of isobutane in the presence of hydrogen over Cs-modified Ni2P supported on active carbon

NASA Astrophysics Data System (ADS)

Xu, Yanli; Sang, Huanxin; Wang, Kang; Wang, Xitao

2014-10-01

In this article, an environmentally friendly non-noble-metal class of Cs-Ni2P/active carbon (AC) catalyst was prepared and demonstrated to exhibit enhanced catalytic performance in isobutane dehydrogenation. The results of activity tests reveal that Ni/AC catalyst was highly active for isobutane cracking, which led to the formation of abundant methane and coke. After the introduction of phosphorus through impregnation with ammonium di-hydrogen phosphate and H2-temperature programmed reduction, undesired cracking reactions were effectively inhibited, and the selectivity to isobutene and stability of catalyst increased remarkably. The characterization results indicate that, after the addition of phosphorous, the improvement of dehydrogenation selectivity is ascribed to the partial positive charges carried on Ni surface in Ni2P particles, which decreases the strength of Nisbnd C bond between Ni and carbonium-ion intermediates and the possibility of excessive dehydrogenation. In addition, Cs-modified Ni2P/AC catalysts display much higher catalytic performance as compared to Ni2P/AC catalyst. Cs-Ni2P-6.5 catalyst has the highest catalytic performance, and the selectivity to isobutene higher than 93% can be obtained even after 4 h reaction. The enhancement in catalytic performance of the Cs-modified catalysts is mainly attributed to the function of Cs to improve the dispersion of Ni2P particles, transfer electron from Cs to Ni, and decrease acid site number and strength.

Solid catalyzed isoparaffin alkylation at supercritical fluid and near-supercritical fluid conditions

DOEpatents

Ginosar, Daniel M.; Fox, Robert V.; Kong, Peter C.

2000-01-01

This invention relates to an improved method for the alkylation reaction of isoparaffins with olefins over solid catalysts including contacting a mixture of an isoparaffin, an olefin and a phase-modifying material with a solid acid catalyst member under alkylation conversion conditions at either supercritical fluid, or near-supercritical fluid conditions, at a temperature and a pressure relative to the critical temperature(T.sub.c) and the critical pressure(P.sub.c) of the reaction mixture. The phase-modifying phase-modifying material is employed to promote the reaction's achievement of either a supercritical fluid state or a near-supercritical state while simultaneously allowing for decreased reaction temperature and longer catalyst life.

Heat Extraction from a Hydraulically Fractured Penny-Shaped Crack in Hot Dry Rock

DOE Office of Scientific and Technical Information (OSTI.GOV)

Abe, H.; Mura, T.; Keer, L.M.

1976-12-01

Heat extraction from a penny-shaped crack having both inlet and outlet holes is investigated analytically by considering the hydraulic and thermal growth of the crack when fluid is injected at a constant flow rate. The rock mass is assumed to be infinitely extended, homogeneous, and isotropic. The equations for fluid flow are derived and solved to determine the flow pattern in the crack. Temperature distributions in both rock and fluid are also determined. The crack width change due to thermal contraction and the corresponding flow rate increase are discussed. Some numerical calculations of outlet temperature, thermal power extraction, and crackmore » opening displacement due to thermal contraction of rocks are presented for cracks after they attain stationary states for given inlet flow rate and outlet suction pressure. The present paper is a further development of the previous works of Bodvarsson (1969), Gringarten et al. (1975), Lowell (1976), Harlow and Pracht (1972), McFarland (1975), among others, and considers the two-dimensional rather than the one-dimensional crack. Furthermore, the crack radius and width are quantities to be determined rather than given a priori. 11 refs., 1 tab., 5 figs.« less

Theoretical predicting of permeability evolution in damaged rock under compressive stress

NASA Astrophysics Data System (ADS)

Vu, M. N.; Nguyen, S. T.; To, Q. D.; Dao, N. H.

2017-05-01

This paper outlines an analytical model of crack growth induced permeability changes. A theoretical solution of effective permeability of cracked porous media is derived. The fluid flow obeys Poisseuille's law along the crack and Darcy's law in the porous matrix. This solution exhibits a percolation threshold for any type of crack distribution apart from a parallel crack distribution. The physical behaviour of fluid flow through a cracked porous material is well reproduced by the proposed model. The presence of this effective permeability coupling to analytical expression of crack growth under compression enables the modelling of the permeability variation due to stress-induced cracking in a porous rock. This incorporation allows the prediction of the permeability change of a porous rock embedding an anisotropic crack distribution from any initial crack density, that is, lower, around or upper to percolation threshold. The interaction between cracks is not explicitly taken into account. The model is well applicable both to micro- and macrocracks.

A discontinuous finite element approach to cracking in coupled poro-elastic fluid flow models

NASA Astrophysics Data System (ADS)

Wilson, C. R.; Spiegelman, M. W.; Evans, O.; Ulven, O. I.; Sun, W.

2016-12-01

Reaction-driven cracking is a coupled process whereby fluid-induced reactions drive large volume changes in the host rock which produce stresses leading to crack propagation and failure. This in turn generates new surface area and fluid-flow pathways for subsequent reaction in a potentially self-sustaining system. This mechanism has has been proposed for the pervasive serpentinization and carbonation of peridotite, as well as applications to mineral carbon sequestration and hydrocarbon extraction. The key computational issue in this problem is implementing algorithms that adequately model the formation of discrete fractures. Here we present models using a discontinuous finite element method for modeling fracture formation (Radovitsky et al., 2011). Cracks are introduced along facets of the mesh by the relaxation of penalty parameters once a failure criterion is met. It is fully described in the weak form of the equations, requiring no modification of the underlying mesh structure and allowing fluid properties to be easily adjusted along cracked facets. To develop and test the method, we start by implementing the algorithm for the simplified Biot equations for poro-elasticity using the finite element model assembler TerraFERMA. We consider hydro-fracking around a borehole (Grassl et al., 2015), where elevated fluid pressure in the poro-elastic solid causes it to fail radially in tension. We investigate the effects of varying the Biot coefficient and adjusting the fluid transport properties in the vicinity of the crack and compare our results to related dual-graph models (Ulven & Sun, submitted). We discuss issues arising from this method, including the formation of null spaces and appropriate preconditioning and solution strategies. Initial results suggest that this method provides a promising way to incorporate cracking into our reactive fluid flow models and future work aims to integrate the mechanical and chemical aspects of this process.

Process for upgrading wax from Fischer-Tropsch synthesis

DOEpatents

Derr, W.R. Jr.; Garwood, W.E.; Kuo, J.C.; Leib, T.M.; Nace, D.M.; Tabak, S.A.

1987-08-04

The waxy liquid phase of an oil suspension of Fischer-Tropsch catalyst containing dissolved wax is separated out and the wax is converted by hydrocracking, dewaxing or by catalytic cracking with a low activity catalyst to provide a highly olefinic product which may be further converted to premium quality gasoline and/or distillate fuel. 2 figs.

Nitrogen Chemistry and Coke Transformation of FCC Coked Catalyst during the Regeneration Process

PubMed Central

Shi, Junjun; Guan, Jianyu; Guo, Dawei; Zhang, Jiushun; France, Liam John; Wang, Lefu; Li, Xuehui

2016-01-01

Regeneration of the coked catalyst is an important process of fluid catalytic cracking (FCC) in petroleum refining, however, this process will emit environmentally harmful gases such as nitrogen and carbon oxides. Transformation of N and C containing compounds in industrial FCC coke under thermal decomposition was investigated via TPD and TPO to examine the evolved gaseous species and TGA, NMR and XPS to analyse the residual coke fraction. Two distinct regions of gas evolution are observed during TPD for the first time, and they arise from decomposition of aliphatic carbons and aromatic carbons. Three types of N species, pyrrolic N, pyridinic N and quaternary N are identified in the FCC coke, the former one is unstable and tends to be decomposed into pyridinic and quaternary N. Mechanisms of NO, CO and CO2 evolution during TPD are proposed and lattice oxygen is suggested to be an important oxygen resource. Regeneration process indicates that coke-C tends to preferentially oxidise compared with coke-N. Hence, new technology for promoting nitrogen-containing compounds conversion will benefit the in-situ reduction of NO by CO during FCC regeneration. PMID:27270486

Adhesion strength of norbornene-based self-healing agents to an amine-cured epoxy

NASA Astrophysics Data System (ADS)

Huang, Guang Chun; Lee, Jong Keun; Kessler, Michael R.; Yoon, Sungho

2009-07-01

Self-healing is triggered by crack propagation through embedded microcapsules in an epoxy matrix, which then release the liquid healing agent into the crack plane. Subsequent exposure of the healing agent to the chemical catalyst initiates ring-opening metathesis polymerization (ROMP) and bonding of the crack faces. In order to improve self-healing functionality, it is necessary to enhance adhesion of polymerized healing agent within the crack to the matrix resin. In this study, shear bond strength between different norbornene-based healing agents and an amine-cured epoxy resin was evaluated using the single lap shear test method (ASTM D3163, modified). The healing agents tested include endodicyclopentadiene (endo-DCPD), 5-ethylidene-2-norbornene (ENB) and DCPD/ENB blends. 5-Norbornene-2-methanol (NBM) was used as an adhesion promoter, containing hydroxyl groups to form hydrogen bonds with the amine-cured epoxy. A custom synthesized norbornene-based crosslinking agent was also added to improve adhesion for ENB by increasing the crosslinking density of the adhesive after ROMP. The healing agents were polymerized with varying loadings of the 1st generation Grubbs' catalyst at different reaction times and temperatures.

Application, Deactivation, and Regeneration of Heterogeneous Catalysts in Bio-Oil Upgrading

DOE PAGES

Cheng, Shouyun; Wei, Lin; Zhao, Xianhui; ...

2016-12-07

The massive consumption of fossil fuels and associated environmental issues are leading to an increased interest in alternative resources such as biofuels. The renewable biofuels can be upgraded from bio-oils that are derived from biomass pyrolysis. Catalytic cracking and hydrodeoxygenation (HDO) are two of the most promising bio-oil upgrading processes for biofuel production. Heterogeneous catalysts are essential for upgrading bio-oil into hydrocarbon biofuel. Although advances have been achieved, the deactivation and regeneration of catalysts still remains a challenge. This review focuses on the current progress and challenges of heterogeneous catalyst application, deactivation, and regeneration. The technologies of catalysts deactivation, reduction,more » and regeneration for improving catalyst activity and stability are discussed. Some suggestions for future research including catalyst mechanism, catalyst development, process integration, and biomass modification for the production of hydrocarbon biofuels are provided.« less

Application, Deactivation, and Regeneration of Heterogeneous Catalysts in Bio-Oil Upgrading

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cheng, Shouyun; Wei, Lin; Zhao, Xianhui

The massive consumption of fossil fuels and associated environmental issues are leading to an increased interest in alternative resources such as biofuels. The renewable biofuels can be upgraded from bio-oils that are derived from biomass pyrolysis. Catalytic cracking and hydrodeoxygenation (HDO) are two of the most promising bio-oil upgrading processes for biofuel production. Heterogeneous catalysts are essential for upgrading bio-oil into hydrocarbon biofuel. Although advances have been achieved, the deactivation and regeneration of catalysts still remains a challenge. This review focuses on the current progress and challenges of heterogeneous catalyst application, deactivation, and regeneration. The technologies of catalysts deactivation, reduction,more » and regeneration for improving catalyst activity and stability are discussed. Some suggestions for future research including catalyst mechanism, catalyst development, process integration, and biomass modification for the production of hydrocarbon biofuels are provided.« less

Changes in geophysical properties caused by fluid injection into porous rocks: analytical models: Geophysical changes in porous rocks

DOE PAGES

Pride, Steven R.; Berryman, James G.; Commer, Michael; ...

2016-08-30

Analytical models are provided that describe how the elastic compliance, electrical conductivity, and fluid-flow permeability of rocks depend on stress and fluid pressure. In order to explain published laboratory data on how seismic velocities and electrical conductivity vary in sandstones and granites, the models require a population of cracks to be present in a possibly porous host phase. The central objective is to obtain a consistent mean-field analytical model that shows how each modeled rock property depends on the nature of the crack population. We describe the crack populations by a crack density, a probability distribution for the crack aperturesmore » and radii, and the averaged orientation of the cracks. The possibly anisotropic nature of the elasticity, conductivity, and permeability tensors is allowed for; however, only the isotropic limit is used when comparing to laboratory data. For the transport properties of conductivity and permeability, the percolation effect of the crack population linking up to form a connected path across a sample is modeled. But, this effect is important only in crystalline rock where the host phase has very small conductivity and permeability. In general, the importance of the crack population to the transport properties increases as the host phase becomes less conductive and less permeable.« less

Changes in geophysical properties caused by fluid injection into porous rocks: analytical models: Geophysical changes in porous rocks

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pride, Steven R.; Berryman, James G.; Commer, Michael

Analytical models are provided that describe how the elastic compliance, electrical conductivity, and fluid-flow permeability of rocks depend on stress and fluid pressure. In order to explain published laboratory data on how seismic velocities and electrical conductivity vary in sandstones and granites, the models require a population of cracks to be present in a possibly porous host phase. The central objective is to obtain a consistent mean-field analytical model that shows how each modeled rock property depends on the nature of the crack population. We describe the crack populations by a crack density, a probability distribution for the crack aperturesmore » and radii, and the averaged orientation of the cracks. The possibly anisotropic nature of the elasticity, conductivity, and permeability tensors is allowed for; however, only the isotropic limit is used when comparing to laboratory data. For the transport properties of conductivity and permeability, the percolation effect of the crack population linking up to form a connected path across a sample is modeled. But, this effect is important only in crystalline rock where the host phase has very small conductivity and permeability. In general, the importance of the crack population to the transport properties increases as the host phase becomes less conductive and less permeable.« less

Diesel fuel blending components from mixture of waste animal fat and light cycle oil from fluid catalytic cracking.

PubMed

Hancsók, Jenő; Sági, Dániel; Valyon, József

2018-06-11

Sustainable production of renewable fuels has become an imperative goal but also remains a huge challenge faced by the chemical industry. A variety of low-value, renewable sources of carbon such as wastes and by-products must be evaluated for their potential as feedstock to achieve this goal. Hydrogenation of blends comprising waste animal fat (≤70 wt%) and low-value fluid catalytic cracking light cycle oil (≥30 wt%), with a total aromatic content of 87.2 wt%, was studied on a commercial sulfided NiMo/Al 2 O 3 catalyst. The fuel fraction in the diesel boiling range was separated by fractional distillation from the organic liquid product obtained from the catalytic conversion of the blend of 70 wt% waste animal fat and 30 wt% light cycle oil. Diesel fuel of the best quality was obtained under the following reaction conditions: T = 615-635 K, P = 6 MPa, LHSV = 1.0 h -1 , H 2 /feedstock ratio = 600 Nm 3 /m 3 . The presence of fat in the feedstock was found to promote the conversion of light cycle oil to a paraffinic blending component for diesel fuel. Thus, a value-added alternative fuel with high biocontent can be obtained from low-value refinery stream and waste animal fat. The resultant disposal of waste animal fat, and the use of fuel containing less fossil carbon for combustion helps reduce the emission of pollutants. Copyright © 2018 Elsevier Ltd. All rights reserved.

Flow and Fracture in Drying Nanoparticle Suspensions

NASA Astrophysics Data System (ADS)

Dufresne, E. R.; Corwin, E. I.; Greenblatt, N. A.; Ashmore, J.; Wang, D. Y.; Dinsmore, A. D.; Cheng, J. X.; Xie, X. S.; Hutchinson, J. W.; Weitz, D. A.

2003-11-01

Drying aqueous suspensions of monodisperse silica nanoparticles can fracture in remarkable patterns. As the material solidifies, evenly spaced cracks invade from the drying surface, with individual cracks undergoing intermittent motion. We show that the growth of cracks is limited by the advancement of the compaction front, which is governed by a balance of evaporation and flow of fluid at the drying surface. Surprisingly, the macroscopic dynamics of drying show signatures of molecular-scale fluid effects.

In-vitro characterization of stress corrosion cracking of aluminium-free magnesium alloys for temporary bio-implant applications.

PubMed

Choudhary, Lokesh; Singh Raman, R K; Hofstetter, Joelle; Uggowitzer, Peter J

2014-09-01

The complex interaction between physiological stresses and corrosive human body fluid may cause premature failure of metallic biomaterials due to the phenomenon of stress corrosion cracking. In this study, the susceptibility to stress corrosion cracking of biodegradable and aluminium-free magnesium alloys ZX50, WZ21 and WE43 was investigated by slow strain rate tensile testing in a simulated human body fluid. Slow strain rate tensile testing results indicated that each alloy was susceptible to stress corrosion cracking, and this was confirmed by fractographic features of transgranular and/or intergranular cracking. However, the variation in alloy susceptibility to stress corrosion cracking is explained on the basis of their electrochemical and microstructural characteristics. Copyright © 2014 Elsevier B.V. All rights reserved.

Guided cracking of electrodes by stretching prism-patterned membrane electrode assemblies for high-performance fuel cells.

PubMed

Ahn, Chi-Yeong; Jang, Segeun; Cho, Yong-Hun; Choi, Jiwoo; Kim, Sungjun; Kim, Sang Moon; Sung, Yung-Eun; Choi, Mansoo

2018-01-19

Guided cracks were successfully generated in an electrode using the concentrated surface stress of a prism-patterned Nafion membrane. An electrode with guided cracks was formed by stretching the catalyst-coated Nafion membrane. The morphological features of the stretched membrane electrode assembly (MEA) were investigated with respect to variation in the prism pattern dimension (prism pitches of 20 μm and 50 μm) and applied strain (S ≈ 0.5 and 1.0). The behaviour of water on the surface of the cracked electrode was examined using environmental scanning electron microscopy. Guided cracks in the electrode layer were shown to be efficient water reservoirs and liquid water passages. The MEAs with and without guided cracks were incorporated into fuel cells, and electrochemical measurements were conducted. As expected, all MEAs with guided cracks exhibited better performance than conventional MEAs, mainly because of the improved water transport.

Catalytic converter with fluid injector for catalyst-free enclosure of catalyst bed

DOE Office of Scientific and Technical Information (OSTI.GOV)

Andrew, S.P.S.

1984-09-25

A fluid injection lozenge comprises two tubes supporting a perforate member forming a cage enclosing the space between the tubes. Each tube has a series of perforations along its length so that a fluid can be injected, through the tube, into the enclosed space. The lozenges are of use in catalytic converters of either the axial or radial flow design. In the case of a radial flow converter, a plurality of tubes are provided, preferably connected in pairs by the perforate members, to form a squirrel cage structure, disposed in the catalyst bed.

Synthesis and characterization of mesoporous hydrocracking catalysts

NASA Astrophysics Data System (ADS)

Munir, D.; Usman, M. R.

2016-08-01

Mesoporous catalysts have shown great prospective for catalytic reactions due to their high surface area that aids better distribution of impregnated metal. They have been found to contain more adsorption sites and controlled pore diameter. Hydrocracking, in the presence of mesoporous catalyst is considered more efficient and higher conversion of larger molecules is observed as compared to the cracking reactions in smaller microporous cavities of traditional zeolites. In the present study, a number of silica-alumina based mesoporous catalysts are synthesized in the laboratory. The concentration and type of surfactants and quantities of silica and alumina sources are the variables studied in the preparation of catalyst supports. The supports prepared are well characterized using SEM, EDX, and N2-BET techniques. Finally, the catalysts are tested in a high pressure autoclave reactor to study the activity and selectivity of the catalysts for the hydrocracking of a model mixture of plastics comprising of LDPE, HDPE, PP, and PS.

High-Flux, High Performance H2O2 Catalyst Bed for ISTAR

NASA Technical Reports Server (NTRS)

Ponzo, J.

2005-01-01

On NASA's ISTAR RBCC program packaging and performance requirements exceeded traditional H2O2 catalyst bed capabilities. Aerojet refined a high performance, monolithic 90% H202 catalyst bed previously developed and demonstrated. This approach to catalyst bed design and fabrication was an enabling technology to the ISTAR tri-fluid engine. The catalyst bed demonstrated 55 starts at throughputs greater than 0.60 lbm/s/sq in for a duration of over 900 seconds in a physical envelope approximately 114 of traditional designs. The catalyst bed uses photoetched plates of metal bonded into a single piece monolithic structure. The precise control of the geometry and complete mixing results in repeatable, quick starting, high performing catalyst bed. Three different beds were designed and tested, with the best performing bed used for tri-fluid engine testing.

Designing supported palladium-on-gold bimetallic nano-catalysts for controlled hydrogenation of acetylene in large excess of ethylene

NASA Astrophysics Data System (ADS)

Malla, Pavani

Ethylene is used as a starting point for many chemical intermediates in the petrochemical industry. It is predominantly produced through steam cracking of higher hydrocarbons (ethane, propane, butane, naphtha, and gas oil). During the cracking process, a small amount of acetylene is produced as a side product. However, acetylene must be removed since it acts as a poison for ethylene polymerization catalysts at even ppm concentrations (>5 ppm). Thus, the selective hydrogenation of acetylene to ethylene is an important process for the purification of ethylene. Conventional, low weight loading Pd catalysts are used for this selective reaction in high concentration ethylene streams. Gold was initially considered to be catalytically inactive for a long time. This changed when gold was seen in the context of the nanometric scale, which has indeed shown it to have excellent catalytic activity as a homogeneous or a heterogeneous catalyst. Gold is proved to have high selectivity to ethylene but poor at conversion. Bimetallic Au and Pd catalysts have exhibited superior activity as compared to Pd particles in semi-hydrogenation. Hydrogenation of acetylene was tested using this bimetallic combination. The Pd-on-Au bimetallic catalyst structure provides a new synthesis approach in improving the catalytic properties of monometallic Pd materials. TiO 2 as a support material and 0.05%Pd loading on 1%Au on titania support and used different treatment methods like washing plasma and reduction between the two metal loadings and was observed under 2:1 ratio. In my study there were two set of catalysts which were prepared by a modified incipient wetness impregnation technique. Out of all the reaction condition the catalyst which was reduced after impregnating gold and then impregnating palladium which was further treated in non-thermal hydrogen plasma and then pretreated in hydrogen till 250°C for 1 hour produced the best activity of 76% yield at 225°C. Stability tests were conducted on the catalysts which were followed by TGA analysis to analyze the coke formation on the catalyst in a period of time at a particular temperature. The catalysts were characterized by the hydrogen chemisorption and atomic absorption spectroscopy.

Carbon dioxide-soluble polymers and swellable polymers for carbon dioxide applications

DOEpatents

DeSimone, Joseph M.; Birnbaum, Eva; Carbonell, Ruben G.; Crette, Stephanie; McClain, James B.; McCleskey, T. Mark; Powell, Kimberly R.; Romack, Timothy J.; Tumas, William

2004-06-08

A method for carrying out a catalysis reaction in carbon dioxide comprising contacting a fluid mixture with a catalyst bound to a polymer, the fluid mixture comprising at least one reactant and carbon dioxide, wherein the reactant interacts with the catalyst to form a reaction product. A composition of matter comprises carbon dioxide and a polymer and a reactant present in the carbon dioxide. The polymer has bound thereto a catalyst at a plurality of chains along the length of the polymer, and wherein the reactant interacts with the catalyst to form a reaction product.

Advanced reactors and novel reactions for the conversion of triglyceride based oils into high quality renewable transportation fuels

NASA Astrophysics Data System (ADS)

Linnen, Michael James

Sustainable energy continues to grow more important to all societies, leading to the research and development of a variety of alternative and renewable energy technologies. Of these, renewable liquid transportation fuels may be the most visible to consumers, and this visibility is further magnified by the long-term trend of increasingly expensive petroleum fuels that the public consumes. While first-generation biofuels such as biodiesel and fuel ethanol have been integrated into the existing fuel infrastructures of several countries, the chemical differences between them and their petroleum counterparts reduce their effectiveness. This gives rise to the development and commercialization of second generation biofuels, many of which are intended to have equivalent properties to those of their petroleum counterparts. In this dissertation, the primary reactions for a second-generation biofuel process, known herein as the University of North Dakota noncatalytic cracking process (NCP), have been studied at the fundamental level and improved. The NCP is capable of producing renewable fuels and chemicals that are virtually the same as their petroleum counterparts in performance and quality (i.e., petroleum-equivalent). In addition, a novel analytical method, FIMSDIST was developed which, within certain limitations, can increase the elution capabilities of GC analysis and decrease sample processing times compared to other high resolution methods. These advances are particularly useful for studies of highly heterogeneous fuel and/or organic chemical intermediates, such as those studied for the NCP. However the data from FIMSDIST must be supplemented with data from other methods such as for certain carboxylic acid, to provide accurate, comprehensive results, From a series of TAG cracking experiments that were performed, it was found that coke formation during cracking is most likely the result of excessive temperature and/or residence time in a cracking reactor. Based on this, a tubular cracking reactor was developed that could operate continuously without coke formation. The design also was proven to be scalable. Yields from the reactor were determined under a variety of conditions in order to predict the outputs from the NCP and to establish relationships/correlations between operating parameters and the product distribution. These studies led to the conclusion that the most severe operating conditions which do not induce coking are optimal over the experimental domain. In order to develop economical deoxygenation catalysts for use within the NCP, a series of experiments were performed using nickel catalysts, demonstrating that nickel catalysts could outperform their predecessor, a high cost palladium-based catalyst. A nickel catalyst was then tested in a packed bed reactor in order to determine suitable operating conditions for its commercial utilization in packed bed reactors.

Successful performance of a refinery with Eureka unit

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hirotani, Y.; Takeuchi, T.; Miyabuchi, Y.

1981-03-01

Since starting in February, 1976, 3,400,000 Kl of vacuum residue (13,000,000 Kl of crude oil equivalent) has been successfully processed in the Eureka unit of Fuji Oil refinery complex and more than 2,500,000 Kl of cracked oil and 1,000,000 tons of pitch have been produced. The operation rate has been 94 to 98% except for the annual shutdown period for inspection. The cracked oil is easily desulfurized to make naphta, diesel oil and a large amount of gas oil (low sulfur fuel oil, 0.1 wt % sulfur). As for the desulfurization of cracked oil, the increase in H/sub 2/ consumptionmore » and the decline of catalyst life are observed. However, the operation conditions do not differ much from those for straight run fractions. Processing both hydrotreated and untreated cracked heavy oil (CHO) with FCC unit has proved to be possible. In case of untreated CHO, however, it causes a slight increase in make up catalyst and coke yield. It is demonstrated that heavy crude oils, such as Bachaquero, can effectively be processed in this system. No additional pollution problems have occurred by introducing an Eureka unit to the refinery, although it is located in the district where the most stringent environmental regulations are urged.« less

4D in situ visualization of electrode morphology changes during accelerated degradation in fuel cells by X-ray computed tomography

NASA Astrophysics Data System (ADS)

White, Robin T.; Wu, Alex; Najm, Marina; Orfino, Francesco P.; Dutta, Monica; Kjeang, Erik

2017-05-01

A four-dimensional visualization approach, featuring three dimensions in space and one dimension in time, is proposed to study local electrode degradation effects during voltage cycling in fuel cells. Non-invasive in situ micro X-ray computed tomography (XCT) with a custom fuel cell fixture is utilized to track the same cathode catalyst layer domain throughout various degradation times from beginning-of-life (BOL) to end-of-life (EOL). With this unique approach, new information regarding damage features and trends are revealed, including crack propagation and catalyst layer thinning being quantified by means of image processing and analysis methods. Degradation heterogeneities as a result of local environmental variations under land and channel are also explored, with a higher structural degradation rate under channels being observed. Density and compositional changes resulting from carbon corrosion and catalyst layer collapse and thinning are observed by changes in relative X-ray attenuation from BOL to EOL, which also indicate possible vulnerable regions where crack initiation and propagation may occur. Electrochemical diagnostics and morphological features observed by micro-XCT are correlated by additionally collecting effective catalyst surface area, double layer capacitance, and polarization curves prior to imaging at various stages of degradation.

Influence of Normal and Shear Stress on the Hydraulic Transmissivity of Thin Cracks in a Tight Quartz Sandstone, a Granite, and a Shale

NASA Astrophysics Data System (ADS)

Rutter, Ernest H.; Mecklenburgh, Julian

2018-02-01

Transmissivity of fluids along fractures in rocks is reduced by increasing normal stress acting across them, demonstrated here through gas flow experiments on Bowland shale, and oil flow experiments on Pennant sandstone and Westerly granite. Additionally, the effect of imposing shear stress at constant normal stress was determined, until frictional sliding started. In all cases, increasing shear stress causes an accelerating reduction of transmissivity by 1 to 3 orders of magnitude as slip initiated, as a result of the formation of wear products that block fluid pathways. Only in the case of granite, and to a lesser extent in the sandstone, was there a minor amount of initial increase of transmissivity prior to the onset of slip. These results cast into doubt the commonly applied presumption that cracks with high resolved shear stresses are the most conductive. In the shale, crack transmissivity is commensurate with matrix permeability, such that shales are expected always to be good seals. For the sandstone and granite, unsheared crack transmissivity was respectively 2 and 2.5 orders of magnitude greater than matrix permeability. For these rocks crack transmissivity can dominate fluid flow in the upper crust, potentially enough to permit maintenance of a hydrostatic fluid pressure gradient in a normal (extensional) faulting regime.

Ethylene Formation by Catalytic Dehydration of Ethanol with Industrial Considerations.

PubMed

Fan, Denise; Dai, Der-Jong; Wu, Ho-Shing

2012-12-28

Ethylene is the primary component in most plastics, making it economically valuable. It is produced primarily by steam-cracking of hydrocarbons, but can alternatively be produced by the dehydration of ethanol, which can be produced from fermentation processes using renewable substrates such as glucose, starch and others. Due to rising oil prices, researchers now look at alternative reactions to produce green ethylene, but the process is far from being as economically competitive as using fossil fuels. Many studies have investigated catalysts and new reaction engineering technologies to increase ethylene yield and to lower reaction temperature, in an effort to make the reaction applicable in industry and most cost-efficient. This paper presents various lab synthesized catalysts, reaction conditions, and reactor technologies that achieved high ethylene yield at reasonable reaction temperatures, and evaluates their practicality in industrial application in comparison with steam-cracking plants. The most promising were found to be a nanoscale catalyst HZSM-5 with 99.7% ethylene selectivity at 240 °C and 630 h lifespan, using a microreactor technology with mechanical vapor recompression, and algae-produced ethanol to make ethylene.

Ethylene Formation by Catalytic Dehydration of Ethanol with Industrial Considerations

PubMed Central

Fan, Denise; Dai, Der-Jong; Wu, Ho-Shing

2012-01-01

Ethylene is the primary component in most plastics, making it economically valuable. It is produced primarily by steam-cracking of hydrocarbons, but can alternatively be produced by the dehydration of ethanol, which can be produced from fermentation processes using renewable substrates such as glucose, starch and others. Due to rising oil prices, researchers now look at alternative reactions to produce green ethylene, but the process is far from being as economically competitive as using fossil fuels. Many studies have investigated catalysts and new reaction engineering technologies to increase ethylene yield and to lower reaction temperature, in an effort to make the reaction applicable in industry and most cost-efficient. This paper presents various lab synthesized catalysts, reaction conditions, and reactor technologies that achieved high ethylene yield at reasonable reaction temperatures, and evaluates their practicality in industrial application in comparison with steam-cracking plants. The most promising were found to be a nanoscale catalyst HZSM-5 with 99.7% ethylene selectivity at 240 °C and 630 h lifespan, using a microreactor technology with mechanical vapor recompression, and algae-produced ethanol to make ethylene. PMID:28809297

In situ hydrogenation and decarboxylation of oleic acid into heptadecane over a Cu–Ni alloy catalyst using methanol as a hydrogen carrier

DOE PAGES

Zhang, Zihao; Yang, Qiwei; Chen, Hao; ...

2017-10-13

In this paper, supported Cu–Ni bimetallic catalysts were synthesized and evaluated for the in situ hydrogenation and decarboxylation of oleic acid using methanol as a hydrogen donor. The supported Cu–Ni alloy exhibited a significant improvement in both activity and selectivity towards the production of heptadecane in comparison with monometallic Cu and Ni based catalysts. The formation of the Cu–Ni alloy is demonstrated by high-angle annular dark-field scanning transmission electron microscopy (HADDF-STEM), energy dispersive X-ray spectroscopy (EDS-mapping), X-ray diffraction (XRD) and temperature programmed reduction (TPR). A partially oxidized Cu in the Cu–Ni alloy is revealed by diffuse reflectance infrared Fourier transformmore » spectroscopy (DRIFTS) following CO adsorption and X-ray photoelectron spectroscopy (XPS). The temperature programmed desorption of ethylene and propane (ethylene/propane-TPD) suggested that the formation of the Cu–Ni alloy inhibited the cracking of C–C bonds compared to Ni, and remarkably increased the selectivity to heptadecane. The temperature programmed desorption of acetic acid (acetic acid-TPD) indicated that the bimetallic Cu–Ni alloy and Ni catalysts had a stronger adsorption of acetic acid than that of the Cu catalyst. Finally, the formation of the Cu–Ni alloy and a partially oxidized Cu facilitates the decarboxylation reaction and inhibits the cracking reaction of C–C bonds, leading to enhanced catalytic activity and selectivity.« less

In situ hydrogenation and decarboxylation of oleic acid into heptadecane over a Cu–Ni alloy catalyst using methanol as a hydrogen carrier

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Zihao; Yang, Qiwei; Chen, Hao

In this paper, supported Cu–Ni bimetallic catalysts were synthesized and evaluated for the in situ hydrogenation and decarboxylation of oleic acid using methanol as a hydrogen donor. The supported Cu–Ni alloy exhibited a significant improvement in both activity and selectivity towards the production of heptadecane in comparison with monometallic Cu and Ni based catalysts. The formation of the Cu–Ni alloy is demonstrated by high-angle annular dark-field scanning transmission electron microscopy (HADDF-STEM), energy dispersive X-ray spectroscopy (EDS-mapping), X-ray diffraction (XRD) and temperature programmed reduction (TPR). A partially oxidized Cu in the Cu–Ni alloy is revealed by diffuse reflectance infrared Fourier transformmore » spectroscopy (DRIFTS) following CO adsorption and X-ray photoelectron spectroscopy (XPS). The temperature programmed desorption of ethylene and propane (ethylene/propane-TPD) suggested that the formation of the Cu–Ni alloy inhibited the cracking of C–C bonds compared to Ni, and remarkably increased the selectivity to heptadecane. The temperature programmed desorption of acetic acid (acetic acid-TPD) indicated that the bimetallic Cu–Ni alloy and Ni catalysts had a stronger adsorption of acetic acid than that of the Cu catalyst. Finally, the formation of the Cu–Ni alloy and a partially oxidized Cu facilitates the decarboxylation reaction and inhibits the cracking reaction of C–C bonds, leading to enhanced catalytic activity and selectivity.« less

Thermocatalytic process for CO.sub.2-free production of hydrogen and carbon from hydrocarbons

DOEpatents

Muradov, Nazim Z [Melbourne, FL

2011-08-23

A novel process and apparatus are disclosed for sustainable CO.sub.2-free production of hydrogen and carbon by thermocatalytic decomposition (dissociation, pyrolysis, cracking) of hydrocarbon fuels over carbon-based catalysts in the absence of air and/or water. The apparatus and thermocatalytic process improve the activity and stability of carbon catalysts during the thermocatalytic process and produce both high purity hydrogen (at least, 99.0 volume %) and carbon, from any hydrocarbon fuel, including sulfurous fuels. In a preferred embodiment, production of hydrogen and carbon is achieved by both internal and external activation of carbon catalysts. Internal activation of carbon catalyst is accomplished by recycling of hydrogen-depleted gas containing unsaturated and aromatic hydrocarbons back to the reactor. External activation of the catalyst can be achieved via surface gasification with hot combustion gases during catalyst heating. The process and apparatus can be conveniently integrated with any type of fuel cell to generate electricity.

Water-gas shift reaction on alumina-supported Pt-CeO x catalysts prepared by supercritical fluid deposition

DOE PAGES

Deal, Jacob W.; Le, Phong; Corey, C. Blake; ...

2016-08-25

Alumina-supported platinum catalysts, both with and without ceria, were prepared by supercritical fluid deposition and evaluated for activity for water-gas shift reaction. The organometallic precursor, platinum(II) acetylacetonate, was deposited from solution in supercritical carbon dioxide. Analysis of the catalysts by high resolution scanning transmission electron microscopy indicated that platinum was present in the form of highly dispersed metal nanoparticles. Pretreatment of the alumina-supported ceria in hydrogen prior to the deposition of the platinum precursor resulted in more platinum nucleated on ceria than non-pretreated alumina-supported ceria but varied in both particle size and structure. The ceria-containing catalyst that was not pretreatedmore » exhibited a more uniform particle size, and the Pt particles were encapsulated in crystalline ceria. Reaction rate measurements showed that the catalyst was more active for water-gas shift, with reaction rates per mass of platinum that exceeded most literature values for water-gas shift reaction on Pt-CeO x catalysts. The high activity was attributed to the significant fraction of platinum/ceria interfacial contact. We found that these results show the promise of supercritical fluid deposition as a scalable means of synthesizing highly active supported metal catalysts that offer efficient utilization of precious metals.« less

Dynamic bulk and shear moduli due to grain-scale local fluid flow in fluid-saturated cracked poroelastic rocks: Theoretical model

NASA Astrophysics Data System (ADS)

Song, Yongjia; Hu, Hengshan; Rudnicki, John W.

2016-07-01

Grain-scale local fluid flow is an important loss mechanism for attenuating waves in cracked fluid-saturated poroelastic rocks. In this study, a dynamic elastic modulus model is developed to quantify local flow effect on wave attenuation and velocity dispersion in porous isotropic rocks. The Eshelby transform technique, inclusion-based effective medium model (the Mori-Tanaka scheme), fluid dynamics and mass conservation principle are combined to analyze pore-fluid pressure relaxation and its influences on overall elastic properties. The derivation gives fully analytic, frequency-dependent effective bulk and shear moduli of a fluid-saturated porous rock. It is shown that the derived bulk and shear moduli rigorously satisfy the Biot-Gassmann relationship of poroelasticity in the low-frequency limit, while they are consistent with isolated-pore effective medium theory in the high-frequency limit. In particular, a simplified model is proposed to quantify the squirt-flow dispersion for frequencies lower than stiff-pore relaxation frequency. The main advantage of the proposed model over previous models is its ability to predict the dispersion due to squirt flow between pores and cracks with distributed aspect ratio instead of flow in a simply conceptual double-porosity structure. Independent input parameters include pore aspect ratio distribution, fluid bulk modulus and viscosity, and bulk and shear moduli of the solid grain. Physical assumptions made in this model include (1) pores are inter-connected and (2) crack thickness is smaller than the viscous skin depth. This study is restricted to linear elastic, well-consolidated granular rocks.

International Conference/Workshop on Small Fatigue Cracks (2nd) Held in Santa Barbara, California on 5-10 January 1986.

DTIC Science & Technology

1986-03-31

critical issues thus pertain to the determination of crack tip conditions, as a function of crack length, in terms of the coupled processes of fluid...transport and chemical/electrochemical reactions within the crack, and the determination of the origin of the environmentally-enhanced cracking rates in...Depth in Determining Crack Electrochemistry and Crack Growth" A. Turnbull, National Physical Laboratory, U.K., and R. C. Newmann, UMIST, U.K. 7:30 p.m.-7

China’s Rare Earth Elements Industry: What Can the West Learn?

DTIC Science & Technology

2010-03-01

critical in petroleum refining. By one estimate, lanthanum " cracking -agents" increase refinery yield by as much as 10%, while reducing overall...where it is used as a signal amplifier. Praseodymium salts give color to glasses and enamels . It is also a component of didymium glass, used to make...thermal neutron activation. Therefore, it can be used as catalysts in cracking , alkylation, hydrogenation, and polymerization. Cerium-doped

Regeneration of zinc halide catalyst used in the hydrocracking of polynuclear hydrocarbons

DOEpatents

Gorin, Everett

1978-01-01

Improved recovery of spent molten zinc halide hydro-cracking catalyst is achieved in the oxidative vapor phase regeneration thereof by selective treatment of the zinc oxide carried over by the effluent vapors from the regeneration zone with hydrogen halide gas under conditions favoring the reaction of the zinc oxide with the hydrogen halide, whereby regenerated zinc halide is recovered in a solids-free state with little loss of zinc values.

The Use of Fry (Embalming Fluid and PCP-Laced Cigarettes or Marijuana Sticks) among Crack Cocaine Smokers

ERIC Educational Resources Information Center

Peters, Ronald J.; Williams, Mark; Ross, Michael W.; Atkinson, John; McCurdy, Sherly A.

2009-01-01

Statistics show that the prevalence of crack cocaine use and embalming fluid and phencyclidine (PCP)-laced cigarettes or marijuana sticks, commonly referred to on the street as "fry" or "wet" is a problem; however, the relationship between these substances of abuse and concurrent polydrug use is unknown. In the present study, a…

Source mechanism of long-period events at Kusatsu-Shirane Volcano, Japan, inferred from waveform inversion of the effective excitation functions

USGS Publications Warehouse

Nakano, M.; Kumagai, H.; Chouet, B.A.

2003-01-01

We investigate the source mechanism of long-period (LP) events observed at Kusatsu-Shirane Volcano, Japan, based on waveform inversions of their effective excitation functions. The effective excitation function, which represents the apparent excitation observed at individual receivers, is estimated by applying an autoregressive filter to the LP waveform. Assuming a point source, we apply this method to seven LP events the waveforms of which are characterized by simple decaying and nearly monochromatic oscillations with frequency in the range 1-3 Hz. The results of the waveform inversions show dominant volumetric change components accompanied by single force components, common to all the events analyzed, and suggesting a repeated activation of a sub-horizontal crack located 300 m beneath the summit crater lakes. Based on these results, we propose a model of the source process of LP seismicity, in which a gradual buildup of steam pressure in a hydrothermal crack in response to magmatic heat causes repeated discharges of steam from the crack. The rapid discharge of fluid causes the collapse of the fluid-filled crack and excites acoustic oscillations of the crack, which produce the characteristic waveforms observed in the LP events. The presence of a single force synchronous with the collapse of the crack is interpreted as the release of gravitational energy that occurs as the slug of steam ejected from the crack ascends toward the surface and is replaced by cooler water flowing downward in a fluid-filled conduit linking the crack and the base of the crater lake. ?? 2003 Elsevier Science B.V. All rights reserved.

Insights into Volcanic Tremor: A Linear Stability Analysis of Waves Propagating Along Fluid-Filled Cracks

NASA Astrophysics Data System (ADS)

Lipovsky, B.; Dunham, E. M.

2012-12-01

Crack waves are guided waves along fluid-filled cracks that propagate with phase velocity less than the sound wave speed. Chouet (JGR, 1986) and Ferrazzini and Aki (JGR, 1977) have shown that such waves could explain volcanic tremor in terms of the resonant modes of a finite length magma-filled crack. Based on an idealized lumped-parameter model, Julian (JGR, 1994) further proposed that the steady flow of a viscous magma in a volcanic conduit is unstable to perturbations, leading to self-excited oscillations of the conduit walls and radiation of seismic waves. Our objective is to evaluate the possibility of self-excited oscillations within a rigorous, continuum framework. Our specific focus has been on basaltic fissure eruptions. In a typical basaltic fissure system, the magnitudes of the wave restoring forces, fluid compressibility and wall elasticity, are highly depth dependent. Because of the elevated fluid compressibility from gas exsolution at shallow depths, fluid pressure perturbations in this regime propagate as acoustic waves with effectively rigid conduit walls. Below the exsolution depth, the conduit walls are more compliant relative to the magma compressibility and perturbations propagate as dispersive crack waves. Viscous magma flow through such a fissure will evolve to a fully developed state characterized by a parabolic velocity profile in several to tens of seconds. This time scale is greater than harmonic tremor periods, typically 0.1 to 1 second. A rigorous treatment of the wave response to pressure perturbations therefore requires a general analysis of conduit flow that is not in a fully developed state. We present a linearized analysis of the coupled fluid and elastic response to general flow perturbations. We assume that deformation of the wall is linear elastic. As our focus is on wavelengths greatly exceeding the crack width, fluid flow is described by a quasi-one dimensional, or width-averaged, model. We account for conservation of magma mass and momentum including compressibility and viscous drag. Our analysis further assumes small perturbations about a steady background flow, a linearized isothermal equation of state, and a nominally constant width channel. We confirm Julian's results that sufficiently rapid flow through a deformable-walled conduit is unstable to perturbations in the form of crack waves. Instability occurs when drag reduction from opening the conduit exceeds the increase in drag from increased fluid velocity. Crack waves are most unstable at long wavelengths, where the conduit becomes more compliant. In the long wavelength limit, we find a simple expression for the critical flow speed beyond which crack waves are unstable: u = c / 2, where c is the crack wave phase velocity. The instability condition is remarkably independent of viscosity. This result more rigorously confirms the conclusion of Dunham and Ogden (2012, J. App. Mech.), who found the same instability criterion under the limiting assumption of fully developed flow. In a typical basaltic system the occurrence of this instability requires flow speeds exceeding ~50 m/s at depths where magma is primarily liquid melt with little exsolved gas. At these depths, flow speeds of this order are unlikely to occur. We conclude that harmonic tremor due to self-excited oscillations is unlikely to occur in nature.

Hydrodesulfurization reactions of atmospheric gas oil over CoMo/alumina-aluminum borate catalysts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chiuping Li; Jungchung Wu; Yuwen Chen

1993-08-01

A precipitation technique at constant pH value was used to prepare a series of alumina-aluminum borates (AABs) with various Al/B atomic ratios. These materials were used as the supports of Co-Mo catalysts. Hydrodesulfurization (HDS) of Kuwait atmospheric gas (AGO) oil was carried out over these presulfided catalysts in a bench-scale trickle bed reactor at 400 psi and 340 C. All CoMo/AAB catalysts are much more active than the conventional CoMo/Al[sub 2]O[sub 3] catalyst on HDS reactions. A correlation exists between the acidity and the HDS activity of the catalysts. The high activities of the CoMo/AAB catalysts can be rationalized onmore » the presence of boron. On one hand, it can increase the metal dispersions and hydrogenation capabilities. On the other hand, it can enhance the acidities and cracking abilities of the catalysts. The desulfurization data can be fitted with a pseudo-second-order rate equation. The activation energy for desulfurization is found to be 26 kcal/mol.« less

Cresol Izomerization in the Presence of Acid Catalysts

NASA Astrophysics Data System (ADS)

Tarasov, A. L.; Dunaev, S. F.; Kustov, L. M.

2018-02-01

It is shown for toluene oxidation with nitrous oxide that modifying HZSM-5 zeolite with zinc oxide nanoparticles considerably improves the selectivity and yield of cresols. It is found that a 2% ZnO/HZSM-5 composite catalyst also exhibits enhanced and stable activity at high temperatures. For the o-cresol isomerization reaction, this modification of HZSM-5 zeolite greatly reduces the contribution from disproportionation and cracking reactions proceeding with formation of phenol, C6-C9 aromatic hydrocarbons, and xylenols. The regularities of their formation in the presence of the studied catalysts are determined using the results from thermodynamic calculations for the equilibrium concentrations of cresol isomers.

Task 3.9 -- Catalytic tar cracking. Semi-annual report, January 1--June 30, 1995

DOE Office of Scientific and Technical Information (OSTI.GOV)

Young, B.C.; Timpe, R.C.

1995-12-31

Tar produced in the gasification of coal is deleterious to the operation of downstream equipment including fuel cells, gas turbines, hot-gas stream cleanup filters, and pressure swing adsorption systems. Catalytic cracking of tars to smaller hydrocarbons can be an effective means to remove these tars from gas streams and, in the process, generate useful products, e.g., methane gas, which is crucial to the operation of molten carbonate fuel cells. The objectives of this project are to investigate whether gasification tars can be cracked by synthetic nickel-substituted micamontmorillonite, zeolite, or dolomite material; and whether the tars can be cracked selectively bymore » these catalysts to produce a desired liquid and/or gas stream. Results to date are presented in the cited papers.« less

Origin of the pulse-like signature of shallow long-period volcano seismicity

USGS Publications Warehouse

Chouet, Bernard A.; Dawson, Phillip B.

2016-01-01

Short-duration, pulse-like long-period (LP) events are a characteristic type of seismicity accompanying eruptive activity at Mount Etna in Italy in 2004 and 2008 and at Turrialba Volcano in Costa Rica and Ubinas Volcano in Peru in 2009. We use the discrete wave number method to compute the free surface response in the near field of a rectangular tensile crack embedded in a homogeneous elastic half space and to gain insights into the origin of the LP pulses. Two source models are considered, including (1) a vertical fluid-driven crack and (2) a unilateral tensile rupture growing at a fixed sub-Rayleigh velocity with constant opening on a vertical crack. We apply cross correlation to the synthetics and data to demonstrate that a fluid-driven crack provides a natural explanation for these data with realistic source sizes and fluid properties. Our modeling points to shallow sources (<1 km depth), whose signatures are representative of the Rayleigh pulse sampled at epicentral distances >∼1 km. While a slow-rupture failure provides another potential model for these events, the synthetics and resulting fits to the data are not optimal in this model compared to a fluid-driven source. We infer that pulse-like LP signatures are parts of the continuum of responses produced by shallow fluid-driven sources in volcanoes.

DEVELOPMENT OF IMPROVED TITANIUM ORGANIC COMPOUNDS FOR USE AS HYDRAULIC FLUIDS

DTIC Science & Technology

HYDRAULIC FLUIDS, *METALORGANIC COMPOUNDS, *TITANATES, *TITANIUM COMPOUNDS, ALKYL RADICALS, CATALYSTS , CHLORIDES, COMPLEX COMPOUNDS, FLUIDS, PHOSPHORIC ACIDS, PROPYL RADICALS, VISCOSITY, ZINC COMPOUNDS

Torrefaction reduction of coke formation on catalysts used in esterification and cracking of biofuels from pyrolysed lignocellulosic feedstocks

DOEpatents

Kastner, James R; Mani, Sudhagar; Hilten, Roger; Das, Keshav C

2015-11-04

A bio-oil production process involving torrefaction pretreatment, catalytic esterification, pyrolysis, and secondary catalytic processing significantly reduces yields of reactor char, catalyst coke, and catalyst tar relative to the best-case conditions using non-torrefied feedstock. The reduction in coke as a result of torrefaction was 28.5% relative to the respective control for slow pyrolysis bio-oil upgrading. In fast pyrolysis bio-oil processing, the greatest reduction in coke was 34.9%. Torrefaction at 275.degree. C. reduced levels of acid products including acetic acid and formic acid in the bio-oil, which reduced catalyst coking and increased catalyst effectiveness and aromatic hydrocarbon yields in the upgraded oils. The process of bio-oil generation further comprises a catalytic esterification of acids and aldehydes to generate such as ethyl levulinate from lignified biomass feedstock.

The effects of catalysts on the conversion of organic matter and bio-fuel production in the microwave pyrolysis of sludge at different temperatures.

PubMed

Ma, Rui; Huang, Xiaofei; Zhou, Yang; Fang, Lin; Sun, Shichang; Zhang, Peixin; Zhang, Xianghua; Zhao, Xuxin

2017-08-01

Adding catalyst could improve the yields and qualities of bio-gas and bio-oil, and realize the oriented production. Results showed that the catalytic gas-production capacities of CaO were higher than those of Fe 2 O 3 , and the bio-gas yield at 800°C reached a maximum of 35.1%. Because the polar cracking active sites of CaO reduced the activation energy of the pyrolysis reaction and resulted in high catalytic cracking efficiencies. In addition, the quality of bio-oil produced by CaO was superior to that by Fe 2 O 3 , although the bio-oil yield of CaO was relatively weak. The light bio-fuel oriented catalytic pyrolysis could be realized when adding different catalysts. At 800°C, CaO was 45% higher than Fe 2 O 3 in aspect of H 2 production while Fe 2 O 3 was 103% higher than CaO in aspect of CH 4 production. Therefore, CaO was more suitable for H 2 production and Fe 2 O 3 was more suitable for CH 4 production. Copyright © 2017 Elsevier Ltd. All rights reserved.

Influence of circumferential notch and fatigue crack on the mechanical integrity of biodegradable magnesium-based alloy in simulated body fluid.

PubMed

Bobby Kannan, M; Singh Raman, R K; Witte, F; Blawert, C; Dietzel, W

2011-02-01

Applications of magnesium alloys as biodegradable orthopaedic implants are critically dependent on the mechanical integrity of the implant during service. In this study, the mechanical integrity of an AZ91 magnesium alloy was studied using a constant extension rate tensile (CERT) method. The samples in two different geometries that is, circumferentially notched (CN), and circumferentially notched and fatigue cracked (CNFC), were tested in air and in simulated body fluid (SBF). The test results show that the mechanical integrity of the AZ91 magnesium alloy decreased substantially (∼50%) in both the CN and CNFC samples exposed to SBF. Fracture surface analysis revealed secondary cracks suggesting stress corrosion cracking susceptibility of the alloy in SBF. Copyright © 2010 Wiley Periodicals, Inc.

Fast pyrolysis oil from pinewood chips co-processing with vacuum gas oil in an FCC unit for second generation fuel production

DOE PAGES

Pinho, Andrea de Rezende; de Almeida, Marlon B. B.; Mendes, Fabio Leal; ...

2016-10-15

Raw bio-oil produced from fast pyrolysis of pine woodchips was co-processed with standard Brazilian vacuum gasoil (VGO) and tested in a 200 kg•h -1 fluid catalytic cracking (FCC) demonstration-scale unit using a commercial FCC equilibrium catalyst. Two different bio-oil/VGO weight ratios were used: 5/95 and 10/90. Co-processing of raw bio-oil in FCC was shown to be technically feasible. Bio-oil could be directly co-processed with a regular gasoil FCC feed up to 10 wt%. The bio-oil and the conventional gasoil were cracked into valuable liquid products such as gasoline and diesel range products. Most of the oxygen present in the bio-oilmore » was eliminated as water and carbon monoxide as these yields were always higher than that of carbon dioxide. Product quality analysis shows that trace oxygenates, primarily alkyl phenols, in FCC gasoline and diesel products are present with or without co-processing oxygenated intermediates. The oxygenate concentrations increase with co-processing, but have not resulted in increased concerns with quality of fuel properties. The presence of renewable carbon was confirmed in gasoline and diesel cuts through 14C isotopic analysis, showing that renewable carbon is not only being converted into coke, CO, and CO 2, but also into valuable refining liquid products. Thus, gasoline and diesel could be produced from lignocellulosic raw materials through a conventional refining scheme, which uses the catalytic cracking process. As a result, the bio-oil renewable carbon conversion into liquid products (carbon efficiency) was approximately 30%, well above the efficiency found in literature for FCC bio-oil upgrading.« less

Fast pyrolysis oil from pinewood chips co-processing with vacuum gas oil in an FCC unit for second generation fuel production

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pinho, Andrea de Rezende; de Almeida, Marlon B. B.; Mendes, Fabio Leal

Raw bio-oil produced from fast pyrolysis of pine woodchips was co-processed with standard Brazilian vacuum gasoil (VGO) and tested in a 200 kg•h -1 fluid catalytic cracking (FCC) demonstration-scale unit using a commercial FCC equilibrium catalyst. Two different bio-oil/VGO weight ratios were used: 5/95 and 10/90. Co-processing of raw bio-oil in FCC was shown to be technically feasible. Bio-oil could be directly co-processed with a regular gasoil FCC feed up to 10 wt%. The bio-oil and the conventional gasoil were cracked into valuable liquid products such as gasoline and diesel range products. Most of the oxygen present in the bio-oilmore » was eliminated as water and carbon monoxide as these yields were always higher than that of carbon dioxide. Product quality analysis shows that trace oxygenates, primarily alkyl phenols, in FCC gasoline and diesel products are present with or without co-processing oxygenated intermediates. The oxygenate concentrations increase with co-processing, but have not resulted in increased concerns with quality of fuel properties. The presence of renewable carbon was confirmed in gasoline and diesel cuts through 14C isotopic analysis, showing that renewable carbon is not only being converted into coke, CO, and CO 2, but also into valuable refining liquid products. Thus, gasoline and diesel could be produced from lignocellulosic raw materials through a conventional refining scheme, which uses the catalytic cracking process. As a result, the bio-oil renewable carbon conversion into liquid products (carbon efficiency) was approximately 30%, well above the efficiency found in literature for FCC bio-oil upgrading.« less

Recycling of waste spent catalyst in road construction and masonry blocks.

PubMed

Taha, Ramzi; Al-Kamyani, Zahran; Al-Jabri, Khalifa; Baawain, Mahad; Al-Shamsi, Khalid

2012-08-30

Waste spent catalyst is generated in Oman as a result of the cracking process of petroleum oil in the Mina Al-Fahl and Sohar Refineries. The disposal of spent catalyst is of a major concern to oil refineries. Stabilized spent catalyst was evaluated for use in road construction as a whole replacement for crushed aggregates in the sub-base and base layers and as a partial replacement for Portland cement in masonry blocks manufacturing. Stabilization is necessary as the waste spent catalyst exists in a powder form and binders are needed to attain the necessary strength required to qualify its use in road construction. Raw spent catalyst was also blended with other virgin aggregates, as a sand or filler replacement, for use in road construction. Compaction, unconfined compressive strength and leaching tests were performed on the stabilized mixtures. For its use in masonry construction, blocks were tested for unconfined compressive strength at various curing periods. Results indicate that the spent catalyst has a promising potential for use in road construction and masonry blocks without causing any negative environmental impacts. Copyright © 2012 Elsevier B.V. All rights reserved.

Vibrational modes of hydraulic fractures: Inference of fracture geometry from resonant frequencies and attenuation

NASA Astrophysics Data System (ADS)

Lipovsky, Bradley P.; Dunham, Eric M.

2015-02-01

Oscillatory seismic signals arising from resonant vibrations of hydraulic fractures are observed in many geologic systems, including volcanoes, glaciers and ice sheets, and hydrocarbon and geothermal reservoirs. To better quantify the physical dimensions of fluid-filled cracks and properties of the fluids within them, we study wave motion along a thin hydraulic fracture waveguide. We present a linearized analysis, valid at wavelengths greater than the fracture aperture, that accounts for quasi-static elastic deformation of the fracture walls, as well as fluid viscosity, inertia, and compressibility. In the long-wavelength limit, anomalously dispersed guided waves known as crack or Krauklis waves propagate with restoring force from fracture wall elasticity. At shorter wavelengths, the waves become sound waves within the fluid channel. Wave attenuation in our model is due to fluid viscosity, rather than seismic radiation from crack tips or fracture wall roughness. We characterize viscous damping at both low frequencies, where the flow is always fully developed, and at high frequencies, where the flow has a nearly constant velocity profile away from viscous boundary layers near the fracture walls. Most observable seismic signals from resonating fractures likely arise in the boundary layer crack wave limit, where fluid-solid coupling is pronounced and attenuation is minimal. We present a method to estimate the aperture and length of a resonating hydraulic fracture using both the seismically observed quality factor and characteristic frequency. Finally, we develop scaling relations between seismic moment and characteristic frequency that might be useful when interpreting the statistics of hydraulic fracture events.

Characterization of asphaltene molecular structures by cracking under hydrogenation conditions and prediction of the viscosity reduction from visbreaking of heavy oils

NASA Astrophysics Data System (ADS)

Rueda Velasquez, Rosa Imelda

The chemical building blocks that comprise petroleum asphaltenes were determined by cracking samples under conditions that minimized alterations to aromatic and cycloalkyl groups. Hydrogenation conditions that used tetralin as hydrogen-donor solvent, with an iron-based catalyst, allowed asphaltenes from different geological regions to yield 50-60 wt% of distillates (<538°C fraction), with coke yields below 10 wt%. Control experiments with phenanthrene and 5alpha-cholestane confirmed low hydrogenation catalytic activity, and preservation of the cycloalkyl structures. Quantitative recovery of cracking products and characterization of the distillates, by gas chromatography-field ionization--time of flight high resolution mass spectrometry, displayed remarkable similarity in molecular composition for the different asphaltenes. Paraffins and 1-3 ring aromatics were the most abundant building blocks. The diversity of molecules identified, and the high yield of paraffins were consistent with high heterogeneity and complexity of molecules, built up by smaller fragments attached to each other by bridges. The sum of material remaining as vacuum residue and coke was in the range of 35-45 wt%; this total represents the maximum amount of large clusters in asphaltenes that could not be converted to lighter compounds under the evaluated cracking conditions. These analytical data for Cold Lake asphaltenes were transformed into probability density functions that described the molecular weight distributions of the building blocks. These distributions were input for a Monte Carlo approach that allowed stochastic construction of asphaltenes and simulation of their cracking reactions to examine differences in the distributions of products associated to the molecular topology. The construction algorithm evidenced that a significant amount of asphaltenes would consist of 3-5 building blocks. The results did not show significant differences between linear and dendritic molecular architectures, but suggested that dendritic molecules would experience slower reaction rates as they required more breakages to reach a given yield of distillates. Thermal cracking of asphaltenes in heavy oils and bitumens can dramatically reduce viscosity, enabling pipeline transportation with less solvent addition. The viscosities of the products from visbreaking reactions of two different heavy oils were modeled with lumped kinetics based on boiling point pseudo-components, and with the estimation of their individual fluid properties. The model was tuned with experimental viscosity data, and provided estimations of viscosities at different temperatures with absolute average deviations lower than 31%.

Cracking and aromatization of C{sub 6}-C{sub 10} n-alkanes and n-alkenes on a zeolite-containing catalyst

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gairbekov, T.M.; Takaeva, M.I.; Khadzhiev, S.N.

1992-05-10

Despite the extensive studies on catalysis on zeolites, the question of the mechanism of the reactions of cracking and aromatization of hydrocarbons is still debated. The classic Whitmore theory hypothesizes that cracking of alkanes and alkenes takes place through the formation of the same intermediate trivalent carbenium ions of the (C{sub n}H{sub 2n+1}){sup +} type. Ola`s protolytic mechanism hypothesizes nonclassic five- (four-)coordinated ions of the (C{sub n}H{sub 2n+3}){sup +} type for cracking of alkanes and classic carbenium ions for alkenes. When the classic mechanism occurs on zeolites, an analogous effect on the rate of the reactions of alkanes and alkenesmore » with the molecular weight of the starting hydrocarbons and similar compositions of the products obtained should be predicted. The authors investigated the transformation of individual n-alkanes and n-1-alkenes of C{sub 6}-C{sub 10} composition in the presence of a catalyst synthesized by addition of 30 wt.% decationized ultrahigh-silicon zeolite of the ZSM type (Si/Al - 16) modified with 1 wt.% zinc on {gamma}-Al{sub 2}O{sub 3}. The experiment was conducted on a flow-type laboratory setup at 425{degrees}C in conditions of the minimum effect of diffusion factors with the method described in detail previously. 13 refs., 4 figs., 1 tab.« less

Transportation fuel production by combination of LDPE thermal cracking and catalytic hydroreforming.

PubMed

Escola, J M; Aguado, J; Serrano, D P; Briones, L

2014-11-01

Fuel production from plastics is a promising way to reduce landfilling rates while obtaining valuable products. The usage of Ni-supported hierarchical Beta zeolite (h-Beta) for the hydroreforming of the oils coming from LDPE thermal cracking has proved to produce high selectivities to gasoline and diesel fuels (>80%). In the present work, the effect of the Ni loading on Ni/h-Beta is investigated in the hydroreforming of the oils form LDPE thermal cracking. h-Beta samples were impregnated with Ni nitrate, calcined and reduced in H2 up to 550°C to achieve different Ni contents: 1.5%, 4%, 7% and 10%. Larger and more easily reducible metal particles were obtained on Ni 7%/h-Beta and Ni 10%/h-Beta. Hydroreforming tests were carried out in autoclave reactor at 310°C, under 20 bar H2, for 45 min. Ni content progressively increased the amount of gases at the expenses of diesel fractions, while gasoline remained approximately constant about 52-54%. Maximum selectivity to automotive fuels (∼81%) was obtained with Ni 7%/h-Beta. Ni loading also enhanced olefins saturation up to Ni 7%/h-Beta. High cetane indices (71-86) and octane numbers (89-91) were obtained over all the catalysts. Regarding the different studied Ni contents, Ni 7%/h-Beta constitutes a rather promising catalyst for obtaining high quality fuels from LDPE thermal cracking oils. Copyright © 2014 Elsevier Ltd. All rights reserved.

Seismic waves in rocks with fluids and fractures

DOE Office of Scientific and Technical Information (OSTI.GOV)

Berryman, J.G.

2007-05-14

Seismic wave propagation through the earth is often stronglyaffected by the presence of fractures. When these fractures are filledwith fluids (oil, gas, water, CO2, etc.), the type and state of the fluid(liquid or gas) can make a large difference in the response of theseismic waves. This paper summarizes recent work on methods ofdeconstructing the effects of fractures, and any fluids within thesefractures, on seismic wave propagation as observed in reflection seismicdata. One method explored here is Thomsen's weak anisotropy approximationfor wave moveout (since fractures often induce elastic anisotropy due tononuniform crack-orientation statistics). Another method makes use ofsome very convenient fracturemore » parameters introduced previously thatpermit a relatively simple deconstruction of the elastic and wavepropagation behavior in terms of a small number of fracture parameters(whenever this is appropriate, as is certainly the case for small crackdensities). Then, the quantitative effects of fluids on thesecrack-influence parameters are shown to be directly related to Skempton scoefficient B of undrained poroelasticity (where B typically ranges from0 to 1). In particular, the rigorous result obtained for the low crackdensity limit is that the crack-influence parameters are multiplied by afactor (1 ? B) for undrained systems. It is also shown how fractureanisotropy affects Rayleigh wave speed, and how measured Rayleigh wavespeeds can be used to infer shear wave speed of the fractured medium.Higher crack density results are also presented by incorporating recentsimulation data on such cracked systems.« less

Analogy between fluid cavitation and fracture mechanics

NASA Astrophysics Data System (ADS)

Hendricks, R. C.; Mullen, R. L.; Braun, M. J.

When the stresses imposed on a fluid are sufficiently large, rupture or cavitation can occur. Such conditions can exist in many two-phase flow applications, such as the choked flows, which can occur in seals and bearings. Nonspherical bubbles with large aspect ratios have been observed in fluids under rapid acceleration and high shear fields. These bubbles are geometrically similar to fracture surface patterns (Griffith crack model) existing in solids. Analogies between crack growth in solid and fluid cavitation are proposed and supported by analysis and observation (photographs). Healing phenomena (void condensation), well accepted in fluid mechanics, have been observed in some polymers and hypothesized in solid mechanics. By drawing on the strengths of the theories of solid mechanics and cavitation, a more complete unified theory can be developed.

Analogy between fluid cavitation and fracture mechanics

NASA Technical Reports Server (NTRS)

Hendricks, R. C.; Mullen, R. L.; Braun, M. J.

1983-01-01

When the stresses imposed on a fluid are sufficiently large, rupture or cavitation can occur. Such conditions can exist in many two-phase flow applications, such as the choked flows, which can occur in seals and bearings. Nonspherical bubbles with large aspect ratios have been observed in fluids under rapid acceleration and high shear fields. These bubbles are geometrically similar to fracture surface patterns (Griffith crack model) existing in solids. Analogies between crack growth in solid and fluid cavitation are proposed and supported by analysis and observation (photographs). Healing phenomena (void condensation), well accepted in fluid mechanics, have been observed in some polymers and hypothesized in solid mechanics. By drawing on the strengths of the theories of solid mechanics and cavitation, a more complete unified theory can be developed.

Process for producing biodiesel, lubricants, and fuel and lubricant additives in a critical fluid medium

DOEpatents

Ginosar, Daniel M.; Fox, Robert V.

2005-05-03

A process for producing alkyl esters useful in biofuels and lubricants by transesterifying glyceride- or esterifying free fatty acid-containing substances in a single critical phase medium is disclosed. The critical phase medium provides increased reaction rates, decreases the loss of catalyst or catalyst activity and improves the overall yield of desired product. The process involves the steps of dissolving an input glyceride- or free fatty acid-containing substance with an alcohol or water into a critical fluid medium; reacting the glyceride- or free fatty acid-containing substance with the alcohol or water input over either a solid or liquid acidic or basic catalyst and sequentially separating the products from each other and from the critical fluid medium, which critical fluid medium can then be recycled back in the process. The process significantly reduces the cost of producing additives or alternatives to automotive fuels and lubricants utilizing inexpensive glyceride- or free fatty acid-containing substances, such as animal fats, vegetable oils, rendered fats, and restaurant grease.

Pyrolysis of aseptic packages (tetrapak) in a laboratory screw type reactor and secondary thermal/catalytic tar decomposition.

PubMed

Haydary, J; Susa, D; Dudáš, J

2013-05-01

Pyrolysis of aseptic packages (tetrapak cartons) in a laboratory apparatus using a flow screw type reactor and a secondary catalytic reactor for tar cracking was studied. The pyrolysis experiments were realized at temperatures ranging from 650 °C to 850 °C aimed at maximizing of the amount of the gas product and reducing its tar content. Distribution of tetrapak into the product yields at different conditions was obtained. The presence of H2, CO, CH4, CO2 and light hydrocarbons, HCx, in the gas product was observed. The Aluminum foil was easily separated from the solid product. The rest part of char was characterized by proximate and elemental analysis and calorimetric measurements. The total organic carbon in the tar product was estimated by elemental analysis of tars. Two types of catalysts (dolomite and red clay marked AFRC) were used for catalytic thermal tar decomposition. Three series of experiments (without catalyst in a secondary cracking reactor, with dolomite and with AFRC) at temperatures of 650, 700, 750, 800 and 850 °C were carried out. Both types of catalysts have significantly affected the content of tars and other components in pyrolytic gases. The effect of catalyst on the tetrapack distribution into the product yield on the composition of gas and on the total organic carbon in the tar product is presented in this work. Copyright © 2013 Elsevier Ltd. All rights reserved.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Haydary, J., E-mail: juma.haydary@stuba.sk; Susa, D.; Dudáš, J.

Highlights: ► Pyrolysis of aseptic packages was carried out in a laboratory flow reactor. ► Distribution of tetrapak into the product yields was obtained. ► Composition of the pyrolysis products was estimated. ► Secondary thermal and catalytic decomposition of tars was studied. ► Two types of catalysts (dolomite and red clay marked AFRC) were used. - Abstract: Pyrolysis of aseptic packages (tetrapak cartons) in a laboratory apparatus using a flow screw type reactor and a secondary catalytic reactor for tar cracking was studied. The pyrolysis experiments were realized at temperatures ranging from 650 °C to 850 °C aimed at maximizingmore » of the amount of the gas product and reducing its tar content. Distribution of tetrapak into the product yields at different conditions was obtained. The presence of H{sub 2}, CO, CH{sub 4}, CO{sub 2} and light hydrocarbons, HCx, in the gas product was observed. The Aluminum foil was easily separated from the solid product. The rest part of char was characterized by proximate and elemental analysis and calorimetric measurements. The total organic carbon in the tar product was estimated by elemental analysis of tars. Two types of catalysts (dolomite and red clay marked AFRC) were used for catalytic thermal tar decomposition. Three series of experiments (without catalyst in a secondary cracking reactor, with dolomite and with AFRC) at temperatures of 650, 700, 750, 800 and 850 °C were carried out. Both types of catalysts have significantly affected the content of tars and other components in pyrolytic gases. The effect of catalyst on the tetrapack distribution into the product yield on the composition of gas and on the total organic carbon in the tar product is presented in this work.« less

Multifunctional two-stage riser fluid catalytic cracking process.

PubMed

Zhang, Jinhong; Shan, Honghong; Chen, Xiaobo; Li, Chunyi; Yang, Chaohe

This paper described the discovering process of some shortcomings of the conventional fluid catalytic cracking (FCC) process and the proposed two-stage riser (TSR) FCC process for decreasing dry gas and coke yields and increasing light oil yield, which has been successfully applied in 12 industrial units. Furthermore, the multifunctional two-stage riser (MFT) FCC process proposed on the basis of the TSR FCC process was described, which were carried out by the optimization of reaction conditions for fresh feedstock and cycle oil catalytic cracking, respectively, by the coupling of cycle oil cracking and light FCC naphtha upgrading processes in the second-stage riser, and the specially designed reactor for further reducing the olefin content of gasoline. The pilot test showed that it can further improve the product quality, increase the diesel yield, and enhance the conversion of heavy oil.

Normal compression wave scattering by a permeable crack in a fluid-saturated poroelastic solid

NASA Astrophysics Data System (ADS)

Song, Yongjia; Hu, Hengshan; Rudnicki, John W.

2017-04-01

A mathematical formulation is presented for the dynamic stress intensity factor (mode I) of a finite permeable crack subjected to a time-harmonic propagating longitudinal wave in an infinite poroelastic solid. In particular, the effect of the wave-induced fluid flow due to the presence of a liquid-saturated crack on the dynamic stress intensity factor is analyzed. Fourier sine and cosine integral transforms in conjunction with Helmholtz potential theory are used to formulate the mixed boundary-value problem as dual integral equations in the frequency domain. The dual integral equations are reduced to a Fredholm integral equation of the second kind. It is found that the stress intensity factor monotonically decreases with increasing frequency, decreasing the fastest when the crack width and the slow wave wavelength are of the same order. The characteristic frequency at which the stress intensity factor decays the fastest shifts to higher frequency values when the crack width decreases.

Permeability and elastic properties of cracked glass under pressure

NASA Astrophysics Data System (ADS)

Ougier-Simonin, A.; GuéGuen, Y.; Fortin, J.; Schubnel, A.; Bouyer, F.

2011-07-01

Fluid flow in rocks is allowed through networks of cracks and fractures at all scales. In fact, cracks are of high importance in various applications ranging from rock elastic and transport properties to nuclear waste disposal. The present work aims at investigating thermomechanical cracking effects on elastic wave velocities, mechanical strength, and permeability of cracked glass under pressure. We performed the experiments on a triaxial cell at room temperature which allows for independent controls of the confining pressure, the axial stress, and pore pressure. We produced cracks in original borosilicate glass samples with a reproducible method (thermal treatment with a thermal shock of 300°C). The evolution of the elastic and transport properties have been monitored using elastic wave velocity sensors, strain gage, and flow measurements. The results obtained evidence for (1) a crack family with identified average aspect ratio and crack aperture, (2) a very small permeability which decreases as a power (exponential) function of pressure, and depends on (3) the crack aperture cube. We also show that permeability behavior of a cracked elastic brittle solid is reversible and independent of the fluid nature. Two independent methods (permeability and elastic wave velocity measurements) give these consistent results. This study provides data on the mechanical and transport properties of an almost ideal elastic brittle solid in which a crack population has been introduced. Comparisons with similar data on rocks allow for drawing interesting conclusions. Over the timescale of our experiments, our results do not provide any data on stress corrosion, which should be considered in further study.

Commercialization of the Chevron FCC vanadium trap

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kennedy, J.V.; Kuehler, C.W.; Krishna, A.S.

1995-09-01

Vanadium, present to varying degrees in FCC feed, deposits on the catalyst virtually quantitatively in the cracking process. In resid operations, vanadium levels on catalyst can reach 10,000 ppm at typical catalyst make-up rates. Once on the catalyst, vanadium destroys the zeolite and restricts access to active sites. This reduces catalyst activity. A vanadium trap is a material that when introduced into the catalyst inventory selectively reacts with migrating vanadium, thus protecting the zeolite and other active components of the catalyst. The trap may be incorporated into the catalyst, or introduced as a separate particle. Only a limited amount ofmore » trap can be incorporated into the catalyst without limiting the amount of zeolite that can be included. Gulf began development of a vanadium trap during the early 1980`s. The work produced a variety of promising materials whose use as vanadium traps was subsequently patented. The work ultimately led to a formulation with a phase very active for trapping vanadium while still quite sulfur tolerant. Based on these results, an extensive pilot plant evaluation was undertaken by Chevron after the Chevron-Gulf merger to better simulate commercial operation. The paper describes pilot plant tests as well as 3 commercial tests of this vanadium trap.« less

A time step criterion for the stable numerical simulation of hydraulic fracturing

NASA Astrophysics Data System (ADS)

Juan-Lien Ramirez, Alina; Löhnert, Stefan; Neuweiler, Insa

2017-04-01

The process of propagating or widening cracks in rock formations by means of fluid flow, known as hydraulic fracturing, has been gaining attention in the last couple of decades. There is growing interest in its numerical simulation to make predictions. Due to the complexity of the processes taking place, e.g. solid deformation, fluid flow in an open channel, fluid flow in a porous medium and crack propagation, this is a challenging task. Hydraulic fracturing has been numerically simulated for some years now [1] and new methods to take more of its processes into account (increasing accuracy) while modeling in an efficient way (lower computational effort) have been developed in recent years. An example is the use of the Extended Finite Element Method (XFEM), whose application originated within the framework of solid mechanics, but is now seen as an effective method for the simulation of discontinuities with no need for re-meshing [2]. While more focus has been put to the correct coupling of the processes mentioned above, less attention has been paid to the stability of the model. When using a quasi-static approach for the simulation of hydraulic fracturing, choosing an adequate time step is not trivial. This is in particular true if the equations are solved in a staggered way. The difficulty lies within the inconsistency between the static behavior of the solid and the dynamic behavior of the fluid. It has been shown that too small time steps may lead to instabilities early into the simulation time [3]. While the solid reaches a stationary state instantly, the fluid is not able to achieve equilibrium with its new surrounding immediately. This is why a time step criterion has been developed to quantify the instability of the model concerning the time step. The presented results were created with a 2D poroelastic model, using the XFEM for both the solid and the fluid phases. An embedded crack propagates following the energy release rate criteria when the fluid pressure within the crack rises. The fluid flow within the crack and in the porous medium are simulated using the mass balance for water and Darcy's law for flow. The equations for flow and deformation in the rock and that for flow in the fracture are solved in a staggered manner. The two sets of equations are coupled via Lagrange multipliers. We present a time step criterion for the stability of the scheme and illustrate this criterion with test examples of crack propagation. [1] T. Boone and A. Ingraffea. A numerical procedure for simulation of hydraulically-driven fracture propagation in poroelastic media. Int. J. Numer. Anal. Met. 14, 27-47, (1990) [2] T. Mohammadnejad and A. Khoei. An extended finite element method for hydraulic fracture propagation in deformable porous media with the cohesive crack model. Finite Elements in Analysis and Design. 73, 77-95, (2013) [3] E.W. Remij, J.J.C. Remmers, J.M. Huyghe, D.M.J. Smeulders. The enhanced local pressure model for the accurate analysis of fluid pressure driven fracture in porous materials. Comput. Methods Appl. Mech. Engrg. 286, 293-312, (2015)

Long-period events, the most characteristic seismicity accompanying the emplacement and extrusion of a lava dome in Galeras Volcano, Colombia, in 1991

USGS Publications Warehouse

Gil, Cruz F.; Chouet, B.A.

1997-01-01

Since its reactivation in 1988 the principal eruptions of Galeras Volcano occurred on May 4-9, 1989, July 16, 1992, and January 14, March 23, April 3, April 14 and June 7, 1993. The initial eruption was a phreatic event which clearly marked a new period of activity. A lava dome was extruded within the main crater in October 1991 and subsequently destroyed in an explosive eruption on July 16, 1992. The eruptions that followed were all vulcanian-type explosions. The seismicity accompanying the emplacement, extrusion, and destruction of the lava dome was dominated by a mix of long-period (LP) events and tremor displaying a variety of waveforms. Repetitive LP events with dominant periods in the range 0.2-1 s were observed in October and November 1991 and visually correlated with short energetic pulses of gas venting through a crack bisecting the dome surface. Each LP event was characterized by a weak precursory signal with dominant periods in the range 0.05-0.1 s lasting roughly 7 s. Using the fluid-driven crack model of Chouet (1988, 1992), we infer that two distinct cracks may have acted as sources for the LP and precursor signals. Spectral analyses of the data yield the following parameters for the LP source: crack length, 240-360 m; crack width, 130-150 m; crack aperture, 0.5-3.4 mm; crack stiffness, 100-500; sound speed of fluid, 880 m/s; and excess pressure, 0.01-0.19 MPa. Similar analyses yield the parameters of the precursor source: crack length, 20-30 m; crack width, 15-25 m; crack aperture, 2.3-8.7 mm; crack stiffness, 5-15; sound speed of fluid, 140 m/s; and excess pressure, 0.06-0.15 MPa. Combined with geologic and thermodynamic constraints obtained from field observations, these seismic parameters suggest a gas-release mechanism in which the episodic collapse of a foam layer trapped at the top of the magma column subjacent to the dome releases a slug of pressurized gas which escapes to the surface while dilating a preexisting system of cracks in the dome structure. Accordingly, the fracture observed on the crystallized dome body is the surface extension of the LP-source crack, where LP activity is induced by the rapid emission and expansion of gas flowing through this conduit. The width and aperture of the crack estimated in the model are in good agreement with the length and aperture of the fracture estimated from visual observations. The source parameters of the precursor signal are suggestive of a nozzle-like conduit connecting the LP-source crack to the underlying magma reservoir. Excitation of this conduit segment is attributed to the rapid emission and acceleration of the frothy fluid resulting from the collapse of the foam layer at the top of the reservoir. The calculated periodicity of foam collapse events is in agreement with the observed average rate of thirteen LP events per hour.

Microscale X-ray tomographic investigation of the interfacial morphology between the catalyst and micro porous layers in proton exchange membrane fuel cells

NASA Astrophysics Data System (ADS)

Prass, Sebastian; Hasanpour, Sadegh; Sow, Pradeep Kumar; Phillion, André B.; Mérida, Walter

2016-07-01

The interfacial morphology between the catalyst layer (CL) and micro porous layer (MPL) influences the performance of proton exchange membrane fuel cells (PEMFCs). Here we report a direct method to investigate the CL-MPL interfacial morphology of stacked and compressed gas diffusion layer (GDL with MPL)-catalyst coated membrane (CCM) assemblies. The area, origin and dimensions of interfacial gaps are studied with high-resolution X-ray micro computed tomography (X-μCT). The projected gap area (fraction of the CL-MPL interface separated by gaps) is higher for GDL-CCM assemblies with large differences in the surface roughness between CL and MPL but reduces with increasing compression and similarity in roughness. Relatively large continuous gaps are found in proximity to cracks in the MPL. These are hypothesized to form due to the presence of large pores on the surface of the GDL. Smaller gaps are induced by the surface roughness features throughout the CL-MPL interface. By modification of the pore sizes on the GDL surface serving as substrate for the MPL, the number and dimension of MPL crack induced gaps can be manipulated. Moreover, adjusting the CL and MPL surface roughness parameters to achieve similar orders of roughness can improve the surface mating characteristics of these two components.

Fluid-driven cracks in an elastic matrix in the toughness-dominated limit

PubMed Central

Lai, Ching-Yao; Zheng, Zhong; Dressaire, Emilie

2016-01-01

The dynamics of fluid-driven cracks in an elastic matrix is studied experimentally. We report the crack radius R(t) as a function of time, as well as the crack shapes w(r,t) as a function of space and time. A dimensionless parameter, the pressure ratio Δpf/Δpv, is identified to gauge the relative importance between the toughness (Δpf) and viscous (Δpv) effects. In our previous paper (Lai et al. 2015 Proc. R. Soc. A 471, 20150255. (doi:10.1098/rspa.2015.0255)), we investigated the viscous limit experimentally when the toughness-related stresses are negligible for the crack propagation. In this paper, the experimental parameters, i.e. Young’s modulus E of the gelatin, viscosity μ of the fracturing liquid and the injection flow rate Q, were chosen so that the viscous effects in the flow are negligible compared with the toughness effects, i.e. Δpf/Δpv≫1. In this limit, the crack dynamics can be described by the toughness-dominated scaling laws, which give the crack radius R(t)∝t2/5 and the half maximum crack thickness W(t)∝t1/5. The experimental results are in good agreement with the predictions of the toughness scaling laws: the experimental data for crack radius R(t) for a wide range of parameters (E,μ,Q) collapse after being rescaled by the toughness scaling laws, and the rescaled crack shapes w(r,t) also collapse to a dimensionless shape, which demonstrates the self-similarity of the crack shape. The appropriate choice of the viscous or toughness scaling laws is important to accurately describe the crack dynamics. This article is part of the themed issue ‘Energy and the subsurface’. PMID:27597782

Combustion characteristics of crude jatropha oil droplets using rhodium liquid as a homogeneous combustion catalyst

NASA Astrophysics Data System (ADS)

Nanlohy, Hendry Y.; Wardana, I. N. G.; Hamidi, N.; Yuliati, L.

2018-01-01

Combustion characteristics of crude jatropha oil droplet at room temperature with and without catalyst have been studied experimentally. Its combustion characteristics have been observed by igniting the oil droplet on a junction of a thermocouple, and the combustion characteristics of oil droplets are observed using a high-speed camera. The results show that the uniqueness of crude jatropha oil as alternative fuel is evidenced by the different stages of combustion caused by thermal cracking in burning droplets. The results also show that the role of the catalyst is not only an accelerator agent, but there are other unique functions and roles as a stabilizer. Moreover, the results also found that the catalyst was able to shorten the ignition timing and burnout time. This phenomenon proves that the presence of catalysts alters and weakens the structure of the triglyceride geometry so that the viscosity and flash point is reduced, the fuel absorbs heat well and flammable.

Attrition resistant fluidizable reforming catalyst

DOEpatents

Parent, Yves O [Golden, CO; Magrini, Kim [Golden, CO; Landin, Steven M [Conifer, CO; Ritland, Marcus A [Palm Beach Shores, FL

2011-03-29

A method of preparing a steam reforming catalyst characterized by improved resistance to attrition loss when used for cracking, reforming, water gas shift and gasification reactions on feedstock in a fluidized bed reactor, comprising: fabricating the ceramic support particle, coating a ceramic support by adding an aqueous solution of a precursor salt of a metal selected from the group consisting of Ni, Pt, Pd, Ru, Rh, Cr, Co, Mn, Mg, K, La and Fe and mixtures thereof to the ceramic support and calcining the coated ceramic in air to convert the metal salts to metal oxides.

Comparision of real waste (MSW and MPW) pyrolysis in batch reactor over different catalysts. Part I: product yields, gas and pyrolysis oil properties.

PubMed

Ateş, Funda; Miskolczi, Norbert; Borsodi, Nikolett

2013-04-01

Pyrolysis of municipal solid waste (MSW) and municipal plastic waste (MPW) have been investigated in batch reactor at 500, 550 and 600°C both in absence and presence of catalysts (Y-zeolite, β-zeolite, equilibrium FCC, MoO3, Ni-Mo-catalyst, HZSM-5 and Al(OH)3). The effect of the parameters on the product properties was investigated. Products were characterized using gas-chromatography, GC/MS, (13)C NMR. Yields of volatile fractions increased, while reaction time necessity for the total cracking decreased in the presence of catalysts. Catalysts have productivity and selectivity in converting aliphatic hydrocarbons to aromatic and cyclic compounds in oil products. Gases from MSW consisted of hydrogen CO, CO2, while exclusively hydrogen and hydrocarbons were detected from MPW. Catalyst efficiency was higher using MPW than MSW. Pyrolysis oils contained aliphatic hydrocarbons, aromatics, cyclic compounds and less ketones, alcohols, acids or esters depending on the raw materials. Copyright © 2013 Elsevier Ltd. All rights reserved.

Nanoparticulate-catalyzed oxygen transfer processes

DOEpatents

Hunt, Andrew T [Atlanta, GA; Breitkopf, Richard C [Dunwoody, GA

2009-12-01

Nanoparticulates of oxygen transfer materials that are oxides of rare earth metals, combinations of rare earth metals, and combinations of transition metals and rare earth metals are used as catalysts in a variety of processes. Unexpectedly large thermal efficiencies are achieved relative to micron sized particulates. Processes that use these catalysts are exemplified in a multistage reactor. The exemplified reactor cracks C6 to C20 hydrocarbons, desulfurizes the hydrocarbon stream and reforms the hydrocarbons in the stream to produce hydrogen. In a first reactor stage the steam and hydrocarbon are passed through particulate mixed rare earth metal oxide to crack larger hydrocarbon molecules. In a second stage, the steam and hydrocarbon are passed through particulate material that desulfurizes the hydrocarbon. In a third stage, the hydrocarbon and steam are passed through a heated, mixed transition metal/rare earth metal oxide to reform the lower hydrocarbons and thereby produce hydrogen. Stages can be alone or combined. Parallel reactors can provide continuous reactant flow. Each of the processes can be carried out individually.

A probabilistic method for determining the volume fraction of pre-embedded capsules in self-healing materials

NASA Astrophysics Data System (ADS)

Lv, Zhong; Chen, Huisu

2014-10-01

Autonomous healing of cracks using pre-embedded capsules containing healing agent is becoming a promising approach to restore the strength of damaged structures. In addition to the material properties, the size and volume fraction of capsules influence crack healing in the matrix. Understanding the crack and capsule interaction is critical in the development and design of structures made of self-healing materials. Assuming that the pre-embedded capsules are randomly dispersed we theoretically model flat ellipsoidal crack interaction with capsules and determine the probability of a crack intersecting the pre-embedded capsules i.e. the self-healing probability. We also develop a probabilistic model of a crack simultaneously meeting with capsules and catalyst carriers in two-component self-healing system matrix. Using a risk-based healing approach, we determine the volume fraction and size of the pre-embedded capsules that are required to achieve a certain self-healing probability. To understand the effect of the shape of the capsules on self-healing we theoretically modeled crack interaction with spherical and cylindrical capsules. We compared the results of our theoretical model with Monte-Carlo simulations of crack interaction with capsules. The formulae presented in this paper will provide guidelines for engineers working with self-healing structures in material selection and sustenance.

Elastic anisotropy due to aligned cracks in porous rock

DOE Office of Scientific and Technical Information (OSTI.GOV)

Thomsen, L.

1995-08-01

All theoretical expression which relate the characteristics of saturated aligned cracks to the associated elastic anisotropy are restricted in some important way, for example to the case of stiff pore fluids, or of the absence of equate porosity, or of a moderately high frequency band. Because of these restrictions, previous theory is not suitable for application to the upper crust, where the pore fluid is brine (K{sub f}{approx}K{sub s}/20), the equant porosity is often substantial ({phi}{sub p}>0.1), and the frequency band is sonic to seismic. This work removes these particular restrictions, recognizing in the process an important mechanism of dispersion.more » A notable feature of these more general expressions is their insensitivity, at low frequency, to the aspect ratio of the cracks; only the crack density is critical. An important conclusion of this more general model is that many insights previously achieved, concerning the shear-wave splitting due to vertical aligned saturated cracks, are sustained. However, conclusions on crack orientation or crack aspect ratio, which were derived from P-wave data or from shear-wave `critical angles`, may need to be reconsidered. Further, the non-linear coupling between pores and cracks, due to pressure equalization effects, means that the (linear) Schoenberg-Muir calculus may not be applied to such systems. The theory received strong support from recent data by Rathore et al. on artificial samples with controlled crack geometry.« less

Method for the photocatalytic conversion of methane

DOEpatents

Noceti, R.P.; Taylor, C.E.; D`Este, J.R.

1998-02-24

A method for converting methane to methanol is provided comprising subjecting the methane to visible light in the presence of a catalyst and an electron transfer agent. Another embodiment of the invention provides for a method for reacting methane and water to produce methanol and hydrogen comprising preparing a fluid containing methane, an electron transfer agent and a photolysis catalyst, and subjecting said fluid to visible light for an effective period of time. 3 figs.

Method for the photocatalytic conversion of methane

DOEpatents

Noceti, Richard P.; Taylor, Charles E.; D'Este, Joseph R.

1998-01-01

A method for converting methane to methanol is provided comprising subjecting the methane to visible light in the presence of a catalyst and an electron transfer agent. Another embodiment of the invention provides for a method for reacting methane and water to produce methanol and hydrogen comprising preparing a fluid containing methane, an electron transfer agent and a photolysis catalyst, and subjecting said fluid to visible light for an effective period of time.

Co-cracking of real MSW into bio-oil over natural kaolin

NASA Astrophysics Data System (ADS)

Gandidi, I. M.; Susila, M. D.; Pambudi, N. A.

2017-03-01

Municipal solid waste (MSW) is a potential material that can be converted into bio-oil through thermal degradation process or pyrolysis. The efficiency and productivity of pyrolysis can be increased with the use of natural catalyst like kaolin. The addition of catalyst also reduces the overall cost of conversion process. In this study conversion of MSW into Bio Fuel using Pyrolysis in the presence of of natural kaolin as catalyst has been investigated for 60 min at 400°C temperature. During the process 0.5 w/w catalyst to MSW ratio was maintained. Gas chromatography-mass spectrometry (GC-MS) was used to analyse the chemical composition of bio fuel. It is found that bio-oil production increases substantially with the use of catalyst. It is observed that the production of bio-oil is 23.6 % with the use of catalyst in process, which was only 15.2 % without the use of catalyst. The hydrocarbon range distribution of oil produced through pyrolysis reveals that gasoline and diesel fuel (C5-C20) are its main constituents. The functional group detected in bio-oil by GC-MS analysis is similar to that of diesel-48 in which paraffin and olefin are major mass species.

Biphasic catalysis in water/carbon dioxide micellar systems

DOEpatents

Jacobson, Gunilla B.; Tumas, William; Johnston, Keith P.

2002-01-01

A process is provided for catalyzing an organic reaction to form a reaction product by placing reactants and a catalyst for the organic reaction, the catalyst of a metal complex and at least one ligand soluble within one of the phases of said aqueous biphasic system, within an aqueous biphasic system including a water phase, a dense phase fluid, and a surfactant adapted for forming an emulsion or microemulsion within the aqueous biphasic system, the reactants soluble within one of the phases of the aqueous biphasic system and convertible in the presence of the catalyst to a product having low solubility in the phase in which the catalyst is soluble; and, maintaining the aqueous biphasic system under pressures, at temperatures, and for a period of time sufficient for the organic reaction to occur and form the reaction product and to maintain sufficient density on the dense phase fluid, the reaction product characterized as having low solubility in the phase in which the catalyst is soluble.

Autothermal and partial oxidation reformer-based fuel processor, method for improving catalyst function in autothermal and partial oxidation reformer-based processors

DOEpatents

Ahmed, Shabbir; Papadias, Dionissios D.; Lee, Sheldon H. D.; Ahluwalia, Rajesh K.

2013-01-08

The invention provides a fuel processor comprising a linear flow structure having an upstream portion and a downstream portion; a first catalyst supported at the upstream portion; and a second catalyst supported at the downstream portion, wherein the first catalyst is in fluid communication with the second catalyst. Also provided is a method for reforming fuel, the method comprising contacting the fuel to an oxidation catalyst so as to partially oxidize the fuel and generate heat; warming incoming fuel with the heat while simultaneously warming a reforming catalyst with the heat; and reacting the partially oxidized fuel with steam using the reforming catalyst.

The fracture criticality of crustal rocks

NASA Astrophysics Data System (ADS)

Crampin, Stuart

1994-08-01

The shear-wave splitting observed along almost all shear-wave ray paths in the Earth's crust is interpreted as the effects of stress-aligned fluid-filled cracks, microcracks, and preferentially oriented pore space. Once away from the free surface, where open joints and fractures may lead to strong anisotropy of 10 per cent or greater, intact ostensibly unfractured crustal rock exhibits a limited range of shear-wave splitting from about 1.5 to 4.5 per cent differential shear-wave velocity anisotropy. Interpreting this velocity anisotropy as normalized crack densities, a factor of less than two in crack radius covers the range from the minimum 1.5 per cent anisotropy observed in intact rock to the 10 per cent observed in heavily cracked almost disaggregated near-surface rocks. This narrow range of crack dimensions and the pronounced effect on rock cohesion suggests that there is a state of fracture criticality at some level of anisotropy between 4.5 and 10 per cent marking the boundary between essentially intact, and heavily fractured rock. When the level of fracture criticality is exceeded, cracking is so severe that there is a breakdown in shear strength, the likelihood of progressive fracturing and the dispersal of pore fluids through enhanced permeability. The range of normalized crack dimensions below fracture criticality is so small in intact rock, that any modification to the crack geometry by even minor changes of conditions or minor deformation (particularly in the presence of high pore-fluid pressures) may change rock from being essentially intact (below fracture criticality) to heavily fractured (above fracture criticality). This recognition of the essential compliance of most crustal rocks, and its effect on shear-wave splitting, has implications for monitoring changes in any conditions affecting the rock mass. These include monitoring changes in reservoir evolution during hydrocarbon production and enhanced oil recovery, and in monitoring changes before and after earthquakes, amongst others.

Reactivation of a Propped Hydraulic Fracture

NASA Astrophysics Data System (ADS)

Sarvaramini, E.; Garagash, D.

2014-12-01

The problem of massive fluid injection into a pre-existing fracture has many applications in petroleum industry including underground liquid waste disposal and waterflooding to increase recovery from a hydrocarbon reservoir. Understanding the conditions leading to the re-activation of pre-existing fractures and ensuing propagation is critical for a successful injection project design, and it may also help to mitigate potential environmental hazards, such as contamination of underground aquifers and induced seismicity. The problem of injection of a low viscosity fluid into a permeable formation can be distinguished from conventional hydraulic fracture by the mechanism of fluid leak-off. In conventional fracturing, high viscosity and cake building properties of injected fluid limit leak-off to a 1-D boundary layer incasing the crack. In the case of injection of low viscosity fluid into a fracture, leak-off and related pore fluid diffusion will take place over wider range of scales, from 1-D to 2 or 3-D. We consider a pre-existing stationary propped hydraulic fracture with constrained height into which a fluid is injected under constant flow rate. Although the net effective stress on the crack is initially compressive, the proppant keeps the crack open. It is worthwhile to note that during injection and related pressurization of a propped crack, the fracture breakdown is to be achieved prior to the fracture re-opening. Therefore, the effect of the change of the propped fracture storage on the pressurization dynamics can be neglected. The objective of this work is to study the transient pressurization and the onset of the propagation for a propped fracture. To the end, we formulate and solve a general problem of injection into a fracture accounting for viscous dissipation (i.e. non-uniform pressure distribution). We quantify how the fracture breakdown condition depends upon the rock and fluid properties, the in-situ stress and the fluid injection rate. We also establish a criterion when the assumption of negligible viscous dissipation is justified. The obtained solution is also transportable to the production well test analysis of a fractured well (Cinco et al., SPE 1978).

Method and apparatus for a catalytic firebox reactor

DOEpatents

Smith, Lance L.; Etemad, Shahrokh; Ulkarim, Hasan; Castaldi, Marco J.; Pfefferle, William C.

2001-01-01

A catalytic firebox reactor employing an exothermic catalytic reaction channel and multiple cooling conduits for creating a partially reacted fuel/oxidant mixture. An oxidation catalyst is deposited on the walls forming the boundary between the multiple cooling conduits and the exothermic catalytic reaction channel, on the side of the walls facing the exothermic catalytic reaction channel. This configuration allows the oxidation catalyst to be backside cooled by any fluid passing through the cooling conduits. The heat of reaction is added to both the fluid in the exothermic catalytic reaction channel and the fluid passing through the cooling conduits. After discharge of the fluids from the exothermic catalytic reaction channel, the fluids mix to create a single combined flow. A further innovation in the reactor incorporates geometric changes in the exothermic catalytic reaction channel to provide streamwise variation of the velocity of the fluids in the reactor.

Subcritical growth of natural hydraulic fractures

NASA Astrophysics Data System (ADS)

Garagash, D.

2014-12-01

Joints are the most common example of brittle tensile failure in the crust. Their genesis at depth is linked to the natural hydraulic fracturing, which requires pore fluid pressure in excess of the minimum in situ stress [Pollard and Aidyn, JSG1988]. Depending on the geological setting, high pore pressure can result form burial compaction of interbedded strata, diagenesis, or tectonics. Common to these loading scenarios is slow build-up of pore pressure over a geological timescale, until conditions for initiation of crack growth are met on favorably oriented/sized flaws. The flaws can vary in size from grain-size cracks in igneous rocks to a fossil-size flaws in clastic rock, and once activated, are inferred to propagate mostly subcritically [Segall JGR 1984; Olson JGR 1993]. Despite many observational studies of natural hydraulic fractures, the modeling attempts appear to be few [Renshaw and Harvey JGR 1994]. Here, we use boundary integral formulation for the pore fluid inflow from the permeable rock into a propagating joint [Berchenko et al. IJRMMS 1997] coupled with the criteria for subcritical propagation assisted by the environmental effects of pore fluid at the crack tip to solve for the evolution of a penny-shape joint, which, in interbedded rock, may eventually evolve to short-blade geometry (propagation confined to a bed). Initial growth is exceedingly slow, paced by the stress corrosion reaction kinetics at the crack tip. During this stage the crack is fully-drained (i.e. the fluid pressure in the crack is equilibrated with the ambient pore pressure). This "slow" stage is followed by a rapid acceleration, driven by the increase of the mechanical stress intensity factor with the crack length, towards the terminal joint velocity. We provide an analytical expression for the latter as a function of the rock diffusivity, net pressure loading at the initiation (or flaw lengthscale), and parameters describing resistance to fracture growth. Due to a much slower rate of the crack volume expansion of short-blade joints compared to that of penny-shape joints, the former would propagate much faster than the latter under otherwise identical conditions. Finally, we speculate about possible relation of the predicted patterns of joint development with morphology of joint fracture surfaces observed in sedimentary rock.

Hybrid Mo-CT nanowires as highly efficient catalysts for direct dehydrogenation of isobutane.

PubMed

Mu, Jiali; Shi, Junjun; France, Liam John; Wu, Yongshan; Zeng, Qiang; Liu, Baoan; Jiang, Lilong; Long, Jinxing; Li, Xuehui

2018-06-20

Direct dehydrogenation of isobutane to isobutene has drawn extensive attention for synthesizing various chemicals. The Mo-based catalysts hold promise as an alternative to the toxic CrOx- and scarce Pt-based catalysts. However, the low activity and rapid deactivation of the Mo-based catalysts greatly hinder their practical applications. Herein, we demonstrate a feasible approach towards the development of efficient and non-noble metal dehydrogenation catalysts basing on Mo-CT hybrid nanowires calcined at different temperatures. In particular, the optimal Mo-C700 catalyst exhibits isobutane consumption rate of 3.9 mmol g-1 h-1, and isobutene selectivity of 73% with production rate of 2.8 mmol g-1 h-1. The catalyst maintained 90% of its initial activity after 50 h of reaction. Extensive characterizations reveal that such prominent performance is well-correlated with the adsorption abilities of isobutane and isobutene, and the formation of η-MoC species. By contrast, the generation of β-Mo2C crystalline phase during long-term reaction causes minor decline in activity. Compared to MoO2 and β-Mo2C, η-MoC plays a role more likely in suppressing the cracking reaction. This work demonstrates a feasible approach towards the development of efficient and non-noble metal dehydrogenation catalysts.

Evaluation of biochars by temperature programmed oxidation/mass spectrometry

Treesearch

Michael Jackson; Thomas Eberhardt; Akwasi Boateng; Charles Mullen; Les Groom

2013-01-01

Biochars produced from thermochemical conversions of biomass were evaluated by temperature programmed oxidation (TPO). This technique, used to characterize carbon deposits on petroleum cracking catalysts, provides information on the oxidative stability of carbonaceous solids, where higher temperature reactivity indicates greater structural order, an important property...

Liquid phase fluid dynamic (methanol) run in the LaPorte alternative fuels development unit

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bharat L. Bhatt

1997-05-01

A fluid dynamic study was successfully completed in a bubble column at DOE's Alternative Fuels Development Unit (AFDU) in LaPorte, Texas. Significant fluid dynamic information was gathered at pilot scale during three weeks of Liquid Phase Methanol (LPMEOJP) operations in June 1995. In addition to the usual nuclear density and temperature measurements, unique differential pressure data were collected using Sandia's high-speed data acquisition system to gain insight on flow regime characteristics and bubble size distribution. Statistical analysis of the fluctuations in the pressure data suggests that the column was being operated in the churn turbulent regime at most of themore » velocities considered. Dynamic gas disengagement experiments showed a different behavior than seen in low-pressure, cold-flow work. Operation with a superficial gas velocity of 1.2 ft/sec was achieved during this run, with stable fluid dynamics and catalyst performance. Improvements included for catalyst activation in the design of the Clean Coal III LPMEOH{trademark} plant at Kingsport, Tennessee, were also confirmed. In addition, an alternate catalyst was demonstrated for LPMEOH{trademark}.« less

Features of CO2 fracturing deduced from acoustic emission and microscopy in laboratory experiments

NASA Astrophysics Data System (ADS)

Ishida, Tsuyoshi; Chen, Youqing; Bennour, Ziad; Yamashita, Hiroto; Inui, Shuhei; Nagaya, Yuya; Naoi, Makoto; Chen, Qu; Nakayama, Yoshiki; Nagano, Yu

2016-11-01

We conducted hydraulic fracturing (HF) experiments on 170 mm cubic granite specimens with a 20 mm diameter central hole to investigate how fluid viscosity affects HF process and crack properties. In experiments using supercritical carbon dioxide (SC-CO2), liquid carbon dioxide (L-CO2), water, and viscous oil with viscosity of 0.051-336.6 mPa · s, we compared the results for breakdown pressure, the distribution and fracturing mechanism of acoustic emission, and the microstructure of induced cracks revealed by using an acrylic resin containing a fluorescent compound. Fracturing with low-viscosity fluid induced three-dimensionally sinuous cracks with many secondary branches, which seem to be desirable pathways for enhanced geothermal system, shale gas recovery, and other processes.

Time-Resolved and Operando XAS Studies on Heterogeneous Catalysts - From the Gas Phase Towards Reactions in Supercritical Fluids

DOE Office of Scientific and Technical Information (OSTI.GOV)

Grunwaldt, Jan-Dierk; Baiker, Alfons

2007-02-02

x-ray absorption spectroscopy is a well-suited technique to uncover the structure of heterogeneous catalysts under reaction conditions. Different aspects of in situ cell design suitable for dynamic and catalytic studies are discussed. In addition, criteria are presented that allow estimating the influence external and internal mass transfer. Starting with studies on gas-solid reactions, including structure-activity relationships, this concept is extended to liquid-solid reactions, reactions at high pressure and in supercritical fluids. The following examples are discussed in more detail: partial oxidation of methane over Pt-Rh/Al2O3, reduction of a Cu/ZnO catalyst, alcohol oxidation over Bi-promoted Pd/Al2O3 in liquid phase and overmore » Pd/Al2O3 in supercritical CO2, and batch reactions (e.g. CO2-fixation over zinc-based catalysts)« less

A mesostructured Y zeolite as a superior FCC catalyst--lab to refinery.

PubMed

García-Martínez, Javier; Li, Kunhao; Krishnaiah, Gautham

2012-12-18

A mesostructured Y zeolite was prepared by a surfactant-templated process at the commercial scale and tested in a refinery, showing superior hydrothermal stability and catalytic cracking selectivity, which demonstrates, for the first time, the promising future of mesoporous zeolites in large scale industrial applications.

Effective properties of a poroelastic medium containing a distribution of aligned cracks

NASA Astrophysics Data System (ADS)

Galvin, R. J.; Gurevich, B.

2009-07-01

We simulate the effect of fractures by considering them to be thin circular cracks in a poroelastic background. Using the solution of the scattering problem for a single-crack and multiple-scattering theory, we estimate the attenuation and dispersion of elastic waves in a porous medium containing a sparse distribution of cracks. When comparing with a similar model, in which multiple-scattering effects are neglected, we find that there is agreement at high frequencies and discrepancies at low frequencies. We conclude that the interaction between cracks should not be neglected at low frequencies, even in the limit of weak crack density. Since the models only agree with each other at high frequencies, when the time available for fluid diffusion is small, we conclude that the interaction between cracks, which is a result of fluid diffusion, is negligible at high frequencies. We also compare our results with a model for spherical inclusions and find that the attenuation for spherical inclusions has exactly the same dependence upon frequency but a difference in magnitude, which depends upon frequency. Since the attenuation curves are very close at low frequencies, we conclude that the effective medium properties are not sensitive to the shape of an inclusion at wavelengths that are large compared with the inclusion size. However, at frequencies such that the wavelength is comparable to or smaller than the inclusion size, the effective properties are sensitive to the greater compliance of the flat cracks, and more attenuation occurs at a given frequency as a result.

Experimental measurements of seismic attenuation in microfracture sedimentary rock

DOE Office of Scientific and Technical Information (OSTI.GOV)

Peacock, S.; McCann, C.; Sothcott, J.

1994-09-01

In a previous paper (Peacock et al., 1994), the authors related ultrasonic velocities in water-saturated Carrara Marble to crack densities in polished sections to verify Hudson's (1980, 1981, 1986) theory for velocities in cracked rock. They describe the empirical relationships between attenuation and crack density that they established during these experiments in the hope of clarifying the mechanism of attenuation in rocks with fluid-filled cracks. Relating seismic velocity and attenuation to crack density is important in predicting the productivity of fractured petroleum reservoirs such as the North Sea Brent Field. It also allows cracks to be used as stress indicatorsmore » throughout the shallow crust (Crampin and Lovell, 1991).« less

Catalytic cracking of Mayan gas oil and selected hydrotreated products: Topical report

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wells, J.W.; Zagula, E.J.; Brinkman, D.W.

1988-01-01

The catalytic cracking of a Mayan vacuum gas oil and the products from mild, moderate, and severe hydrotreating of this gas oil was evaluated over a low-metal equilibrium catalyst in a microconfined bed unit (MCBU). Results obtained with the Mayan feedstocks are compared with those of an earlier study conducted with similar feedstocks obtained from a Wilmington (CA) crude oil. Two levels of catalytic cracking severity were used in the evaluation. Performance and product analysis showed that hydrotreating improves the yields obtained from catalytic cracking and the quality of the resultant products. In contrast to results obtained with the Wilmingtonmore » feedstocks, conversion and gasoline yield do not improve with severity of the hydrotreating of the Mayan vacuum gas oils. The insensitivity of the cracking performance to hydrotreating severity may reflect the more facile removal of polar compounds (heteroatom compounds) on hydrotreating of the Mayan gas oil in comparison to the Wilmington. Sulfur and nitrogen contents of the liquid products (gasoline, light cycle oil, heavy cycle oil) decreased as the severity of the feed hydrotreating increased. 7 refs., 12 figs., 15 tabs.« less

A stable solid acid material: Sulfated ZrO2 dispersed on alumina nanotubes

NASA Astrophysics Data System (ADS)

Feng, Yu; Jiaqi, Chen; Xu, Wang; Rui-Feng, Li

2017-02-01

A tubular solid acid catalyst was designed by loading sulfated zirconia into γ-Al2O3 nanotubes using the method of stepwise deposition. The XRD, N2 adsorption-desorption characterization demonstrated that introducing alumina nanotube and SO4 2- anions have played an important role in stabilizing the metastable tetragonal ZrO2 phase, and the sulfated zirconia on the surface of the γ-Al2O3 nanotube has high dispersion and stability. The catalyst reused repeatedly possesses large amounts of acid sites and good acidity, exhibiting high catalytic activity and stability for isopropylbenzene cracking.

Nitrogen-doped graphene catalysts: High energy wet ball milling synthesis and characterizations of functional groups and particle size variation with time and speed

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhuang, Shiqiang; Nunna, Bharath Babu; Boscoboinik, Jorge Anibal

Nitrogen-doped graphene (N-G) catalyst emerges as one of the promising non-platinum group metal (non-PGM) catalysts with the advantages of low cost, high oxygen reduction reaction (ORR) activity, stability, and selectivity to replace expensive PGM catalysts in electrochemical systems. This research investigated nanoscale high energy wet (NHEW) ball milling for the synthesis of N-G catalysts to make conventional problems such as sintering or localized overheating issues negligible. The successful synthesis of N-G catalysts with comparable catalytic performance to 10 wt% Pt/C by using this method has been published. This paper focuses on understanding the effect of grinding speed and grinding timemore » on the particle size and chemical state of N-G catalysts through the physical and chemical characterization. The research result shows that (1) the final particle size, nitrogen doping percentage, and nitrogen bonding composition of synthesized N-G catalysts are predictable and controllable by adjusting the grinding time, the grinding speed, and other relative experimental parameters; (2) the final particle size of N-G catalysts could be estimated from the derived relation between the cracking energy density and the particle size of ground material in the NHEW ball milling process with specified experimental parameters; and (3) the chemical composition of N-G catalysts synthesized by NHEW ball milling is controllable by adjusting the grinding time and grinding speed.« less

Nitrogen-doped graphene catalysts: High energy wet ball milling synthesis and characterizations of functional groups and particle size variation with time and speed

DOE PAGES

Zhuang, Shiqiang; Nunna, Bharath Babu; Boscoboinik, Jorge Anibal; ...

2017-07-26

Nitrogen-doped graphene (N-G) catalyst emerges as one of the promising non-platinum group metal (non-PGM) catalysts with the advantages of low cost, high oxygen reduction reaction (ORR) activity, stability, and selectivity to replace expensive PGM catalysts in electrochemical systems. This research investigated nanoscale high energy wet (NHEW) ball milling for the synthesis of N-G catalysts to make conventional problems such as sintering or localized overheating issues negligible. The successful synthesis of N-G catalysts with comparable catalytic performance to 10 wt% Pt/C by using this method has been published. This paper focuses on understanding the effect of grinding speed and grinding timemore » on the particle size and chemical state of N-G catalysts through the physical and chemical characterization. The research result shows that (1) the final particle size, nitrogen doping percentage, and nitrogen bonding composition of synthesized N-G catalysts are predictable and controllable by adjusting the grinding time, the grinding speed, and other relative experimental parameters; (2) the final particle size of N-G catalysts could be estimated from the derived relation between the cracking energy density and the particle size of ground material in the NHEW ball milling process with specified experimental parameters; and (3) the chemical composition of N-G catalysts synthesized by NHEW ball milling is controllable by adjusting the grinding time and grinding speed.« less

Influences of synthesis methods and modifier addition on the properties of Ni-based catalysts supported on reticulated ceramic foams

NASA Astrophysics Data System (ADS)

Nikolić, Vesna; Kamberović, Željko; Anđić, Zoran; Korać, Marija; Sokić, Miroslav; Maksimović, Vesna

2014-08-01

A method of synthesizing Ni-based catalysts supported on α-Al2O3-based foams was developed. The foams were impregnated with aqueous solutions of metal chlorides under an air atmosphere using an aerosol route. Separate procedures involved calcination to form oxides and drying to obtain chlorides on the foam surface. The synthesized samples were subsequently reduced with hydrogen. With respect to the Ni/Al2O3 catalysts, the chloride reduction route enabled the formation of a Ni coating without agglomerates or cracks. Further research included catalyst modification by the addition of Pd, Cu, and Fe. The influences of the additives on the degree of reduction and on the low-temperature reduction effectiveness (533 and 633 K) were examined and compared for the catalysts obtained from oxides and chlorides. Greater degrees of reduction were achieved with chlorides, whereas Pd was the most effective modifier among those investigated. The reduction process was nearly complete at 533 K in the sample that contained 0.1wt% Pd. A lower reduction temperature was utilized, and the calcination step was avoided, which may enhance the economical and technological aspects of the developed catalyst production method.

Simple models of the hydrofracture process

NASA Astrophysics Data System (ADS)

Marder, M.; Chen, Chih-Hung; Patzek, T.

2015-12-01

Hydrofracturing to recover natural gas and oil relies on the creation of a fracture network with pressurized water. We analyze the creation of the network in two ways. First, we assemble a collection of analytical estimates for pressure-driven crack motion in simple geometries, including crack speed as a function of length, energy dissipated by fluid viscosity and used to break rock, and the conditions under which a second crack will initiate while a first is running. We develop a pseudo-three-dimensional numerical model that couples fluid motion with solid mechanics and can generate branching crack structures not specified in advance. One of our main conclusions is that the typical spacing between fractures must be on the order of a meter, and this conclusion arises in two separate ways. First, it arises from analysis of gas production rates, given the diffusion constants for gas in the rock. Second, it arises from the number of fractures that should be generated given the scale of the affected region and the amounts of water pumped into the rock.

Free Oscillations of a Fluid-filled Cavity in an Infinite Elastic Medium

NASA Astrophysics Data System (ADS)

Sakuraba, A.

2016-12-01

Volcanic low-frequency earthquakes and tremor have been widely recognized as a good indicator of hidden activities of volcanoes. It is likely that existence or movement of underground magma and geothermal fluids play a crucial role in their generation mechanisms, but there are still many unknowns. This presentation aims to give a fundamental contribution to understanding and interpreting volcanic low-frequency seismic events. The problem we consider is to compute eigen modes of free oscillations of a fluid-filled cavity surrounded by an infinite linearly elastic medium. A standard boundary element method is used to solve fluid and elastic motion around a cavity of arbitrary shape. Nonlinear advection term is neglected, but viscosity is generally considered in a fluid medium. Of a great importance is to find not only characteristic frequencies but attenuation properties of the oscillations, the latter being determined by both viscous dissipation in the fluid cavity and elastic wave radiation to infinity. One of the simplest cases may be resonance of a fluid-filled crack, which has been studied numerically (Chouet, JGR 1986; Yamamoto and Kawakatsu, GJI 2008) and analytically (Maeda and Kumagai, GRL 2013). In the present study, we generally consider a three-dimensional cavity with emphasis on treating the crack model and other simplest models such as spherical and cylindrical resonators as the extreme cases. In order to reduce computational costs, we assume symmetries about three orthogonal planes and calculate the eigen modes separately for each symmetry. The current status of this project is that the computational code has been checked through comparison to eigen modes of a spherical inviscid cavity (Sakuraba et al., EPS 2002), and another comparison to resonance of a fluid-filled crack is undertook.

Production of biofuel from waste cooking palm oil using nanocrystalline zeolite as catalyst: process optimization studies.

PubMed

Taufiqurrahmi, Niken; Mohamed, Abdul Rahman; Bhatia, Subhash

2011-11-01

The catalytic cracking of waste cooking palm oil to biofuel was studied over different types of nano-crystalline zeolite catalysts in a fixed bed reactor. The effect of reaction temperature (400-500 °C), catalyst-to-oil ratio (6-14) and catalyst pore size of different nanocrystalline zeolites (0.54-0.80 nm) were studied over the conversion of waste cooking palm oil, yields of Organic Liquid Product (OLP) and gasoline fraction in the OLP following central composite design (CCD). The response surface methodology was used to determine the optimum value of the operating variables for maximum conversion as well as maximum yield of OLP and gasoline fraction, respectively. The optimum reaction temperature of 458 °C with oil/catalyst ratio=6 over the nanocrystalline zeolite Y with pore size of 0.67 nm gave 86.4 wt% oil conversion, 46.5 wt% OLP yield and 33.5 wt% gasoline fraction yield, respectively. The experimental results were in agreement with the simulated values within an experimental error of less than 5%. Copyright © 2011 Elsevier Ltd. All rights reserved.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vaidheeswaran, Avinash; Shaffer, Franklin; Gopalan, Balaji

Here, the statistics of fluctuating velocity components are studied in the riser of a closed-loop circulating fluidized bed with fluid catalytic cracking catalyst particles. Our analysis shows distinct similarities as well as deviations compared to existing theories and bench-scale experiments. The study confirms anisotropic and non-Maxwellian distribution of fluctuating velocity components. The velocity distribution functions (VDFs) corresponding to transverse fluctuations exhibit symmetry, and follow a stretched-exponential behavior up to three standard deviations. The form of the transverse VDF is largely determined by interparticle interactions. The tails become more overpopulated with an increase in particle loading. The observed deviations from themore » Gaussian distribution are represented using the leading order term in the Sonine expansion, which is commonly used to approximate the VDFs in kinetic theory for granular flows. The vertical fluctuating VDFs are asymmetric and the skewness shifts as the wall is approached. In comparison to transverse fluctuations, the vertical VDF is determined by the local hydrodynamics. This is an observation of particle velocity fluctuations in a large-scale system and their quantitative comparison with the Maxwell-Boltzmann statistics.« less

40 CFR 63.1082 - What definitions do I need to know?

Code of Federal Regulations, 2010 CFR

2010-07-01

...) National Emission Standards for Ethylene Manufacturing Process Units: Heat Exchange Systems and Waste... resulting from the quench and compression of cracked gas (the cracking furnace effluent) at an ethylene... within an ethylene production unit. Process wastewater is not organic wastes, process fluids, product...

Experiments on the Effects of Confining Pressure During Reaction-Driven Cracking

NASA Astrophysics Data System (ADS)

Skarbek, R. M.; Savage, H. M.; Kelemen, P. B.; Lambart, S.; Robinson, B.

2016-12-01

Cracking caused by reaction-driven volume increase is an important process in many geological settings. In particular, the interaction of brittle rocks with reactive fluids can create fractures that modify the permeability and reactive surface area, leading to a large variety of feedbacks. The conditions controlling reaction-driven cracking are poorly understood, especially at geologically relevant confining pressures. We conducted two sets of experiments to study the effects of confining pressure on cracking during the formation of gypsum from anhydrite CaSO4 + 2H2O = CaSO4•2H2O, and portlandite from calcium oxide CaO + H2O = Ca(OH)2. In the first set of experiments, we cold-pressed CaSO4, or CaO powder to form cylinders. Samples were confined in steel, and compressed with an axial load of 0.1 to 4 MPa. Water was allowed to infiltrate the initially unsaturated samples through the bottom face via capillary and Darcian flow across a micro-porous frit. The height of the sample was recorded during the experiment, and serves as a measure of volume change due to the hydration reaction. We also recorded acoustic emissions (AEs) using piezoelectric transducers (PZTs), to serve as a measure of cracking during an experiment. Experiments were stopped when the recorded volume change reached 80% - 100% of the stoichiometrically calculated volume change of the reaction. In a second set of experiments, we pressed CaSO4 powder to form cylinders 8.9 cm in length and 3.5 cm in diameter for testing in a tri-axial press with ports for fluid input and output, across the top and bottom faces of the sample. The tri-axial experiments were set up to investigate the reaction-driven cracking process for a range of confining pressures. Cracking during experiments was monitored using strain gauges and PZTs attached to the sample. We measured permeability during experiments by imposing a fluid pressure gradient across the sample. These experiments elucidate the role of cracking caused by crystallization pressure in many important hydration reactions.

InSAR analysis for detecting the route of hydrothermal fluid to the surface during the 2015 phreatic eruption of Hakone Volcano, Japan

NASA Astrophysics Data System (ADS)

Doke, Ryosuke; Harada, Masatake; Mannen, Kazutaka; Itadera, Kazuhiro; Takenaka, Jun

2018-04-01

Although the 2015 Hakone Volcano eruption was a small-scale phreatic eruption with a discharged mass of only about 100 tons, interferometric synthetic aperture radar successfully detected surface deformations related to the eruption. Inversion model of the underground hydrothermal system based on measured ground displacements by ALOS-2/PALSAR-2 images showed that a crack opened at an elevation of about 530-830 m, probably at the time of the eruption. A geomorphological analysis detected several old NW-SE trending fissures, and the open crack was located just beneath one of the fissures. Thus, the crack that opened during the 2015 eruption could have been a preexisting crack that formed during a more voluminous hydrothermal eruption. In addition, the inversion model implies that a sill deflation occurred at an elevation of about 225 m, probably at the time of the eruption. The deflation of sill-like body represents a preexisting hydrothermal reservoir at an elevation of 100-400 m, which intruded fluid in the open crack prior to eruption. The volume changes of the open crack and the sill were calculated to be 1.14 × 105 m3 (inflation) and 0.49 × 105 m3 (deflation), respectively. A very local swelling (about 200 m in diameter) was also detected at the eruption center 2 months before the eruption. The local swelling, whose rate in satellite line-of-sight was 0.7-0.9 cm/day during May 2015 and declined in June, had been monitored until the time of the eruption, when its uplift halted. This was modeled as a point pressure source at an elevation of about 900 m (at a depth of about 80-90 m from the ground surface) and is considered to be a minor hydrothermal reservoir just beneath the fumarolic field. Our analysis shows that the northernmost tip of the open crack reached within 200 m of the surface. Thus, it is reasonable to assume that the hydrothermal fluid in the open crack found a way to the surface and formed the eruption.[Figure not available: see fulltext.

Demonstrating the Effect of Interphase Mass Transfer in a Transparent Fluidized Bed Reactor

ERIC Educational Resources Information Center

Saayman, Jean; Nicol, Willie

2011-01-01

A demonstration experiment is described that employs the ozone decomposition reaction at ambient conditions on Fe2O3 impregnated Fluidized Catalytic Cracking (FCC) catalyst. Using a two-dimensional see-through column the importance of interphase mass transfer is clearly illustrated by the significant difference in ozone conversion between the…

40 CFR Table 3 to Subpart Uuu of... - Continous Monitoring Systems for Metal HAP Emissions From Catalytic Cracking Units

Code of Federal Regulations, 2010 CFR

2010-07-01

... system to measure and record the opacity of emissions from each catalyst regnerator vent. 4. Option 3: Ni... monitoring system to measure and record the gas flow rate 1. 5. Option 4: Ni lb/1,000 lbs of coke burn-off...

40 CFR Table 3 to Subpart Uuu of... - Continous Monitoring Systems for Metal HAP Emissions From Catalytic Cracking Units

Code of Federal Regulations, 2011 CFR

2011-07-01

... system to measure and record the opacity of emissions from each catalyst regnerator vent. 4. Option 3: Ni... monitoring system to measure and record the gas flow rate 1. 5. Option 4: Ni lb/1,000 lbs of coke burn-off...

Catalytic pyrolysis of oil fractions separated from food waste leachate over nanoporous acid catalysts.

PubMed

Kim, Seung-Soo; Heo, Hyeon Su; Kim, Sang Guk; Ryoo, Ryong; Kim, Jeongnam; Jeon, Jong-Ki; Park, Sung Hoon; Park, Young-Kwon

2011-07-01

Oil fractions, separated from food waste leachate, can be used as an energy source. Especially, high quality oil can be obtained by catalytic cracking. In this study, nanoporous catalysts such as Al-MCM-41 and mesoporous MFI type zeolite were applied to the catalytic cracking of oil fractions using the pyrolysis gas chromatography/mass spectrometry. Mesoporous MFI type zeolite showed better textural porosity than Al-MCM-41. In addition, mesoporous MFI type zeolite had strong Brönsted acidity while Al-MCM-41 had weak acidity. Significant amount of acid components in the food waste oil fractions were converted to mainly oxygenates and aromatics. As a result of its well-defined nanopores and strong acidity, the use of a mesoporous MFI type zeolite produced large amounts of gaseous and aromatic compounds. High yields of hydrocarbons within the gasoline range were also obtained in the case of mesoporous MFI type zeolite, whereas the use of Al-MCM-41, which exhibits relatively weak acidity, resulted in high yields of oxygenates and diesel range hydrocarbons.

Reactor for in situ measurements of spatially resolved kinetic data in heterogeneous catalysis

NASA Astrophysics Data System (ADS)

Horn, R.; Korup, O.; Geske, M.; Zavyalova, U.; Oprea, I.; Schlögl, R.

2010-06-01

The present work describes a reactor that allows in situ measurements of spatially resolved kinetic data in heterogeneous catalysis. The reactor design allows measurements up to temperatures of 1300 °C and 45 bar pressure, i.e., conditions of industrial relevance. The reactor involves reactants flowing through a solid catalyst bed containing a sampling capillary with a side sampling orifice through which a small fraction of the reacting fluid (gas or liquid) is transferred into an analytical device (e.g., mass spectrometer, gas chromatograph, high pressure liquid chromatograph) for quantitative analysis. The sampling capillary can be moved with μm resolution in or against flow direction to measure species profiles through the catalyst bed. Rotation of the sampling capillary allows averaging over several scan lines. The position of the sampling orifice is such that the capillary channel through the catalyst bed remains always occupied by the capillary preventing flow disturbance and fluid bypassing. The second function of the sampling capillary is to provide a well which can accommodate temperature probes such as a thermocouple or a pyrometer fiber. If a thermocouple is inserted in the sampling capillary and aligned with the sampling orifice fluid temperature profiles can be measured. A pyrometer fiber can be used to measure the temperature profile of the solid catalyst bed. Spatial profile measurements are demonstrated for methane oxidation on Pt and methane oxidative coupling on Li/MgO, both catalysts supported on reticulated α -Al2O3 foam supports.

Transient radon signals driven by fluid pressure pulse, micro-crack closure, and failure during granite deformation experiments

NASA Astrophysics Data System (ADS)

Girault, Frédéric; Schubnel, Alexandre; Pili, Éric

2017-09-01

In seismically active fault zones, various crustal fluids including gases are released at the surface. Radon-222, a radioactive gas naturally produced in rocks, is used in volcanic and tectonic contexts to illuminate crustal deformation or earthquake mechanisms. At some locations, intriguing radon signals have been recorded before, during, or after tectonic events, but such observations remain controversial, mainly because physical characterization of potential radon anomalies from the upper crust is lacking. Here we conducted several month-long deformation experiments under controlled dry upper crustal conditions with a triaxial cell to continuously monitor radon emission from crustal rocks affected by three main effects: a fluid pressure pulse, micro-crack closure, and differential stress increase to macroscopic failure. We found that these effects are systematically associated with a variety of radon signals that can be explained using a first-order advective model of radon transport. First, connection to a source of deep fluid pressure (a fluid pressure pulse) is associated with a large transient radon emission increase (factor of 3-7) compared with the background level. We reason that peak amplitude is governed by the accumulation time and the radon source term, and that peak duration is controlled by radioactive decay, permeability, and advective losses of radon. Second, increasing isostatic compression is first accompanied by an increase in radon emission followed by a decrease beyond a critical pressure representing the depth below which crack closure hampers radon emission (150-250 MPa, ca. 5.5-9.5 km depth in our experiments). Third, the increase of differential stress, and associated shear and volumetric deformation, systematically triggers significant radon peaks (ca. 25-350% above background level) before macroscopic failure, by connecting isolated cracks, which dramatically enhances permeability. The detection of transient radon signals before rupture indicates that connection of initially isolated cracks in crustal rocks may occur before rupture and potentially lead to radon transients measurable at the surface in tectonically active regions. This study offers thus an experimental and physical basis for understanding predicted or reported radon anomalies.

Transient radon signals driven by fluid pressure pulse, micro-crack closure, and failure during granite deformation experiments

NASA Astrophysics Data System (ADS)

Schubnel, A.; Girault, F.; Pili, E.

2017-12-01

In seismically active fault zones, various crustal fluids including gases are released at the surface. Radon-222, a radioactive gas naturally produced in rocks, is used in volcanic and tectonic contexts to illuminate crustal deformation or earthquake mechanisms. At some locations, intriguing radon signals have been recorded before, during, or after tectonic events, but such observations remain controversial, mainly because physical characterization of potential radon anomalies from the upper crust is lacking. Here we conducted several month-long deformation experiments under controlled dry upper crustal conditions with a triaxial cell to continuously monitor radon emission from crustal rocks affected by three main effects: a fluid pressure pulse, micro-crack closure, and differential stress increase to macroscopic failure. We found that these effects are systematically associated with a variety of radon signals that can be explained using a first-order advective model of radon transport. First, connection to a source of deep fluid pressure (a fluid pressure pulse) is associated with a large transient radon emission increase (factor of 3-7) compared with the background level. We reason that peak amplitude is governed by the accumulation time and the radon source term, and that peak duration is controlled by radioactive decay, permeability, and advective losses of radon. Second, increasing isostatic compression is first accompanied by an increase in radon emission followed by a decrease beyond a critical pressure representing the depth below which crack closure hampers radon emission (150-250 MPa, ca. 5.5-9.5 km depth in our experiments). Third, the increase of differential stress, and associated shear and volumetric deformation, systematically triggers significant radon peaks (ca. 25-350% above background level) before macroscopic failure, by connecting isolated cracks, which dramatically enhances permeability. The detection of transient radon signals before rupture indicates that connection of initially isolated cracks in crustal rocks may occur before rupture and potentially lead to radon transients measurable at the surface in tectonically active regions. This study offers thus an experimental and physical basis for understanding predicted or reported radon anomalies.

Production of hydrocarbon fuels from pyrolysis of soybean oils using a basic catalyst.

PubMed

Xu, Junming; Jiang, Jianchun; Sun, Yunjuan; Chen, Jie

2010-12-01

Triglycerides obtained from animals and plants have attracted great attention from researchers for developing an environmental friendly and high-quality fuel, free of nitrogen and sulfur. In the present work, the production of biofuel by catalytic cracking of soybean oil over a basic catalyst in a continuous pyrolysis reactor at atmospheric pressure has been studied. Experiments were designed to study the effect of different types of catalysts on the yield and acid value of the diesel and gasoline fractions from the pyrolytic oil. It was found that basic catalyst gave a product with relatively low acid number. These pyrolytic oils were also further reacted with alcohol in order to decrease their acid value. After esterification, the physico-chemical properties of these biofuels were characterized, and compared with Chinese specifications for conventional diesel fuels. The results showed that esterification of pyrolytic oil from triglycerides represents an alternative technique for producing biofuels from soybean oils with characteristics similar to those of petroleum fuels. Published by Elsevier Ltd.

Catalytic decomposition of tar derived from wood waste pyrolysis using Indonesian low grade iron ore as catalyst

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wicakso, Doni Rahmat; Chemical Engineering Department, Faculty of Engineering, Gadjah Mada University, Jalan Grafika No. 2 Bulaksumur, Yogyakarta, 55281; Sutijan

Low grade iron ore can be used as an alternative catalyst for bio-tar decomposition. Compared to other catalysts, such as Ni, Rd, Ru, Pd and Pt, iron ore is cheaper. The objective of this research was to investigate the effect of using low grade iron ore as catalyst for tar catalytic decomposition in fixed bed reactor. Tar used in this experiment was pyrolysis product of wood waste while the catalyst was Indonesian low grade iron ore. The variables studied were temperatures between 500 – 600 °C and catalyst weight between 0 – 40 gram. The first step, tar was evaporatedmore » at 450 °C to produce tar vapor. Then, tar vapor was flowed to fixed bed reactor filled low grade iron ore. Gas and tar vapor from reactor was cooled, then the liquid and uncondensable gas were analyzed by GC/MS. The catalyst, after experiment, was weighed to calculate total carbon deposited into catalyst pores. The results showed that the tar components that were heavy and light hydrocarbon were decomposed and cracked within the iron ore pores to from gases, light hydrocarbon (bio-oil) and carbon, thus decreasing content tar in bio-oil and increasing the total gas product. In conclusion, the more low grade iron ore used as catalyst, the tar content in the liquid decrease, the H{sup 2} productivity increased and calorimetric value of bio-oil increased.« less

In-vitro biodegradation and corrosion-assisted cracking of a coated magnesium alloy in modified-simulated body fluid.

PubMed

Jafari, Sajjad; Singh Raman, R K

2017-09-01

A calcium phosphate coating was directly synthesized on AZ91D magnesium (Mg) alloy. Resistance of this coating to corrosion in a modified-simulated body fluid (m-SBF) was investigated by potentiodynamic polarization and electrochemical impedance spectroscopy (EIS). Mechanical properties of the bare and coated alloy were investigated using slow strain rate tensile (SSRT) and fatigue testing in air and m-SBF. Very little is reported in the literature on human-body-fluid-assisted cracking of Mg alloys, viz., resistance to corrosion fatigue (CF) and stress corrosion cracking (SCC). This study has a particular emphasis on the effect of bio-compatible coatings on mechanical and electrochemical degradations of Mg alloys for their applications as implants. The results suggest the coating to improve the general as well as pitting corrosion resistance of the alloy. The coating also provides visible improvement in resistance to SCC, but little improvement in CF resistance. This is explained on the basis of pitting behaviour in the presence and absence of the coating. Copyright © 2017 Elsevier B.V. All rights reserved.

Natural abundance 17O DNP NMR provides precise O–H distances and insights into the Brønsted acidity of heterogeneous catalysts

DOE PAGES

Perras, Frederic A.; Wang, Zhuoran; Naik, Pranjali; ...

2017-05-12

Heterogeneous Brønsted acid catalysts are tremendously important in industry, particularly in catalytic cracking processes. Here we show that these Brønsted acid sites can be directly observed at natural abundance by 17O DNP surface-enhanced NMR spectroscopy (SENS). We additionally show that the O–H bond length in these catalysts can be measured with sub-picometer precision, to enable a direct structural gauge of the lability of protons in a given material, which is correlated with the pH of the zero point of charge of the material. As a result, experiments performed on materials impregnated with pyridine also allow for the direct detection ofmore » intermolecular hydrogen bonding interactions through the lengthening of O–H bonds.« less

Natural abundance 17O DNP NMR provides precise O–H distances and insights into the Brønsted acidity of heterogeneous catalysts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Perras, Frederic A.; Wang, Zhuoran; Naik, Pranjali

Heterogeneous Brønsted acid catalysts are tremendously important in industry, particularly in catalytic cracking processes. Here we show that these Brønsted acid sites can be directly observed at natural abundance by 17O DNP surface-enhanced NMR spectroscopy (SENS). We additionally show that the O–H bond length in these catalysts can be measured with sub-picometer precision, to enable a direct structural gauge of the lability of protons in a given material, which is correlated with the pH of the zero point of charge of the material. As a result, experiments performed on materials impregnated with pyridine also allow for the direct detection ofmore » intermolecular hydrogen bonding interactions through the lengthening of O–H bonds.« less

Enhancement of alkylation catalysts for improved supercritical fluid regeneration

DOEpatents

Ginosar, Daniel M [Idaho Falls, ID; Petkovic, Lucia [Idaho Falls, ID

2009-09-22

A method of modifying an alkylation catalyst to reduce the formation of condensed hydrocarbon species thereon. The method comprises providing an alkylation catalyst comprising a plurality of active sites. The plurality of active sites on the alkylation catalyst may include a plurality of weakly acidic active sites, intermediate acidity active sites, and strongly acidic active sites. A base is adsorbed to a portion of the plurality of active sites, such as the strongly acidic active sites, selectively poisoning the strongly acidic active sites. A method of modifying the alkylation catalyst by providing an alkylation catalyst comprising a pore size distribution that sterically constrains formation of the condensed hydrocarbon species on the alkylation catalyst or by synthesizing the alkylation catalyst to comprise a decreased number of strongly acidic active sites is also disclosed, as is a method of improving a regeneration efficiency of the alkylation catalyst.

Enhancement of alkylation catalysts for improved supercritical fluid regeneration

DOEpatents

Ginosar, Daniel M.; Petkovic, Lucia M.

2010-12-28

A method of modifying an alkylation catalyst to reduce the formation of condensed hydrocarbon species thereon. The method comprises providing an alkylation catalyst comprising a plurality of active sites. The plurality of active sites on the alkylation catalyst may include a plurality of weakly acidic active sites, intermediate acidity active sites, and strongly acidic active sites. A base is adsorbed to a portion of the plurality of active sites, such as the strongly acidic active sites, selectively poisoning the strongly acidic active sites. A method of modifying the alkylation catalyst by providing an alkylation catalyst comprising a pore size distribution that sterically constrains formation of the condensed hydrocarbon species on the alkylation catalyst or by synthesizing the alkylation catalyst to comprise a decreased number of strongly acidic active sites is also disclosed, as is a method of improving a regeneration efficiency of the alkylation catalyst.

Developments in SCC Mitigation by Electrocatalysis

NASA Astrophysics Data System (ADS)

Andresen, Peter L.; Kim, Young J.

SCC is strongly influenced by water chemistry parameters, especially when crack chemistry can be concentrated from differential aeration or thermal gradients or boiling. Mitigation of the effects of the high corrosion potential associated with oxidants is markedly and efficiently accomplished by electrocatalysis, which requires that there be a stoichiometric excess of reductants over oxidants. Mechanisms and criteria for effective SCC mitigation are summarized, with particular focus on the critical location for the catalyst in a crack and experimental support for these concepts. Optimization of electrocatalysis by OnLine NobleChem- is described, for example where Pt is injected at levels of 0.002 to 0.05 ppb in the reactor water.

Negative electrode catalyst for the iron chromium redox energy storage system

NASA Technical Reports Server (NTRS)

Gahn, R. F.; Hagedorn, N. H. (Inventor)

1985-01-01

A redox cell which operates at elevated temperatures and which utilizes the same two metal couples in each of the two reactant fluids is disclosed. Each fluid includes a bismuth salt and may also include a lead salt. A low cost, cation permselective membrane separates the reactant fluids.

Influence of H 2O and H 2S on the composition, activity, and stability of sulfided Mo, CoMo, and NiMo supported on MgAl 2O 4 for hydrodeoxygenation of ethylene glycol

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dabros, Trine Marie Hartmann; Gaur, Abhijeet; Pintos, Delfina Garcia

Here in this work, density functional theory (DFT), catalytic activity tests, and in-situ X-ray absorption spectroscopy (XAS) was performed to gain detailed insights into the activity and stability of MoS 2, Ni-MoS 2, and Co-MoS 2 catalysts used for hydrodeoxygenation (HDO) of ethylene glycol upon variation of the partial pressures of H 2O and H 2S. The results show high water tolerance of the catalysts and highlight the importance of promotion and H 2S level during HDO. DFT calculations unraveled that the active edge of MoS 2 could be stabilized against SO exchanges by increasing the partial pressure of Hmore » 2S or by promotion with either Ni or Co. The Mo, NiMo, and CoMo catalysts of the present study were all active and fairly selective for ethylene glycol HDO at 400 °C, 27 bar H 2, and 550–2200 ppm H 2S, and conversions of ≈50–100%. The unpromoted Mo/MgAl 2O 4 catalyst had a lower stability and activity per gram catalyst than the promoted analogues. The NiMo and CoMo catalysts produced ethane, ethylene, and C1 cracking products with a C 2/C 1 ratio of 1.5–2.0 at 550 ppm H 2S. This ratio of HDO to cracking could be increased to ≈2 at 2200 ppm H 2S which also stabilized the activity. Removing H 2S from the feed caused severe catalyst deactivation. Both DFT and catalytic activity tests indicated that increasing the H 2S concentration increased the concentration of SH groups on the catalyst, which correspondingly activated and stabilized the catalytic HDO performance. In-situ XAS further supported that the catalysts were tolerant towards water when exposed to increasing water concentration with H2O/H2S ratios up to 300 at 400–450 °C. Raman spectroscopy and XAS showed that MoS2 was present in the prepared catalysts as small and highly dispersed particles, probably owing to a strong interaction with the support. Linear combination fitting (LCF) analysis of the X-ray absorption near edge structure (XANES) spectra obtained during in-situ sulfidation showed that Ni was sulfided faster than Mo and CoMo, and that Mo was sulfided faster when promoted with Ni. Extended X-ray absorption fine structure (EXAFS) results showed the presence of MoS 2 in all sulfided catalysts. Lastly, sulfided CoMo was present as a mixture of CoMoS and Co 9S 8, whereas sulfided NiMo was present as NiMoS.« less

Influence of H 2O and H 2S on the composition, activity, and stability of sulfided Mo, CoMo, and NiMo supported on MgAl 2O 4 for hydrodeoxygenation of ethylene glycol

DOE PAGES

Dabros, Trine Marie Hartmann; Gaur, Abhijeet; Pintos, Delfina Garcia; ...

2017-12-10

Here in this work, density functional theory (DFT), catalytic activity tests, and in-situ X-ray absorption spectroscopy (XAS) was performed to gain detailed insights into the activity and stability of MoS 2, Ni-MoS 2, and Co-MoS 2 catalysts used for hydrodeoxygenation (HDO) of ethylene glycol upon variation of the partial pressures of H 2O and H 2S. The results show high water tolerance of the catalysts and highlight the importance of promotion and H 2S level during HDO. DFT calculations unraveled that the active edge of MoS 2 could be stabilized against SO exchanges by increasing the partial pressure of Hmore » 2S or by promotion with either Ni or Co. The Mo, NiMo, and CoMo catalysts of the present study were all active and fairly selective for ethylene glycol HDO at 400 °C, 27 bar H 2, and 550–2200 ppm H 2S, and conversions of ≈50–100%. The unpromoted Mo/MgAl 2O 4 catalyst had a lower stability and activity per gram catalyst than the promoted analogues. The NiMo and CoMo catalysts produced ethane, ethylene, and C1 cracking products with a C 2/C 1 ratio of 1.5–2.0 at 550 ppm H 2S. This ratio of HDO to cracking could be increased to ≈2 at 2200 ppm H 2S which also stabilized the activity. Removing H 2S from the feed caused severe catalyst deactivation. Both DFT and catalytic activity tests indicated that increasing the H 2S concentration increased the concentration of SH groups on the catalyst, which correspondingly activated and stabilized the catalytic HDO performance. In-situ XAS further supported that the catalysts were tolerant towards water when exposed to increasing water concentration with H2O/H2S ratios up to 300 at 400–450 °C. Raman spectroscopy and XAS showed that MoS2 was present in the prepared catalysts as small and highly dispersed particles, probably owing to a strong interaction with the support. Linear combination fitting (LCF) analysis of the X-ray absorption near edge structure (XANES) spectra obtained during in-situ sulfidation showed that Ni was sulfided faster than Mo and CoMo, and that Mo was sulfided faster when promoted with Ni. Extended X-ray absorption fine structure (EXAFS) results showed the presence of MoS 2 in all sulfided catalysts. Lastly, sulfided CoMo was present as a mixture of CoMoS and Co 9S 8, whereas sulfided NiMo was present as NiMoS.« less

Influence of patchy saturation on seismic dispersion and attenuation in fractured porous media

NASA Astrophysics Data System (ADS)

Jinwei, Zhang; Handong, Huang; Chunhua, Wu; Sheng, Zhang; Gang, Wu; Fang, Chen

2018-04-01

Wave induced fluid flow due to mesoscopic heterogeneity can explain seismic dispersion and attenuation in the seismic frequency band. The mesoscopic heterogeneity mainly contains lithological variations, patchy saturation and mesoscopic fractures. The patchy saturation models which are locally based on Biot theory for porous media have been deeply studied, but the patchy saturation model for fractured porous media is rarely studied. In this paper, we develop a model to describe the poroelastic characteristics in fractured porous media where the background and fractures are filled with different fluids based on two scales of squirt flow. The seismic dispersion and attenuation in fractured porous media occur in two scales, the microscale due to fluid flow between pores and micro-cracks and mesoscale due to fluid flow between background and heterogeneities. We derive the complex stiffness tensor through the solution of stress equivalence and fluid conservation. Two new parameters embodying the fluid effects are introduced into the model compared with the single fluid phase model. The model is consistent with Gassmann-Wood equation at low frequency limit and consistent with the isolated fracture model at high frequency limit. After the frequency dependent stiffness tensor is obtained, the variations of velocities and inverse quality factors with frequency are analyzed through several numerical examples. We investigated three poroelastic cases: medium including pores and micro-cracks, media including pores, micro-cracks and fractures, media including pores and fractures. The frequency dependent characteristics of patchy saturation model are different with those of single fluid model not only in characteristic frequency but also in the magnitude of the attenuation. Finally, we discuss the results obtained and the special case where the fractures are saturated with gas or dry and the background is filled with water. We also compare our results with those of patchy saturation model and double porosity model. The results will contribute to the actual exploration work to a certain extent, such as the fluid identification in fractured reservoirs.

40 CFR Table 2 to Subpart Uuu of... - Operating Limits for Metal HAP Emissions From Catalytic Cracking Units

Code of Federal Regulations, 2010 CFR

2010-07-01

... daily average liquid-to-gas ratio above the limit established in the performance test. 4. Option 3: Ni.... Electrostatic precipitator Maintain the daily average Ni operating value no higher than the limit established...; maintain the monthly rolling average of the equilibrium catalyst Ni concentration no higher than the limit...

40 CFR Table 2 to Subpart Uuu of... - Operating Limits for Metal HAP Emissions From Catalytic Cracking Units

Code of Federal Regulations, 2011 CFR

2011-07-01

... daily average liquid-to-gas ratio above the limit established in the performance test. 4. Option 3: Ni.... Electrostatic precipitator Maintain the daily average Ni operating value no higher than the limit established...; maintain the monthly rolling average of the equilibrium catalyst Ni concentration no higher than the limit...

Heterogeneously Catalyzed Endothermic Fuel Cracking

DTIC Science & Technology

2016-08-28

Much of this literature is in the context of gas -to- liquids technology and industrial dehydrogenation processes. Based on the published measurements...certain zeolites. Comparisons of conversion, major product distributions and molecular weight growth processes in the gas -phase pyrolysis of model...thereby maximizing the extent of cooling, (b) increase catalyst activity for fuel decomposition, but inhibit gas -phase molecular weight growth

Catalytic propane dehydrogenation over In₂O₃–Ga₂O₃ mixed oxides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tan, Shuai; Gil, Laura Briones; Subramanian, Nachal

2015-08-26

We have investigated the catalytic performance of novel In₂O₃–Ga₂O₃ mixed oxides synthesized by the alcoholic-coprecipitation method for propane dehydrogenation (PDH). Reactivity measurements reveal that the activities of In₂O₃–Ga₂O₃ catalysts are 1–3-fold (on an active metal basis) and 12–28-fold (on a surface area basis) higher than an In₂O₃–Al₂O₃ catalyst in terms of C₃H₈ conversion. The structure, composition, and surface properties of the In₂O₃–Ga₂O₃ catalysts are thoroughly characterized. NH₃-TPD shows that the binary oxide system generates more acid sites than the corresponding single-component catalysts. Raman spectroscopy suggests that catalysts that produce coke of a more graphitic nature suppress cracking reactions, leading tomore » higher C₃H₆ selectivity. Lower reaction temperature also leads to higher C₃H₆ selectivity by slowing down the rate of side reactions. XRD, XPS, and XANES measurements, strongly suggest that metallic indium and In₂O₃ clusters are formed on the catalyst surface during the reaction. The agglomeration of In₂O₃ domains and formation of a metallic indium phase are found to be irreversible under O₂ or H₂ treatment conditions used here, and may be responsible for loss of activity with increasing time on stream.« less

A review of metal recovery from spent petroleum catalysts and ash.

PubMed

Akcil, Ata; Vegliò, Francesco; Ferella, Francesco; Okudan, Mediha Demet; Tuncuk, Aysenur

2015-11-01

With the increase in environmental awareness, the disposal of any form of hazardous waste has become a great concern for the industrial sector. Spent catalysts contribute to a significant amount of the solid waste generated by the petrochemical and petroleum refining industry. Hydro-cracking and hydrodesulfurization (HDS) catalysts are extensively used in the petroleum refining and petrochemical industries. The catalysts used in the refining processes lose their effectiveness over time. When the activity of catalysts decline below the acceptable level, they are usually regenerated and reused but regeneration is not possible every time. Recycling of some industrial waste containing base metals (such as V, Ni, Co, Mo) is estimated as an economical opportunity in the exploitation of these wastes. Alkali roasted catalysts can be leached in water to get the Mo and V in solution (in which temperature plays an important role during leaching). Several techniques are possible to separate the different metals, among those selective precipitation and solvent extraction are the most used. Pyrometallurgical treatment and bio-hydrometallurgical leaching were also proposed in the scientific literature but up to now they did not have any industrial application. An overview on patented and commercial processes was also presented. Copyright © 2015 Elsevier Ltd. All rights reserved.

Slurry hydrocracking of Arab heavy vacuum resid with new bifunctional catalysts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rankel, L.A.

1993-12-31

Co-processing coal with hydrogenated vacuum resids can solubilize coal and aid in metals removals from the hydrotreated resid. Several bifunctional NiW catalysts were evaluated for resid hydrocracking in a slurry reactor. Autoclave runs were made to determine whether a hydrogenative metal function (NiW) plus support with cracking activity might be an effective catalyst for high resid 1000F{degrees}{sup +} conversion, H-content enrichment, deS, and demetallation at low coke make. An Arab Heavy 895{degrees}F{sup +} vacuum resid (262 ppm Ni+V, 5.3% S and 24% CCR) was hydrocracked over sulfided and unsulfided NiW catalysts on alumina, silica-alumina, US-Y, etc. at 800{degrees}F and 2000more » psig hydrogen in a batch reactor and compared to oil soluble mixtures of Ni and W homogenous organometallics. Of the catalysts tested here, results indicate that addition of sulfided NiW/aluminum to slurry type processing might improve hydrogenation activity and produce more 1000{degrees}F{sup +} conversion at a particular severity while generating the low coke make necessary for a continuous process. Once the resid is hydrotreated, coal could be added to the NiW bifunctional catalyst/resid slurry for co-processing.« less

Towards an understanding of the role of clay minerals in crude oil formation, migration and accumulation

NASA Astrophysics Data System (ADS)

Wu, Lin Mei; Zhou, Chun Hui; Keeling, John; Tong, Dong Shen; Yu, Wei Hua

2012-12-01

This article reviews progress in the understanding of the role of clay minerals in crude oil formation, migration and accumulation. Clay minerals are involved in the formation of kerogen, catalytic cracking of kerogen into petroleum hydrocarbon, the migration of crude oil, and the continued change to hydrocarbon composition in underground petroleum reservoirs. In kerogen formation, clay minerals act as catalysts and sorbents to immobilize organic matter through ligand exchange, hydrophobic interactions and cation bridges by the mechanisms of Maillard reactions, polyphenol theory, selective preservation and sorptive protection. Clay minerals also serve as catalysts in acid-catalyzed cracking of kerogen into petroleum hydrocarbon through Lewis and Brønsted acid sites on the clay surface. The amount and type of clay mineral affect the composition of the petroleum. Brønsted acidity of clay minerals is affected by the presence and state of interlayer water, and displacement of this water is a probable driver in crude oil migration from source rocks. During crude oil migration and accumulation in reservoirs, the composition of petroleum is continually modified by interaction with clay minerals. The clays continue to function as sorbents and catalysts even while they are being transformed by diagenetic processes. The detail of chemical interactions and reaction mechanisms between clay minerals and crude oil formation remains to be fully explained but promises to provide insights with broader application, including catalytic conversion of biomass as a source of sustainable energy into the future.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Holcomb, Gordon R.

A presentation of the US-UK Phase 3 Task 1 Oxidation in Supercritical Fluids. Includes slides on Supercritical Steam, sCO 2 Power Cycles – Indirect, sCO 2 Power Cycles – Direct, Experimental Exposures, Alloys, Why Si, Results—Ni-xCr Alloys (5-24Cr), Fatigue Crack Growth$-$Experiment, and Alloys and Samples, Fatigue Crack Growth—Results (H282).

Microwave-assisted Extraction of Rare Earth Elements from Petroleum Refining Catalysts and Ambient Fine Aerosols Prior to Inductively Coupled Plasma - Mass Spectrometry

NASA Technical Reports Server (NTRS)

Mittlefehldt, David W.; Kulkarni, Pranav; Chellam, Shankar

2006-01-01

In the absence of a certified reference material, a robust microwave-assisted acid digestion procedure followed by inductively coupled plasma - mass spectrometry (ICP-MS) was developed to quantify rare earth elements (REEs) in fluidized-bed catalytic cracking (FCC) catalysts and atmospheric fine particulate matter (PM2.5). High temperature (200 C), high pressure (200 psig), acid digestion (HNO3, HF, and H3BO3) with 20 minute dwell time effectively solubilized REEs from six fresh catalysts, a spent catalyst, and PM2.5. This method was also employed to measure 27 non-REEs including Na, Mg, Al, Si, K, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, As, Se, Rb, Sr, Zr, Mo, Cd, Cs, Ba, Pb, and U. Complete extraction of several REEs (Y, La, Ce, Pr, Nd, Tb, Dy, and Er) required HF indicating that they were closely associated with the aluminosilicate structure of the zeolite FCC catalysts. Internal standardization using 115In quantitatively corrected non-spectral interferences in the catalyst digestate matrix. Inter-laboratory comparison using ICP-optical emission spectroscopy (ICP-OES) and instrumental neutron activation analysis (INAA) demonstrated the applicability of the newly developed analytical method for accurate analysis of REEs in FCC catalysts. The method developed for FCC catalysts was also successfully implemented to measure trace to ultra-trace concentrations of La, Ce, Pr, Nd, Sm, Gd, Eu, and Dy in ambient PM2.5 in an industrial area of Houston, TX.

Near-threshold fatigue behavior of copper alloys in air and aqueous environments: A high cyclic frequency study

NASA Astrophysics Data System (ADS)

Ahmed, Tawfik M.

The near-threshold fatigue crack propagation behavior of alpha-phase copper alloys in desiccated air and several aqueous environments has been investigated. Three commercial alloys of nominal composition Cu-30Ni (Cu-Ni), Cu-30Zn (Cu-Zn) and 90Cu-7Al-3Fe (Cu-Al) were tested. Fatigue tests were conducted using standard prefatigued single edged notched (SEN) specimens loaded in tension at a high frequency of ˜100 Hz. Different R-ratios were employed, mostly at R-ratios of 0.5. Low loading levels were used that corresponded to the threshold and near-threshold regions where Delta Kth ≤ DeltaK ≤ 11 MPa√m. Fatigue tests in the aqueous solutions showed that the effect of different corrosive environments during high frequency testing (˜100 Hz) was not as pronounced as was expected when compared relative to air. Further testing revealed that environmental effects were present and fatigue crack growth rates were influenced by the fluid-induced closure effects which are generally reported in the fatigue literature to be operative only in viscous liquids, not in aqueous solutions. It was concluded that high frequency testing in aqueous environments consistently decreased crack growth rates in a manner similar to crack retardation effects in viscous fluids. Several theoretical models reported in the literature have underestimated, if not failed, to adequately predict the fluid induced closure in aqueous solutions. Results from the desiccated air tests confirmed that, under closure-free conditions (high R-ratios), both threshold values and fatigue crack growth rate of stage II can be related to Young's modulus, in agreement with results from the literature. The role of different mechanical and environmental variables on fatigue behavior becomes most visible in the low R -ratio regime, and contribute to various closure processes.

Catalytic upgrading of oil fractions separated from food waste leachate.

PubMed

Heo, Hyeon Su; Kim, Sang Guk; Jeong, Kwang-Eun; Jeon, Jong-Ki; Park, Sung Hoon; Kim, Ji Man; Kim, Seung-Soo; Park, Young-Kwon

2011-02-01

In this work, catalytic cracking of biomass waste oil fractions separated from food waste leachate was performed using microporous catalysts, such as HY, HZSM-5 and mesoporous Al-MCM-48. The experiments were carried out using pyrolysis gas chromatography/mass spectrometry (Py-GC/MS) to allow the direct analysis of the pyrolytic products. Most acidic components, especially oleic acid, contained in the food waste oil fractions were converted to valuable products, such as oxygenates, hydrocarbons and aromatics. High yields of hydrocarbons within the gasoline-range were obtained when microporous catalysts were used; whereas, the use of Al-MCM-48, which exhibits relatively weak acidity, resulted in high yields of oxygenated and diesel-range hydrocarbons. The HZSM-5 catalyst produced a higher amount of valuable mono aromatics due to its strong acidity and shape selectivity. Especially, the addition of gallium (Ga) to HZSM-5 significantly increased the aromatics content. Copyright © 2010 Elsevier Ltd. All rights reserved.

Reactive flash volatilization of fluid fuels

DOEpatents

Schmidt, Lanny D.; Dauenhauer, Paul J.; Dreyer, Bradon J.; Salge, James R.

2013-01-08

The invention provides methods for the production of synthesis gas. More particularly, various embodiments of the invention relate to systems and methods for volatilizing fluid fuel to produce synthesis gas by using a metal catalyst on a solid support matrix.

Desiccation of a Sessile Drop of Blood: Cracks Formation and Delamination

NASA Astrophysics Data System (ADS)

Sobac, Benjamin; Brutin, David

2011-11-01

The evaporation of drops of biological fluids has been studied since few years du to several applications in medical fields such as medical tests, drug screening, biostabilization... The evaporation of a drop of whole blood leads to the formation of final typical pattern of cracks. Flow motion, adhesion, gelation and fracturation all occur during the evaporation of this complex matter. During the drying, a sol-gel transition develops. The drying kinetics is explained by a simple model of evaporation taking account of the evolution of the gelation front. The system solidifies and when stresses are too important, cracks nucleate. The cracks formation and the structure of the crack pattern are investigated. The initial crack spacing is found in good agreement with the implementation in open geometry of the model of cracks formation induced by evaporation proposed by Allain and Limat. Finally, the drop is still drying after the end of the formation of cracks which leads, like in the situation of colloid suspensions, to the observation of a delamination phenomenon.

Simultaneous Measurements of Harmonic Waves at Fatigue-Cracked Interfaces

NASA Astrophysics Data System (ADS)

Hyunjo, Jeong; Dan, Barnard

2011-08-01

Nonlinear harmonic waves generated at cracked interfaces are investigated theoretically and experimentally. A compact tension specimen is fabricated and the amplitude of the transmitted wave is analyzed as a function of position along the fatigued crack surface. In order to measure as many nonlinear harmonic components as possible, broadband lithium niobate (LiNbO3) transducers are employed together with a calibration technique for making absolute amplitude measurements with fluid-coupled receiving transducers. Cracked interfaces are shown to generate high acoustic nonlinearities, which are manifested as harmonics in the power spectrum of the received signal. The first subharmonic f/2 and the second harmonic 2f waves are found to be dominant nonlinear components for an incident toneburst signal of frequency f. To explain the observed nonlinear behavior, a partially closed crack is modeled by planar half interfaces that can account for crack parameters, such as crack opening displacement and crack surface conditions. The simulation results show reasonable agreement with the experimental results.

Catalyst surfaces for the chromous/chromic redox couple

NASA Technical Reports Server (NTRS)

Giner, J. D.; Cahill, K. J. (Inventor)

1981-01-01

An electricity producing cell of the reduction-oxidation (REDOX) type divided into two compartments by a membrane is disclosed. A ferrous/ferric couple in a chloride solution serves as a cathode fluid to produce a positive electric potential. A chromic/chromous couple in a chloride solution serves as an anode fluid to produce a negative potential. The electrode is an electrically conductive, inert material plated with copper, silver or gold. A thin layer of lead plates onto the copper, silver or gold layer when the cell is being charged, the lead ions being available from lead chloride which has been added to the anode fluid. If the REDOX cell is then discharged, the lead deplates from the negative electrode and the metal coating on the electrode acts as a catalyst to increase current density.

Effect of lubricant composition on the fatigue properties of ultra-high molecular weight polyethylene for total knee replacement.

PubMed

Aurora, A; DesJardins, J D; Joseph, P F; LaBerge, M

2006-05-01

Ultrahigh molecular weight polyethylene (UHMWPE) fatigue is a critical factor affecting the longevity of total knee replacement (TKR) bearings. With the increased need for laboratory studies to mimic near in vivo conditions for accurate characterization of material performance, the present study investigated the role of hyaluronic acid (HA) in testing lubricant on the crack growth response of UHMWPE. It was hypothesized that the change in lubricant viscosity as a result of HA would affect the fatigue life of the polymer. A fracture mechanics approach as per ASTM E 647 was adopted for this study. Surface micrograph and surface chemistry analyses were employed to study the micromechanisms of fatigue failure and protein adsorption of the specimen surfaces. Rheological analysis indicated that the addition of HA to diluted bovine serum increased testing lubricant viscosity. HA concentrations of 2.22, 0.55, and 1.5 g/l closely matched the viscosity ranges reported for osteoarthritis, rheumatoid arthritic diseased joint fluid, and periprosthetic fluids respectively. Results showed that the addition of HA to standard diluted bovine serum lubricants, in concentrations similar to that of periprosthetic fluid, delayed crack initiation and crack growth during fatigue testing.

Catalytic cracking of non-edible sunflower oil over ZSM-5 for hydrocarbon bio-jet fuel.

PubMed

Zhao, Xianhui; Wei, Lin; Julson, James; Qiao, Qiquan; Dubey, Ashish; Anderson, Gary

2015-03-25

Non-edible sunflower oils that were extracted from sunflower residual wastes were catalytically cracked over a ZSM-5 catalyst in a fixed-bed reactor at three different reaction temperatures: 450°C, 500°C and 550°C. The catalyst was characterized using XRD, FT-IR, BET and SEM. Characterizations of the upgraded sunflower oils, hydrocarbon fuels, distillation residues and non-condensable gases were carried out. The effect of the reaction temperature on the yield and quality of liquid products was discussed. The results showed that the reaction temperature affected the hydrocarbon fuel yield but had a minor influence on its properties. The highest conversion efficiency from sunflower oils to hydrocarbon fuels was 30.1%, which was obtained at 550°C. The reaction temperature affected the component content of the non-condensable gases. The non-condensable gases generated at 550°C contained the highest content of light hydrocarbons (C1-C5), CO, CO2 and H2. Compared to raw sunflower oils, the properties of hydrocarbon fuels including the dynamic viscosity, pH, moisture content, density, oxygen content and heating value were improved. Copyright © 2015 Elsevier B.V. All rights reserved.

The concept, reality and utility of single-site heterogeneous catalysts (SSHCs).

PubMed

Thomas, John Meurig

2014-05-07

Very substantial advances have recently been made in the design and construction of solid catalysts and in elucidating both their mode of operation and the factors that determine their selectivity and longevity. This Perspective explains how and why such progress has been made. One important factor, the deployment of single-site heterogeneous and enzymatic catalysts, used either alone or in conjunction with other strategies, including metabolic engineering, enables a multitude of new products (for example, environmentally clean jet fuel) to be readily manufactured. In a practical sense SSHCs enable the advantages of homogeneous and to a lesser degree enzymatic catalysts to be united with those of heterogeneous ones. With the aid of the vastly increasing families of nanoporous solids, desired catalytically active sites may be engineered in atomic detail on their inner, accessible surfaces, thereby opening up new possibilities in synthetic organic chemistry - as in the smooth formation of C-C and C[double bond, length as m-dash]N bonds in a number of intermolecular reactions - as well as in photocatalysts and in fluidized catalytic cracking of hydrocarbons.

Catalytic cracking of a Wilmington vacuum oil gas and selected hydrotreated products: Topical report

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wells, J.W.; Zagula, E.J.

1987-05-01

The catalytic cracking of a Wilmington vacuum gas oil and the products from mild hydrotreating and severe hydrotreating of this gas oil was evaluated over a low metal equilibrium catalyst in a microconfined bed unit (MCBU). Two levels of catalytic cracking severity were evaluated for these three samples. The performance and product analysis showed that hydrotreating improves the quality of catalytic cracker feedstock and the resultant products. The results also indicated that a level of hydrotreating exists above which the quality of the liquid products and the yields of coke and heavy oil are not affected significantly by the severitymore » of the catalytic cracking process. As expected, the sulfur and nitrogen content of the liquid products (gasolines, light cycle oil, and heavy cycle oil) were found to decrease as the severity of the feed hydrotreating increased. The distribution of sulfur and nitrogen in the liquid products was found to be independent of cracking conditions or product yields for a given level of hydrogenation. Analysis of the gas products shows that the degree of hydrogen transfer increases with the severity of hydrogenation. As cracking severity increases, the apparent degree of hydrogen transfer decreases, and the concentration of olefinic compounds increases relative to the saturated compounds. In the future, these results will be compared to similar results from a Mayan vacuum gas oil. 10 refs., 17 figs., 10 tabs.« less

Unlocking the potential of supported liquid phase catalysts with supercritical fluids: low temperature continuous flow catalysis with integrated product separation

PubMed Central

Franciò, Giancarlo; Hintermair, Ulrich; Leitner, Walter

2015-01-01

Solution-phase catalysis using molecular transition metal complexes is an extremely powerful tool for chemical synthesis and a key technology for sustainable manufacturing. However, as the reaction complexity and thermal sensitivity of the catalytic system increase, engineering challenges associated with product separation and catalyst recovery can override the value of the product. This persistent downstream issue often renders industrial exploitation of homogeneous catalysis uneconomical despite impressive batch performance of the catalyst. In this regard, continuous-flow systems that allow steady-state homogeneous turnover in a stationary liquid phase while at the same time effecting integrated product separation at mild process temperatures represent a particularly attractive scenario. While continuous-flow processing is a standard procedure for large volume manufacturing, capitalizing on its potential in the realm of the molecular complexity of organic synthesis is still an emerging area that requires innovative solutions. Here we highlight some recent developments which have succeeded in realizing such systems by the combination of near- and supercritical fluids with homogeneous catalysts in supported liquid phases. The cases discussed exemplify how all three levels of continuous-flow homogeneous catalysis (catalyst system, separation strategy, process scheme) must be matched to locate viable process conditions. PMID:26574523

Unlocking the potential of supported liquid phase catalysts with supercritical fluids: low temperature continuous flow catalysis with integrated product separation.

PubMed

Franciò, Giancarlo; Hintermair, Ulrich; Leitner, Walter

2015-12-28

Solution-phase catalysis using molecular transition metal complexes is an extremely powerful tool for chemical synthesis and a key technology for sustainable manufacturing. However, as the reaction complexity and thermal sensitivity of the catalytic system increase, engineering challenges associated with product separation and catalyst recovery can override the value of the product. This persistent downstream issue often renders industrial exploitation of homogeneous catalysis uneconomical despite impressive batch performance of the catalyst. In this regard, continuous-flow systems that allow steady-state homogeneous turnover in a stationary liquid phase while at the same time effecting integrated product separation at mild process temperatures represent a particularly attractive scenario. While continuous-flow processing is a standard procedure for large volume manufacturing, capitalizing on its potential in the realm of the molecular complexity of organic synthesis is still an emerging area that requires innovative solutions. Here we highlight some recent developments which have succeeded in realizing such systems by the combination of near- and supercritical fluids with homogeneous catalysts in supported liquid phases. The cases discussed exemplify how all three levels of continuous-flow homogeneous catalysis (catalyst system, separation strategy, process scheme) must be matched to locate viable process conditions. © 2015 The Authors.

Heterogeneous catalysis in complex, condensed reaction media

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cantu, David C.; Wang, Yang-Gang; Yoon, Yeohoon

Many reactions required for the upgrading of biomass into fuels and chemicals—hydrogenation, hydrodeoxygenation, hydrocracking—are ostensibly similar to those practiced in the upgrading of petroleum into fuels. But, repurposing hydroprocessing catalysts from refinery operations to treat bio-oil has proved to be unsatisfactory. New catalysts are needed because the composition of the biogenic reactants differs from that of petroleum-derived feedstocks (e.g. the low concentration of sulfur in cellulose-derived biomass precludes use of metal sulfide catalysts unless sulfur is added to the reaction stream). New processes are needed because bio-oils oligomerize rapidly, forming intractable coke and “gunk”, at temperatures so low that themore » desired upgrading reactions are impractically slow, and so low that the bio-oil upgrading must be handled as a condensed fluid. Ideally, the new catalysts and processes would exploit the properties of the multiple phases present in condensed bio-oil, notably the polarizability and structure of the fluid near a catalyst’s surface in the cybotactic region. The results of preliminary modeling of the cybotactic region of different catalyst surfaces in the hydrogenation of phenol suggest that Pd catalysts supported on hydrophilic surfaces are more active than catalysts based on lipophilic supports because the former serve to enhance the concentration of the phenol in the vicinity of the Pd. The effect stems from thermodynamics, not the rate of mass transport. This work was supported by the US Department of Energy, Office of Energy Efficiency and Renewable Energy, Bioenergy Technologies Office. Pacific Northwest National Laboratory (PNNL) is a multiprogram national laboratory operated for DOE by Battelle.« less

Metaloxide--ZrO2 catalysts for the esterification and transesterification of free fatty acids and triglycerides to obtain bio-diesel

DOEpatents

Kim, Manhoe; Salley, Steven O.; Ng, K. Y. Simon

2016-09-06

Mixed metal oxide catalysts (ZnO, CeO, La2O3, NiO, Al203, SiO2, TiO2, Nd2O3, Yb2O3, or any combination of these) supported on zirconia (ZrO2) or hydrous zirconia are provided. These mixed metal oxide catalysts can be prepared via coprecipitation, impregnation, or sol-gel methods from metal salt precursors with/without a Zirconium salt precursor. Metal oxides/ZrO2 catalyzes both esterification and transesterification of oil containing free fatty acids in one batch or in single stage. In particular, these mixed metal oxides supported or added on zirconium oxide exhibit good activity and selectivity for esterification and transesterification. The low acid strength of this catalyst can avoid undesirable side reaction such as alcohol dehydration or cracking of fatty acids. Metal oxides/ZrO2 catalysts are not sensitive to any water generated from esterification. Thus, esterification does not require a water free condition or the presence of excess methanol to occur when using the mixed metal oxide catalyst. The FAME yield obtained with metal oxides/ZrO2 is higher than that obtained with homogeneous sulfuric acid catalyst. Metal oxides/ZrO2 catalasts can be prepared as strong pellets and in various shapes for use directly in a flow reactor. Furthermore, the pellet has a strong resistance toward dissolution to aqueous or oil phases.

Influence of Pore-Fluid Pressure on Elastic Wave Velocity and Electrical Conductivity in Water-Saturated Rocks

NASA Astrophysics Data System (ADS)

Higuchi, A.; Watanabe, T.

2013-12-01

Pore-fluid pressure in seismogenic zones can play a key role in the occurrence of earthquakes (e.g., Sibson, 2009). Its evaluation via geophysical observations can lead to a good understanding of seismic activities. The evaluation requires a thorough understanding of the influence of the pore-fluid pressure on geophysical observables like seismic velocity and electrical conductivity. We have studied the influence of pore-fluid pressure on elastic wave velocity and electrical conductivity in water-saturated rocks. Fine grained (100-500μm) biotite granite (Aji, Kagawa pref., Japan) was used as rock samples. The density is 2.658-2.668 g/cm3, and the porosity 0.68-0.87%. The sample is composed of 52.8% plagioclase, 36.0% Quartz, 3.0% K-feldspar, 8.2% biotite. SEM images show that a lot of grain boundaries are open. Few intracrystalline cracks were observed. Following the method proposed by David and Zimmerman (2012), the distribution function of crack aspect ratio was evaluated from the pressure dependence of compressional and shear wave velocities in a dry sample. Cylindrical sample has dimensions of 25 mm in diameter and 30 mm in length, and saturated with 0.01 mol/l KCl aqueous solution. Compressional and shear wave velocities were measured with the pulse transmission technique (PZT transducers, f=2 MHz), and electrical conductivity the two-electrode method (Ag-AgCl electrodes, f=1 Hz-100 kHz). Simultaneous measurements of velocities and conductivity were made using a 200 MPa hydrostatic pressure vessel, in which confining and pore-fluid pressures can be separately controlled. The pore-fluid is electrically insulated from the metal work of the pressure vessel by using a newly designed plastic device (Watanabe and Higuchi, 2013). The confining pressure was progressively increased up to 25 MPa, while the pore-fluid pressure was kept at 0.1 MPa. It took five days or longer for the electrical conductivity to become stationary after increasing the confining pressure. Elastic wave velocities and electrical conductivity showed reproducibly contrasting changes for a small increase in the confining pressure. The elastic wave velocities increased only by 5% as the confining pressure increased from 0.1 MPa to 25 MPa, while the electrical conductivity decreased by an order of magnitude. Based on the SEM examinations, open grain boundaries work as cracks. The changes in elastic wave velocities and electrical conductivity must be caused by the closure of open grain boundaries. Most (˜80%) of the decrease in electrical conductivity occurred below the confining pressure of 5 MPa. As the confining pressure increased from 0.1 MPa to 5 MPa, cracks with the aspect ratio smaller than 7.5×10-5 were closed. The decrease in porosity was only 0.0005%. Such a small change in porosity caused a large change in electrical conductivity. The connectivity of fluid was maintained at the confining pressure of 25 MPa by cracks with the aspect ratio larger than 3.7×10-4. Simultaneous measurements have provided us a lot of information on the microstructure of fluid-bearing rocks.

Characterization of MoVTeNbO x catalysts during oxidation reactions using in situ/operando techniques: A review

DOE PAGES

Lwin, Soe; Diao, Weijian; Baroi, Chinmoy; ...

2017-04-08

The domestic fossil feedstock in recent years is shifting towards light hydrocarbons due to abundance of shale gas from hydraulic fracturing. This shift induces a need for greater flexibility in both new and existing processing plants to produce consumer products (polymers, paints, lubricants, etc.) from new feedstocks. The oxidative catalytic reactions operate at milder conditions than the processing of feedstocks through steam cracking. The conversion of light feedstocks (C3 and shorter hydrocarbons) to high value chemicals through highly selective catalysts in the presence of oxygen plays a crucial role in eliminating wastes, reducing greenhouse gas emissions and lowering market prices.more » Among all catalysts for light hydrocarbon processing through oxidation reactions, bulk mixed metal oxides such as MoVTe(Sb)NbO x catalysts are the most promising due to their performance under favorable reaction conditions (temperature, pressure, etc). Here, state-of-the-art in situ/operando techniques along with transient kinetics can revolutionize the development of catalysts by providing information about the nature of active sites, intermediates and kinetics under realistic industrial conditions. Only through detailed understanding of these catalyst behaviors can new synthesis methods be developed that will improve reactivity, selectivity and lifetimes of these catalysts. In this review, dynamic changes of this mixed oxide catalyst during the reaction (such as changes in surface composition, oxidation states, acidity, etc) are discussed mainly from knowledge and insights obtained from these in situ/operando approaches. The most common oxidation reactions driven by the MoVTeNbO x catalysts and studied under operando/in situ conditions to be discussed here are: (1) oxidative dehydrogenation of light alkanes (ethane and propane), (2) propane ammoxidation to acrylonitrile and (3) selective oxidation of propane to acrylic acid.« less

Characterization of MoVTeNbO x catalysts during oxidation reactions using in situ/operando techniques: A review

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lwin, Soe; Diao, Weijian; Baroi, Chinmoy

The domestic fossil feedstock in recent years is shifting towards light hydrocarbons due to abundance of shale gas from hydraulic fracturing. This shift induces a need for greater flexibility in both new and existing processing plants to produce consumer products (polymers, paints, lubricants, etc.) from new feedstocks. The oxidative catalytic reactions operate at milder conditions than the processing of feedstocks through steam cracking. The conversion of light feedstocks (C3 and shorter hydrocarbons) to high value chemicals through highly selective catalysts in the presence of oxygen plays a crucial role in eliminating wastes, reducing greenhouse gas emissions and lowering market prices.more » Among all catalysts for light hydrocarbon processing through oxidation reactions, bulk mixed metal oxides such as MoVTe(Sb)NbO x catalysts are the most promising due to their performance under favorable reaction conditions (temperature, pressure, etc). Here, state-of-the-art in situ/operando techniques along with transient kinetics can revolutionize the development of catalysts by providing information about the nature of active sites, intermediates and kinetics under realistic industrial conditions. Only through detailed understanding of these catalyst behaviors can new synthesis methods be developed that will improve reactivity, selectivity and lifetimes of these catalysts. In this review, dynamic changes of this mixed oxide catalyst during the reaction (such as changes in surface composition, oxidation states, acidity, etc) are discussed mainly from knowledge and insights obtained from these in situ/operando approaches. The most common oxidation reactions driven by the MoVTeNbO x catalysts and studied under operando/in situ conditions to be discussed here are: (1) oxidative dehydrogenation of light alkanes (ethane and propane), (2) propane ammoxidation to acrylonitrile and (3) selective oxidation of propane to acrylic acid.« less

Investigation of wing crack formation with a combined phase-field and experimental approach

NASA Astrophysics Data System (ADS)

Lee, Sanghyun; Reber, Jacqueline E.; Hayman, Nicholas W.; Wheeler, Mary F.

2016-08-01

Fractures that propagate off of weak slip planes are known as wing cracks and often play important roles in both tectonic deformation and fluid flow across reservoir seals. Previous numerical models have produced the basic kinematics of wing crack openings but generally have not been able to capture fracture geometries seen in nature. Here we present both a phase-field modeling approach and a physical experiment using gelatin for a wing crack formation. By treating the fracture surfaces as diffusive zones instead of as discontinuities, the phase-field model does not require consideration of unpredictable rock properties or stress inhomogeneities around crack tips. It is shown by benchmarking the models with physical experiments that the numerical assumptions in the phase-field approach do not affect the final model predictions of wing crack nucleation and growth. With this study, we demonstrate that it is feasible to implement the formation of wing cracks in large scale phase-field reservoir models.

Transportation fuel production by combination of LDPE thermal cracking and catalytic hydroreforming

DOE Office of Scientific and Technical Information (OSTI.GOV)

Escola, J.M., E-mail: josemaria.escola.saez@urjc.es; Aguado, J.; Serrano, D.P.

2014-11-15

Highlights: • h-Beta samples were impregnated with Ni nitrate to achieve Ni contents of 1.5%, 4%, 7% and 10%. • Larger and more easily reducible metal particles were obtained on Ni 7%/h-Beta and Ni 10%/h-Beta. • Higher Ni contents increased the amount of gases at the expenses of diesel fractions. • Maximum selectivity to automotive fuels (∼81%) was obtained with Ni 7%/h-Beta. • Ni loading also enhanced olefins saturation up to Ni 7%/h-Beta. - Abstract: Fuel production from plastics is a promising way to reduce landfilling rates while obtaining valuable products. The usage of Ni-supported hierarchical Beta zeolite (h-Beta) formore » the hydroreforming of the oils coming from LDPE thermal cracking has proved to produce high selectivities to gasoline and diesel fuels (>80%). In the present work, the effect of the Ni loading on Ni/h-Beta is investigated in the hydroreforming of the oils form LDPE thermal cracking. h-Beta samples were impregnated with Ni nitrate, calcined and reduced in H{sub 2} up to 550 °C to achieve different Ni contents: 1.5%, 4%, 7% and 10%. Larger and more easily reducible metal particles were obtained on Ni 7%/h-Beta and Ni 10%/h-Beta. Hydroreforming tests were carried out in autoclave reactor at 310 °C, under 20 bar H{sub 2}, for 45 min. Ni content progressively increased the amount of gases at the expenses of diesel fractions, while gasoline remained approximately constant about 52–54%. Maximum selectivity to automotive fuels (∼81%) was obtained with Ni 7%/h-Beta. Ni loading also enhanced olefins saturation up to Ni 7%/h-Beta. High cetane indices (71–86) and octane numbers (89–91) were obtained over all the catalysts. Regarding the different studied Ni contents, Ni 7%/h-Beta constitutes a rather promising catalyst for obtaining high quality fuels from LDPE thermal cracking oils.« less

Treatment of gas from an in situ conversion process

DOEpatents

Diaz, Zaida [Katy, TX; Del Paggio, Alan Anthony [Spring, TX; Nair, Vijay [Katy, TX; Roes, Augustinus Wilhelmus Maria [Houston, TX

2011-12-06

A method of producing methane is described. The method includes providing formation fluid from a subsurface in situ conversion process. The formation fluid is separated to produce a liquid stream and a first gas stream. The first gas stream includes olefins. At least the olefins in the first gas stream are contacted with a hydrogen source in the presence of one or more catalysts and steam to produce a second gas stream. The second gas stream is contacted with a hydrogen source in the presence of one or more additional catalysts to produce a third gas stream. The third gas stream includes methane.

A new model of reaction-driven cracking: fluid volume consumption and tensile failure during serpentinization

NASA Astrophysics Data System (ADS)

Eichenbaum-Pikser, J. M.; Spiegelman, M. W.; Kelemen, P. B.; Wilson, C. R.

2013-12-01

Reactive fluid flow plays an important role in a wide range of geodynamic processes, such as melt migration, formation of hydrous minerals on fault surfaces, and chemical weathering. These processes are governed by the complex coupling between fluid transport, reaction, and solid deformation. Reaction-driven cracking is a potentially critical feedback mechanism, by which volume change associated with chemical reaction drives fracture in the surrounding rock. It has been proposed to play a role in both serpentinization and carbonation of peridotite, motivating consideration of its application to mineral carbon sequestration. Previous studies of reactive cracking have focused on the increase in solid volume, and as such, have considered failure in compression. However, if the consumption of fluid is considered in the overall volume budget, the reaction can be net volume reducing, potentially leading to failure in tension. To explore these problems, we have formulated and solved a 2-D model of coupled porous flow, reaction kinetics, and elastic deformation using the finite element model assembler TerraFERMA (Wilson et al, G3 2013 submitted). The model is applied to the serpentinization of peridotite, which can be reasonably approximated as the transfer of a single reactive component (H2O) between fluid and solid phases, making it a simple test case to explore the process. The behavior of the system is controlled by the competition between the rate of volume consumption by the reaction, and the rate of volume replacement by fluid transport, as characterized by a nondimensional parameter χ, which depends on permeability, reaction rate, and the bulk modulus of the solid. Large values of χ correspond to fast fluid transport relative to reaction rate, resulting in a low stress, volume replacing regime. At smaller values of χ, fluid transport cannot keep up with the reaction, resulting in pore fluid under-pressure and tensile solid stresses. For the range of χ relevant to the serpentinization of peridotite, these stresses can reach hundreds of MPa, exceeding the tensile strength of peridotite.

Control system adds to precipitator efficiency

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gurrole, G.

1978-02-01

An electrostatic precipitator in use at Lion Oil Co., Martinez, Calif., in a fluid catalytic cracking and CO boiler application, was upgraded by mechanical sectionalization of the gas passage and a new electronic control system. The electrostatic precipitator is installed upstream of the CO boiler to handle gas flow up to 4.77 ft/sec, and pressure to 4.5 psi. The independent gas chambers in the electrostatic precipitator were divided by installing gas-tight partition walls to form a total of four electrostatic fields. The precipitator was also equipped with adjustable inlet gas flow-control baffles for even gas distribution. Rows of grounded collectingmore » electrodes are parallel with the flow of gas. The emitting electrode system, powered by separate high-energy transformers for each collecting field, uses silicon-controlled rectifiers and analog electronic networks for rapid response to changing gas and dust conditions. Regulatory requirements call for efficient collection of catalyst fines with no more than 40 lb/hr escaping through the boiler stack. Currently, stack losses average about 38 lb/hr. The installation of two additional control systems with transformers and rectifiers should reduce stack losses to 34 lb/hr.« less

Statistics of velocity fluctuations of Geldart A particles in a circulating fluidized bed riser

DOE PAGES

Vaidheeswaran, Avinash; Shaffer, Franklin; Gopalan, Balaji

2017-11-21

Here, the statistics of fluctuating velocity components are studied in the riser of a closed-loop circulating fluidized bed with fluid catalytic cracking catalyst particles. Our analysis shows distinct similarities as well as deviations compared to existing theories and bench-scale experiments. The study confirms anisotropic and non-Maxwellian distribution of fluctuating velocity components. The velocity distribution functions (VDFs) corresponding to transverse fluctuations exhibit symmetry, and follow a stretched-exponential behavior up to three standard deviations. The form of the transverse VDF is largely determined by interparticle interactions. The tails become more overpopulated with an increase in particle loading. The observed deviations from themore » Gaussian distribution are represented using the leading order term in the Sonine expansion, which is commonly used to approximate the VDFs in kinetic theory for granular flows. The vertical fluctuating VDFs are asymmetric and the skewness shifts as the wall is approached. In comparison to transverse fluctuations, the vertical VDF is determined by the local hydrodynamics. This is an observation of particle velocity fluctuations in a large-scale system and their quantitative comparison with the Maxwell-Boltzmann statistics.« less

Process for detoxifying coal tars

DOEpatents

Longwell, John P.; Peters, William A.

1983-01-01

A process for treating liquid hydrocarbons to remove toxic, mutagenic and/or carcinogenic aromatic hydrocarbons comprises feeding the hydrocarbons into a reactor where vapors are thermally treated in contact with a catalyst consisting essentially of calcium oxide or a calcium oxide containing mineral. Thermally treating liquid hydrocarbons in contact with calcium oxide preferentially increases the cracking of aromatics thus producing a product having a reduced amount of aromatic compounds.

Hexagonal boron nitride catalyst in a fixed-bed reactor for exothermic propane oxidation dehydrogenation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tian, Jinshu; Lin, Jinhan; Xu, Mingliang

Hexagonal boron nitride (h-BN) with high thermal conductivity is potentially an effective catalyst for highly exothermic propane oxidative dehydrogenation (ODH) reaction. Here, we report our experimental and theoretic studies of such a catalyst for propane ODH in a fixed-bed reactor. Based on the computational fluid dynamics calculation (CFD) results, the catalyst bed temperature increases by less than 1°C in the h-BN catalyst bed which is much smaller than that (8°C) in the VO x/γ-Al 2O 3 catalyst bed at a similar propane conversion (25%) using a micro-tubular reactor with a diameter of 6 mm. Even in an industrially relevant reactormore » with an inner diameter of 60 mm, a uniform temperature profile can still be maintained using the h-BN catalyst bed due to its excellent thermal conductivity as opposed to a temperature gradient of 47°C in the VO x/γ-Al 2O 3 catalyst bed. The results reported here provide useful information for potential application of h-BN catalyst in propane ODH.« less

Hexagonal boron nitride catalyst in a fixed-bed reactor for exothermic propane oxidation dehydrogenation

DOE PAGES

Tian, Jinshu; Lin, Jinhan; Xu, Mingliang; ...

2018-04-17

Hexagonal boron nitride (h-BN) with high thermal conductivity is potentially an effective catalyst for highly exothermic propane oxidative dehydrogenation (ODH) reaction. Here, we report our experimental and theoretic studies of such a catalyst for propane ODH in a fixed-bed reactor. Based on the computational fluid dynamics calculation (CFD) results, the catalyst bed temperature increases by less than 1°C in the h-BN catalyst bed which is much smaller than that (8°C) in the VO x/γ-Al 2O 3 catalyst bed at a similar propane conversion (25%) using a micro-tubular reactor with a diameter of 6 mm. Even in an industrially relevant reactormore » with an inner diameter of 60 mm, a uniform temperature profile can still be maintained using the h-BN catalyst bed due to its excellent thermal conductivity as opposed to a temperature gradient of 47°C in the VO x/γ-Al 2O 3 catalyst bed. The results reported here provide useful information for potential application of h-BN catalyst in propane ODH.« less

Nanoscale Stress-Corrosion of Geomaterials in Aqueous Solutions

NASA Astrophysics Data System (ADS)

Criscenti, L. J.; Rimsza, J. M.; Matteo, E. N.; Jones, R. E.

2017-12-01

Predicting subcritical crack propagation in low-permeability geo-materials is an unsolved problem crucial to assessing shale caprocks at CO2 sequestration sites, and controlling fracturing for gas and oil extraction. Experiments indicate that chemical reactions at fluid-material interfaces play a major role in subcritical crack growth by weakening the material and altering crack nucleation and growth rates. However, understanding subsurface fracture has been hindered by a lack of understanding of the mechanisms relating chemical environment to mechanical outcome, and a lack of capability directly linking atomistic insight to macroscale observables. We are using both molecular simulation and experiment to develop an atomistic-level understanding of the chemical-mechanical coupling that controls subcritical crack propagation. We are investigating fracture of isotropic silica glass in different environments (air, distilled water, and Na+-rich solutions) and will extend our research to include clay minerals in shales. Molecular simulations are performed with ReaxFF, a reactive force field that allows for explicit modeling of bond breaking and formation processes during crack propagation. A coarse-graining method produces calculated fracture toughness values from the atomistic data. We are performing double cleavage drilled compression (DCDC) experiments in aqueous environmental chambers and monitoring crack propagation with either a confocal or atomic force microscope. Our results show that silica fracture toughness decreases as the environment changes from air to distilled water to Na+-rich solutions. These results suggest that our newly developed computational and experimental techniques can be used to investigate the impact of fluid composition on crack growth in geo-materials and that we will be able to use these methods to understand coupled chemo-mechanical processes and predict crack propagation in shale minerals. Sandia National Laboratories is a multimission laboratory managed and operated by National Technology and Engineering Solutions of Sandia LLC, a wholly owned subsidiary of Honeywell International Inc. for the U.S. Department of Energy's National Nuclear Security Administration under contract DE-NA0003525.

Crack - seal veins - what we learnt since the seminal work of John Ramsay

NASA Astrophysics Data System (ADS)

Urai, Janos L.; Bons, Paul D.

2017-04-01

In the nineteen-eighties, John Ramsay and co-workers have laid the basis for much of our current understanding of tectonic veins, by proposing that tectonic veins accrete in many small increments of cracking and sealing, making the link to cyclic stress and fluid pressure cycles and the earthquake cycle, and by proposing that fibrous veins track the opening trajectory, which has created a toolbox to analyse progressive deformation in rocks. They recognised syntaxial and antitaxial veins, which grow depending on the composition of the wall rock and the vein. Following on these seminal contributions, advances in analysing the microstructure and chemical signature in crack-seal veins made a lot of progress, facilitated by the rapid increase in micro analytical tools like cathodeluminescence and EBSD. Initial modelling of crystal growth in crack- seal veins provided an explanation of how crystals become fibrous without being deformed and explained how fibres sometimes do and sometimes don't follow the opening trajectory. This was followed by numerical models of crystal growth to study the development of crystal facets after larger crack increments, and experimental study of the sealing dynamics of syntaxial veins. These models were initially kinematic, using the ELLE microdynamic simulation package, and more recently incorporating the physics of the growing interface using the Phase Field method, which now allows 3D simulation of both syntaxial and antitaxial veins and can simultaneously compute the evolving permeability of the crack using Lattice Boltzmann techniques. Parallel to these developments we developed an understanding of the strength of the vein cement, and, using Discrete Element Techniques, explored the effects of differences of the strength of the vein and its adhesion to the wall rock on fracture patterns in crack-seal systems in changing stress fields. This presentation will review these developments, showing how the ideas of John Ramsay inspired follow up work leading to a much better understanding of the complex feedback systems between fracture growth, crystal growth and fluid flow in crack-seal systems.

Catalytic and thermal cracking processes of waste cooking oil for bio-gasoline synthesis

NASA Astrophysics Data System (ADS)

Dewanto, Muhammad Andry Rizki; Januartrika, Aulia Azka; Dewajani, Heny; Budiman, Arief

2017-03-01

Non-renewable energy resources such as fossil fuels, and coal were depleted as the increase of global energy demand. Moreover, environmental aspect becomes a major concern which recommends people to utilize bio-based resources. Waste cooking oil is one of the economical sources for biofuel production and become the most used raw material for biodiesel production. However, the products formed during frying, can affect the trans-esterification reaction and the biodiesel properties. Therefore, it needs to convert low-quality cooking oil directly into biofuel by both thermal and catalytic cracking processes. Thermal and catalytic cracking sometimes are regarded as prospective bio-energy conversion processes. This research was carried out in the packed bed reactor equipped with 2 stages preheater with temperature of reactor was variated in the range of 450-550°C. At the same temperature, catalytic cracking had been involved in this experiment, using activated ZSM-5 catalyst with 1 cm in length. The organic liquid product was recovered by three stages of double pipe condensers. The composition of cracking products were analyzed using GC-MS instrument and the caloric contents were analyzed using Bomb calorimeter. The results reveal that ZSM-5 was highly selective toward aromatic and long aliphatic compounds formation. The percentage recovery of organic liquid product from the cracking process varies start from 8.31% and the optimal results was 54.08%. The highest heating value of liquid product was resulted from catalytic cracking process at temperature of 450°C with value of 10880.48 cal/gr and the highest product yield with 54.08% recovery was achieved from thermal cracking process with temperature of 450°C.

Low Cost Olefin Production from Shale Gas by Laser Enhanced Pyrolysis through Spatial Beam Decoherence. Phase 1 Final Report.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hutton, Phillip N.

This report describes research into an innovative laser-enhanced catalytic pyrolysis technology that has the potential to significantly decrease the cost of cracking ethane and other alkanes found in shale gas ethylene. Similar to how water is resonantly heated by microwaves, a CO 2 laser can resonantly heat ethylene, producing radicals that convert ethane to ethylene at lower reactor temperatures. Proof of concept experiments were performed to determine if commercial grade CO 2 lasers at one-twenty fifth the cost of scientific grade lasers could crack ethane at lower temperatures than conventional technology. Cr doped MgO catalyst was then inserted in themore » reaction chamber to further increase conersion rates.« less

Mechanics of the injected pulsejet into gelatin gel and evaluation of the effect by puncture and crack generation and growth

NASA Astrophysics Data System (ADS)

Kato, T.; Arafune, T.; Washio, T.; Nakagawa, A.; Ogawa, Y.; Tominaga, T.; Sakuma, I.; Kobayashi, E.

2014-08-01

Recently, fluid jets have become widely used in medical devices and have been created and evaluated in clinical environments. Such devices are classified into two broad groups; those adopting continuous jets and those adopting discrete (or pulsed) jets. We developed a discrete jet device for brain cancer treatment, called a laser-induced liquid jet (LILJ) system. Although several studies have evaluated the availability and described the treatment mechanisms of fluid jet devices, the mechanisms of the fluid and injected material remain under-investigated. In this paper, we report the mechanism of frequent pulsejet injections into a viscoelastic biological material; namely, simulated gelatin brain tissue. The mechanism is evaluated by the injection depth, an easily measured parameter. To explain the injection mechanism, we propose that the pulsejet is pressured by forces introduced by resistance on the side surface of the hole and the reaction force proportionate to the injection depth. The pulsejet generated and propagated cracks in the gelatin, and the resistance eventually fractured the side surface of the hole. We evaluated the proposed model by measuring the behavior of pulsejets injected into gelatin by the LILJ. From the results, the following conclusions were obtained. First, the proposed model accurately describes the behavior of the injected pulsejet. Second, whether the hole or crack growth largely increases the final injection depth can be evaluated from differences in the decay constant. Finally, crack growth increases the final injection depth when the number of the injected pulsejets is greater than the inverse of the decay constant.

Use of GC/MS Analysis to Distinguish Between Vapor Intrusion and Indoor Sources of VOCs - Standardized Protocol for On-Site Evaluation of Vapor Intrusion

DTIC Science & Technology

2014-07-01

Testing a Sealed Crack in a Concrete Floor .................................................................. 14 Figure 5: VOC Responses to...Engineered Fluid Toluene Some paints and adhesives SprayPAK Enamel , Minwax Wood Finish Xylenes Adhesives, paints, gasoline Bonide Tree Sprays and...expansion joints, plumbing penetrations, or cracks . 3 Note that if indoor air concentrations are

A Mesopore-Dependent Catalytic Cracking of n-Hexane Over Mesoporous Nanostructured ZSM-5.

PubMed

Qamar, M; Ahmed, M I; Qamaruddin, M; Asif, M; Sanhoob, M; Muraza, O; Khan, M Y

2018-08-01

Herein, pore size, crystalinity, and Si/Al ratio of mesoporous ZSM-5 (MFI) nanocrystals was controlled by synthesis parameters, such as surfactant concentration ([3-(trimethoxysilyl)propyl] hexa-decyl dimethyl ammonium chloride), sodium hydroxide concentrations, synthesis temperature and time. The morphology, surface structure and composition of the MFI particles was systematically investigated. More notably, the mesopore-dependent catalytic activity of ZSM-5 was evaluated by studying the cracking of n-hexane. The findings suggest the porosity has pronounced impact on the catalytic activity, selectivity and stability of ZSM-5 nanocrystals. Critical surface attributes such as nature of acid sites (Brønsted and Lewis), concentration, and strength are obtained by the infrared study of adsorbed probe molecules (pyridine) and the temperature programmed desorption. In spite of being weaker in Si/Al ratio or acidic strength, mesoporous catalysts showed more stable and efficient cracking of n-hexane suggesting that acidity seems not the predominant factor operative in the activity, selectivity and stability.

Differing responses of zircon, chevkinite-(Ce), monazite-(Ce) and fergusonite-(Y) to hydrothermal alteration: Evidence from the Keivy alkaline province, Kola Peninsula, Russia

NASA Astrophysics Data System (ADS)

Macdonald, Ray; Bagiński, Bogusław; Zozulya, Dmitry

2017-09-01

A quartzolite from the Rova occurrence, Keivy alkali granite province, Kola Peninsula, Russia, is used to examine the differing responses of certain rare-metal minerals during interaction with hydrothermal fluids. The minerals are two silicates [chevkinite-(Ce) and zircon], a phosphate [monazite-(Ce)] and an oxide [fergusonite-(Y)]. Textural evidence is taken to show that the dominant alteration mechanism was interface-coupled dissolution-reprecipitation. Zircon was the most pervasively altered, possibly by broadening of cleavage planes or fractures; the other minerals were altered mainly on their rims and along cracks. The importance of cracks in promoting fluid access is stressed. The compositional effects of the alteration of each phase are documented. The hydrothermal fluids carried few ligands capable of transporting significant amounts of rare-earth elements (REE), high field strength elements (HFSE) and actinides; alteration is inferred to have been promoted by mildly alkaline, Ca-bearing fluids. Expansion cracks emanating from fergusonite-(Y) are filled with unidentified material containing up to 35 wt% UO2 and 25 wt% REE2O3, indicating late-stage, short-distance mobility of these elements. Electron microprobe chemical dating of monazite yielded an age of 1665 ± 22 Ma, much younger than the formation age of the Keivy province (2.65-2.67 Ga) but comparable to that of the Svecofennian metamorphic event which affected the area (1.9-1.7 Ga) or during fluid-thermal activation of the region during rapakivi granite magmatism (1.66-1.56 Ga). Dates for altered monazite range from 2592 ± 244 Ma to 773 ± 88 Ma and reflect disturbance of the U-Th-Pb system during alteration.

Wood-derived olefins by steam cracking of hydrodeoxygenated tall oils.

PubMed

Pyl, Steven P; Dijkmans, Thomas; Antonykutty, Jinto M; Reyniers, Marie-Françoise; Harlin, Ali; Van Geem, Kevin M; Marin, Guy B

2012-12-01

Tall oil fractions obtained from Norwegian spruce pulping were hydrodeoxygenated (HDO) at pilot scale using a commercial NiMo hydrotreating catalyst. Comprehensive two dimensional gas chromatography (GC×GC) showed that HDO of both tall oil fatty acids (TOFA) and distilled tall oil (DTO) produced highly paraffinic hydrocarbon liquids. The hydrotreated fractions also contained fatty acid methyl esters and norabietane and norabietatriene isomers. Steam cracking of HDO-TOFA in a pilot plant revealed that high light olefin yields can be obtained, with 35.4 wt.% of ethene and 18.2 wt.% of propene at a coil outlet pressure (COP) of 1.7 bara, a dilution of 0.45 kg(steam)/kg(HDO-TOFA) and a coil outlet temperature (COT) of 820 °C. A pilot plant coking experiment indicated that cracking of HDO-TOFA at a COT of 850 °C results in limited fouling in the reactor. Co-cracking of HDO tall oil fractions with a typical fossil-based naphtha showed improved selectivity to desired light olefins, further demonstrating the potential of large scale olefin production from hydrotreated tall oil fractions in conventional crackers. Copyright © 2012 Elsevier Ltd. All rights reserved.

Crack Mitigation in Concrete: Superabsorbent Polymers as Key to Success?

PubMed Central

Mignon, Arn; Snoeck, Didier; Dubruel, Peter; Van Vlierberghe, Sandra; De Belie, Nele

2017-01-01

Cracking is a major concern in building applications. Cracks may arise from shrinkage, freeze/thawing and/or structural stresses, amongst others. Several solutions can be found but superabsorbent polymers (SAPs) seem to be interesting to counteract these problems. At an early age, the absorbed water by the SAPs may be used to mitigate autogenous and plastic shrinkage. The formed macro pores may increase the freeze/thaw resistance. The swelling upon water ingress may seal a crack from intruding fluids and may regain the overall water-tightness. The latter water may promote autogenous healing. The use of superabsorbent polymers is thus very interesting. This review paper summarizes the current research and gives a critical note towards the use of superabsorbent polymers in cementitious materials. PMID:28772599

Crack Mitigation in Concrete: Superabsorbent Polymers as Key to Success?

PubMed

Mignon, Arn; Snoeck, Didier; Dubruel, Peter; Van Vlierberghe, Sandra; De Belie, Nele

2017-02-28

Cracking is a major concern in building applications. Cracks may arise from shrinkage, freeze/thawing and/or structural stresses, amongst others. Several solutions can be found but superabsorbent polymers (SAPs) seem to be interesting to counteract these problems. At an early age, the absorbed water by the SAPs may be used to mitigate autogenous and plastic shrinkage. The formed macro pores may increase the freeze/thaw resistance. The swelling upon water ingress may seal a crack from intruding fluids and may regain the overall water-tightness. The latter water may promote autogenous healing. The use of superabsorbent polymers is thus very interesting. This review paper summarizes the current research and gives a critical note towards the use of superabsorbent polymers in cementitious materials.

Bio-oil from fast pyrolysis of lignin: Effects of process and upgrading parameters.

PubMed

Fan, Liangliang; Zhang, Yaning; Liu, Shiyu; Zhou, Nan; Chen, Paul; Cheng, Yanling; Addy, Min; Lu, Qian; Omar, Muhammad Mubashar; Liu, Yuhuan; Wang, Yunpu; Dai, Leilei; Anderson, Erik; Peng, Peng; Lei, Hanwu; Ruan, Roger

2017-10-01

Effects of process parameters on the yield and chemical profile of bio-oil from fast pyrolysis of lignin and the processes for lignin-derived bio-oil upgrading were reviewed. Various process parameters including pyrolysis temperature, reactor types, lignin characteristics, residence time, and feeding rate were discussed and the optimal parameter conditions for improved bio-oil yield and quality were concluded. In terms of lignin-derived bio-oil upgrading, three routes including pretreatment of lignin, catalytic upgrading, and co-pyrolysis of hydrogen-rich materials have been investigated. Zeolite cracking and hydrodeoxygenation (HDO) treatment are two main methods for catalytic upgrading of lignin-derived bio-oil. Factors affecting zeolite activity and the main zeolite catalytic mechanisms for lignin conversion were analyzed. Noble metal-based catalysts and metal sulfide catalysts are normally used as the HDO catalysts and the conversion mechanisms associated with a series of reactions have been proposed. Copyright © 2017 Elsevier Ltd. All rights reserved.

Coupling fluid-structure interaction with phase-field fracture

NASA Astrophysics Data System (ADS)

Wick, Thomas

2016-12-01

In this work, a concept for coupling fluid-structure interaction with brittle fracture in elasticity is proposed. The fluid-structure interaction problem is modeled in terms of the arbitrary Lagrangian-Eulerian technique and couples the isothermal, incompressible Navier-Stokes equations with nonlinear elastodynamics using the Saint-Venant Kirchhoff solid model. The brittle fracture model is based on a phase-field approach for cracks in elasticity and pressurized elastic solids. In order to derive a common framework, the phase-field approach is re-formulated in Lagrangian coordinates to combine it with fluid-structure interaction. A crack irreversibility condition, that is mathematically characterized as an inequality constraint in time, is enforced with the help of an augmented Lagrangian iteration. The resulting problem is highly nonlinear and solved with a modified Newton method (e.g., error-oriented) that specifically allows for a temporary increase of the residuals. The proposed framework is substantiated with several numerical tests. In these examples, computational stability in space and time is shown for several goal functionals, which demonstrates reliability of numerical modeling and algorithmic techniques. But also current limitations such as the necessity of using solid damping are addressed.

Multistage crack seal vein and hydrothermal Ni enrichment in serpentinized ultramafic rocks (Koniambo massif, New Caledonia)

NASA Astrophysics Data System (ADS)

Cathelineau, Michel; Myagkiy, Andrey; Quesnel, Benoit; Boiron, Marie-Christine; Gautier, Pierre; Boulvais, Philippe; Ulrich, Marc; Truche, Laurent; Golfier, Fabrice; Drouillet, Maxime

2017-10-01

Sets of fractures and breccia sealed by Ni-rich silicates and quartz occur within saprock of the New Caledonian regolith developed over ultramafic rocks. The crystallization sequence in fractures is as follows: (1) serpentine stage: lizardite > polygonal serpentine > white lizardite; (2) Ni stage: Ni-Mg kerolite followed by red-brown microcrystalline quartz; and (3) supergene stages. The red-brown microcrystalline quartz corresponds to the very last stage of the Ni sequence and is inferred to have precipitated within the 50-95 °C temperature range. It constitutes also the main cement of breccia that has all the typical features of hydraulic fracturing. The whole sequence is therefore interpreted as the result of hydrothermal fluid circulation under medium to low temperature and fluctuating fluid pressure. Although frequently described as the result of a single downward redistribution of Ni and Mg leached in the upper part of the regolith under ambient temperature, the Ni silicate veins thus appear as the result of recurrent crack and seal process, corresponding to upward medium temperature fluid convection, hydraulic fracturing and subsequent fluid mixing, and mineral deposition.

Thermal oxidative degradation reactions of linear perfluoroalky lethers

NASA Technical Reports Server (NTRS)

Jones, W. R., Jr.; Paciorek, K. J. L.; Ito, T. I.; Kratzer, R. H.

1982-01-01

Thermal and thermal oxidative stability studies were performed on linear perfluoro alkyl ether fluids. The effect on degradation by metal catalysts and degradation inhibitors are reported. The liner perfluoro alkylethers are inherently unstable at 316 C in an oxidizing atmosphere. The metal catalysts greatly increased the rate of degradation in oxidizing atmospheres. In the presence of these metals in an oxidizing atmosphere, the degradation inhibitors were highly effective in arresting degradation at 288 C. However, the inhibitors had only limited effectiveness at 316 C. The metals promote degradation by chain scission. Based on elemental analysis and oxygen consumption data, the linear perfluoro alkylether fluids have a structural arrangement based on difluoroformyl and tetrafluoroethylene oxide units, with the former predominating.

Conversion of Small Algal Oil Sample to JP-8

DTIC Science & Technology

2012-01-01

cracking of Algal Oil to SPK Hydroprocessing Lab Plant uop Nitrogen Hydrogen Product ., __ Small Scale Lab Hydprocessing plant - Down flow trickle ... bed configuration - Capable of retaining 25 cc of catalyst bed Meter UOP ·CONFIDENTIAL File Number The catalytic deoxygenation stage of the...content which combined with the samples acidity, is a challenge to reactor metallurgy. None the less, an attempt was made to convert this sample to

Supercritical fluid attachment of palladium nanoparticles on aligned carbon nanotubes.

PubMed

Ye, Xiang-Rong; Lin, Yuehe; Wai, Chien M; Talbot, Jan B; Jin, Sungho

2005-06-01

Nanocomposite materials consisting of Pd nanoparticles deposited on aligned multi-walled carbon nanotubes have been fabricated through hydrogen reduction of palladium-beta-diketone precursor in supercritical carbon dioxide. The supercritical fluid processing allowed deposition of high-density Pd nanoparticles (approximately 5-10 nm) on both as-grown (unfunctionalized) and functionalized (using HNO3 oxidation) nanotubes. However, the wet processing for functionalization results in pre-agglomerated, bundle-shaped nanotubes, thus significantly reducing the effective surface area for Pd particle deposition, although the bundling provides more secure, lock-in-place positioning of nanotubes and Pd catalyst particles. The nanotube bundling is substantially mitigated by Pd nanoparticle deposition on the unfunctionalized and geometrically separated nanotubes, which provides much higher catalyst surface area. Such nanocomposite materials utilizing geometrically secured and aligned nanotubes can be useful for providing much enhanced catalytic activities to chemical and electrochemical reactions (e.g., fuel cell reactions), and eliminate the need for tedious catalyst recovery process after the reaction is completed.

A complete two-phase model of a porous cathode of a PEM fuel cell

NASA Astrophysics Data System (ADS)

Hwang, J. J.

This paper has developed a complete two-phase model of a proton exchange membrane (PEM) fuel cell by considering fluid flow, heat transfer and current simultaneously. In fluid flow, two momentum equations governing separately the gaseous-mixture velocity (u g) and the liquid-water velocity (u w) illustrate the behaviors of the two-phase flow in a porous electrode. Correlations for the capillary pressure and the saturation level connect the above two-fluid transports. In heat transfer, a local thermal non-equilibrium (LTNE) model accounting for intrinsic heat transfer between the reactant fluids and the solid matrices depicts the interactions between the reactant-fluid temperature (T f) and the solid-matrix temperature (T s). The irreversibility heating due to electrochemical reactions, Joule heating arising from Ohmic resistance, and latent heat of water condensation/evaporation are considered in the present non-isothermal model. In current, Ohm's law is applied to yield the conservations in ionic current (i m) and electronic current (i s) in the catalyst layer. The Butler-Volmer correlation describes the relation of the potential difference (overpotential) and the transfer current between the electrolyte (such as Nafion™) and the catalyst (such as Pt/C).

Pyrolysis of polyolefins for increasing the yield of monomers' recovery

DOE Office of Scientific and Technical Information (OSTI.GOV)

Donaj, Pawel J., E-mail: pawel@mse.kth.se; Kaminsky, W.; Buzeto, F.

2012-05-15

Highlights: Black-Right-Pointing-Pointer Thermal and catalytic pyrolysis of mixed polyolefins in fluidized bed has been studied. Black-Right-Pointing-Pointer We tested applicability of a commercial Ziegler-Natta catalyst (Z-N: TiCl{sub 4}/MgCl{sub 2}). Black-Right-Pointing-Pointer The catalyst has a strong influence on product distribution, increasing gas fraction. Black-Right-Pointing-Pointer At 650 Degree-Sign C the monomer generation increased by 55% when the catalyst was used. Black-Right-Pointing-Pointer We showed the concept of treatment of mixed polyolefins without a need of separation. - Abstract: Pyrolysis of plastic waste is an alternative way of plastic recovery and could be a potential solution for the increasing stream of solid waste. The objectivemore » of this work was to increase the yield the gaseous olefins (monomers) as feedstock for polymerization process and to test the applicability of a commercial Ziegler-Natta (Z-N): TiCl{sub 4}/MgCl{sub 2} for cracking a mixture of polyolefins consisted of 46% wt. of low density polyethylene (LDPE), 30% wt. of high density polyethylene (HDPE) and 24% wt. of polypropylene (PP). Two sets of experiments have been carried out at 500 and 650 Degree-Sign C via catalytic pyrolysis (1% of Z-N catalyst) and at 650 and 730 Degree-Sign C via only-thermal pyrolysis. These experiments have been conducted in a lab-scale, fluidized quartz-bed reactor of a capacity of 1-3 kg/h at Hamburg University. The results revealed a strong influence of temperature and presence of catalyst on the product distribution. The ratios of gas/liquid/solid mass fractions via thermal pyrolysis were: 36.9/48.4/15.7% wt. and 42.4/44.7/13.9% wt. at 650 and 730 Degree-Sign C while via catalytic pyrolysis were: 6.5/89.0/4.5% wt. and 54.3/41.9/3.8% wt. at 500 and 650 Degree-Sign C, respectively. At 650 Degree-Sign C the monomer generation increased by 55% up to 23.6% wt. of total pyrolysis products distribution while the catalyst was added. Obtained yields of olefins were compared with the naphtha steam cracking process and other potentially attractive processes for feedstock generation. The concept of closed cycle material flow for polyolefins has been discussed, showing the potential benefits of feedstock recycling in a plastic waste management.« less

Changes in crack shape and saturation during water penetration into stressed rock

NASA Astrophysics Data System (ADS)

Masuda, K.; Nishizawa, O.

2012-12-01

Open cracks and cavities in rocks play important roles in fluid transport. Water penetration induced microcrack activities and caused the failure of rocks. Fluids in cracks affect earthquake generation mechanism through physical and physicochemical effects. Methods of characterizing crack shape and water saturation of rocks underground are needed for many scientific and industrial applications. It would be desirable to estimate the status of cracks using readily observable data such as elastic-wave velocities. We demonstrate a laboratory method for estimating crack status inside a cylindrical rock sample based on least-squares fitting of a cracked solid model to measured P- and S-wave velocities, and porosity derived from strain data. We used a cylinder (50 mm in diameter and 100 mm in length) of medium-grained granite. We applied a differential stress of 370 MPa, which corresponds to about 70% of fracture strength, to the rock sample under 30 MPa confining pressure and held it constant throughout the experiment. When the primary creep stage and acoustic emission (AE) caused by the initial loading had ceased, we injected distilled water into the bottom end of the sample at a constant pressure of 25 MPa until macroscopic fracture occurred. During water migration, we measured P waves and S waves (Sv and Sh), in five directions parallel to the top and bottom surfaces of the sample. We also measured strains of the sample surface and monitored AE. We created X-ray computer tomography (CT) images of the rock sample after the experiment in order to recognize the location and shape of fractured surfaces. We observed the different patterns of velocity changes in the upper and lower portions of the rock sample. Changes in P-wave velocities can be interpreted based on the crack density. S-waves showed the splitting with Vsv being faster than Vsh, corresponding to the second kind of anisotropy. We estimated two crack characteristics, crack shape and the degree of water saturation, and their changes during the loading and water migration into a granitic rock subjected to confining pressure and differential stress. We found that during injection of water to induce failure of a stressed rock sample, the aspect ratio of cracks increased and the degree of water saturation increased to about 70%. Laboratory derived method can be applicable for the well-planned observation in the field experiments. Monitoring in situ crack situations with seismic waves are useful for industrial and scientific applications such as sequestrations of carbon dioxide and waste, and measuring the regional stress field.

Synthesis of biodiesel fuel additives from glycerol using green chemistry and supercritical fluids

USDA-ARS?s Scientific Manuscript database

For every 3 moles of fatty acid esters produced, 1 mole of glycerol remains, ~11% of the biodiesel volume. One new method of glycerol use could be as a biodiesel fuel additive/extender using eco-friendly heterogeneous catalysts and supercritical fluids (SFs). SFs have advantages such as greater diff...

Review on stress corrosion and corrosion fatigue failure of centrifugal compressor impeller

NASA Astrophysics Data System (ADS)

Sun, Jiao; Chen, Songying; Qu, Yanpeng; Li, Jianfeng

2015-03-01

Corrosion failure, especially stress corrosion cracking and corrosion fatigue, is the main cause of centrifugal compressor impeller failure. And it is concealed and destructive. This paper summarizes the main theories of stress corrosion cracking and corrosion fatigue and its latest developments, and it also points out that existing stress corrosion cracking theories can be reduced to the anodic dissolution (AD), the hydrogen-induced cracking (HIC), and the combined AD and HIC mechanisms. The corrosion behavior and the mechanism of corrosion fatigue in the crack propagation stage are similar to stress corrosion cracking. The effects of stress ratio, loading frequency, and corrosive medium on the corrosion fatigue crack propagation rate are analyzed and summarized. The corrosion behavior and the mechanism of stress corrosion cracking and corrosion fatigue in corrosive environments, which contain sulfide, chlorides, and carbonate, are analyzed. The working environments of the centrifugal compressor impeller show the behavior and the mechanism of stress corrosion cracking and corrosion fatigue in different corrosive environments. The current research methods for centrifugal compressor impeller corrosion failure are analyzed. Physical analysis, numerical simulation, and the fluid-structure interaction method play an increasingly important role in the research on impeller deformation and stress distribution caused by the joint action of aerodynamic load and centrifugal load.

VLP seismicity from resonant modes of acoustic-gravity waves in a conduit-crack system filled with multiphase magma

NASA Astrophysics Data System (ADS)

Liang, C.; Prochnow, B. N.; OReilly, O. J.; Dunham, E. M.; Karlstrom, L.

2016-12-01

Oscillation of magma in volcanic conduits connected to cracks (dikes and sills) has been suggested as an explanation for very long period (VLP) seismic signals recorded at active basaltic volcanoes such as. Kilauea, Hawaii, and Erebus, Antarctica. We investigate the VLP seismicity using a linearized model for waves in and associated eigenmodes of a coupled conduit-crack system filled with multiphase magma, an extension of the Karlstrom and Dunham (2016) model for acoustic-gravity waves in volcanic conduits. We find that the long period surface displacement (as recorded on broadband seismometers) is dominated by opening/closing of the crack rather than the deformation of the conduit conduit walls. While the fundamental eigenmode is sensitive to the fluid properties and the geometry of the magma plumbing system, a closer scrutiny of various resonant modes reveals that the surface displacement is often more sensitive to higher modes. Here we present a systematic analysis of various long period acoustic-gravity wave resonant modes of a coupled conduit-crack system that the surface displacement is most sensitive to. We extend our previous work on a quasi-one-dimensional conduit model with inviscid magma to a more general axisymmetric conduit model that properly accounts for viscous boundary layers near the conduit walls, based on the numerical method developed by Prochnow et al. (submitted to Computers and Fluids, 2016). The surface displacement is dominated by either the fundamental or higher eigenmodes, depending on magma properties and the geometry of conduit and crack. An examination of the energetics of these modes reveals the complex interplay of different restoring forces (magma compressibility in the conduit, gravity, and elasticity of the crack) driving the VLP oscillations. Both nonequilibrium bubble growth and resorption and viscosity contribute to the damping of VLP signals. Our models thus provide a means to infer properties of open-vent basaltic volcanoes from seismic observations of VLP events.

Materials and methods for autonomous restoration of electrical conductivity

DOEpatents

Blaiszik, Benjamin J; Odom, Susan A; Caruso, Mary M; Jackson, Aaron C; Baginska, Marta B; Ritchey, Joshua A; Finke, Aaron D; White, Scott R; Moore, Jeffrey S; Sottos, Nancy R; Braun, Paul V; Amine, Khalil

2014-03-25

An autonomic conductivity restoration system includes a solid conductor and a plurality of particles. The particles include a conductive fluid, a plurality of conductive microparticles, and/or a conductive material forming agent. The solid conductor has a first end, a second end, and a first conductivity between the first and second ends. When a crack forms between the first and second ends of the conductor, the contents of at least a portion of the particles are released into the crack. The cracked conductor and the released contents of the particles form a restored conductor having a second conductivity, which may be at least 90% of the first conductivity.

Catalytic deoxygenation of microalgae oil to green hydrocarbons

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhao, Chen; Bruck, Thomas; Lercher, Johannes A.

2013-05-14

Microalgae are high potential raw biomass material for triglyceride feedstock, due to their high oil content and rapid growth rate, and because algae cultivation does not compete with edible food on arable land. This review addresses first the microalgae cultivation with an overview of the productivity and growth of microalgae, the recovery of lipids from the microalgae, and chemical compositions of microalgae biomass and microalgal oil. Second, three basic approaches are discussed to downstream processing for the production of green gasoline and diesel hydrocarbons from microalgae oil, including cracking with zeolite, hydrotreating with supported sulfided catalysts and hydrodeoxygenation with non-sulfidemore » metal catalysts. For the triglyceride derived bio-fuels, only “drop-in” gasoline and diesel range components are discussed in this review.« less

40 CFR Table 4 to Subpart Uuu of... - Requirements for Performance Tests for Metal HAP Emissions From Catalytic Cracking Units Not...

Code of Federal Regulations, 2010 CFR

2010-07-01

... 4 of § 63.1564. 4. Option 3: Ni lb/hr a. Measure concentration of Ni and total metal HAP. Method 29 (40 CFR part 60, appendix A). b. Compute Ni emission rate (lb/hr). Equation 5 of § 63.1564. c. Determine the equilibrium catalyst Ni concentration. XRF procedure in appendix A to this subpart1; or EPA...

40 CFR Table 4 to Subpart Uuu of... - Requirements for Performance Tests for Metal HAP Emissions From Catalytic Cracking Units Not...

Code of Federal Regulations, 2011 CFR

2011-07-01

... 4 of § 63.1564. 4. Option 3: Ni lb/hr a. Measure concentration of Ni and total metal HAP. Method 29 (40 CFR part 60, appendix A). b. Compute Ni emission rate (lb/hr). Equation 5 of § 63.1564. c. Determine the equilibrium catalyst Ni concentration. XRF procedure in appendix A to this subpart1; or EPA...

Method for simultaneous recovery of hydrogen from water and from hydrocarbons

DOEpatents

Willms, R. Scott

1996-01-01

Method for simultaneous recovery of hydrogen and hydrogen isotopes from water and from hydrocarbons. A palladium membrane, when utilized in cooperation with a nickel catalyst in a reactor, has been found to drive reactions such as water gas shift, steam reforming and methane cracking to substantial completion by removing the product hydrogen from the reacting mixture. In addition, ultrapure hydrogen is produced, thereby eliminating the need for an additional processing step.

Thermal oxidative degradation reactions of linear perfluoroalkyl ethers

NASA Technical Reports Server (NTRS)

Jones, W. R., Jr.; Paclorek, K. J. L.; Ito, T. I.; Kratzer, R. H.

1983-01-01

Thermal and thermal oxidative stability studies were performed on linear perfluoroalkyl ether fluids. The effect on degradation by metal catalysts and degradation inhibitors is reported. The linear perfluoroalkyl ethers are inherently unstable at 316 C in an oxidizing atmosphere. The metal catalysts greatly increased the rate of degradation in oxidizing atmospheres. In the presence of these metals in an oxidizing atmosphere, the degradation inhibitors were highly effective in arresting degradation at 288 C. However, the inhibitors had only limited effectiveness at 316 C. The metals promote degradation by chain scission. Based on elemental analysis and oxygen consumption data, the linear perfluoroalkyl ether fluids have a structural arrangement based on difluoroformyl and tetrafluoroethylene oxide units, with the former predominating. Previously announced in STAR as N82-26468

Seismic velocities in fractured rocks: An experimental verification of Hudson`s theory

DOE Office of Scientific and Technical Information (OSTI.GOV)

Peacock, S.; McCann, C.; Sothcott, J.

1994-01-01

Flow of fluids in many hydrocarbon reservoirs aquifers is enhanced by the presence of cracks and fractures. These cracks could be detected by their effects on propagation of compressional and shear waves through the reservoir: several theories, including Hudson`s, claim to predict the seismic effects of cracks. Although Hudson`s theory has already been used to calculate crack densities from seismic survey`s, the predictions of the theory have not yet been tested experimentally on rocks containing a known crack distribution. This paper describes an experimental verification of the theory. The rock used, Carrara marble, was chosen for its uniformity and lowmore » porosity, so that the effect of cracks would not be obscured by other influences. Cracks were induced by loading of laboratory specimens. Velocities of compressional and shear waves were measured by ultrasound at 0.85 MHz in dry and water-saturated specimens at high and low effective pressures.The cracks were then counted in polished sections of the specimens. In ``dry`` specimens with both dry and saturated cracks, Hudson`s theory overpredicted observed crack densities by a constant amount that is attributed to the observed value being systematically underestimated. The theory made poor predictions for fully saturated specimens. Shear-wave splitting, caused by anisotropy due to both crystal and crack alignment, was observed. Cracks were seen to follow grain boundaries rather than the direction of maximum compression due to loading. The results demonstrate that Hudson`s theory may be used in some cases to determine crack and fracture densities from compressional- and shear-wave velocity data.« less

Supercritical Fluids: Nanotechnology and Select Emerging Applications

DTIC Science & Technology

2006-01-01

power law functions with respect to the critical point parameters , see Seibert et al. (2001). This has a very important consequence that any results...catalyst support (silica doped alumina) was prepared via the sol–gel approach using two drying methods leading to xerogel and aerogel. The sol–gel...alumina samples doped with silicon sustains thermal treatment at 1200C, or more, for several hours. The active phase (palladium as catalyst) was

Precursory swarms of long-period events at Redoubt Volcano (1989-1990), Alaska: Their origin and use as a forecasting tool

USGS Publications Warehouse

Chouet, B.A.; Page, R.A.; Stephens, C.D.; Lahr, J.C.; Power, J.A.

1994-01-01

During the eruption of Redoubt Volcano from December 1989 through April 1990, the Alaska Volcano Observatory issued advance warnings of several tephra eruptions based on changes in seismic activity related to the occurrence of precursory swarms of long-period (LP) seismic events (dominant period of about 0.5 s). The initial eruption on December 14 occurred after 23 years of quiescence and was heralded by a 23-hour swarm of LP events that ended abruptly with the eruption. After a series of vent-clearing explosions over the next few days, dome growth began on December 21. Another swarm, with LP events similar to those of the first, began on the 26th and ended in a major tephra eruption on January 2. Eruptions continued over the next two weeks and then ceased until February 15, when a large eruption initiated a long phase of repetitive dome-building and dome-destroying episodes that continued into April. Warnings were issued before the major events on December 14 and January 2, but as the eruptive sequence continued after January 2, the energy of the swarms decreased and forecasting became more difficult. A significant but less intense swarm preceded the February 15 eruption, which was not forecast. This eruption destroyed the only seismograph on the volcanic edifice and stymied forecasting until March 4, when the first of three new stations was installed within 3 km of the active vent. From March 4 to the end of the sequence on April 21, there were eight eruptions, six of which were preceded by detectable swarms of LP events. Although weak, these swarms provided the basis for warnings issued before the eruptions on March 23 and April 6. The initial swarm on December 13 had the following features: (1) short duration (23 hours); (2) a rapidly accelerating rate of seismic energy release over the first 18 hours of the swarm, followed by a decline of activity during the 5 hours preceding the eruption; (3) a magnitude range from -0.4 to 1.6; (4) nearly identical LP signatures with a dominant period near 0.5 s; (5) dilatational first motions everywhere; and (6) a stationary source location at a depth of 1.4 km beneath the crater. This occurrence of long-period events suggests a model involving the interaction of magma with groundwater in which magmatic gases, steam and water drive a fixed conduit at a stationary point throughout the swarm. The initiation of that sequence of events is analogous to the failure of a pressure-relief valve connecting a lower, supercharged magma-dominated reservoir to a shallow hydrothermal system. A three-dimensional model of a vibrating fluid-filled crack recently developed by Chouet is found to be compatible with the seismic data and yields the following parameters for the LP source: crack length, 280-380 m; crack width, 140-190 m; crack thickness, 0.05-0.20 m; crack stiffness, 100-200; sound speed of fluid, 0.8-1.3 km/s; compressional-wave speed of rock, 5.1 km/s; density ratio of fluid to rock, ???0.4; and ratio of bulk modulus of fluid to rigidity of rock, 0.03-0.07. The fluid-filled crack is excited intermittently by an impulsive pressure drop that varies in magnitude within the range of 0.4 to 40 bar. Such disturbance appears to be consistent with a triggering mechanism associated with choked flow conditions in the crack. ?? 1994.

Hydroisomerization of n-hexadecane: remarkable selectivity of mesoporous silica post-synthetically modified with aluminum

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sabyrov, Kairat; Musselwhite, Nathan; Melaet, Gérôme

As the impact of acids on catalytically driven chemical transformations is tremendous, fundamental understanding of catalytically relevant factors is essential for the design of more efficient solid acid catalysts. In this work, we employed a post-synthetic doping method to synthesize a highly selective hydroisomerization catalyst and to demonstrate the effect of acid strength and density, catalyst microstructure, and platinum nanoparticle size on the reaction rate and selectivity. Aluminum doped mesoporous silica catalyzed gas-phase n-hexadecane isomerization with remarkably high selectivity to monobranched isomers (~95%), producing a substantially higher amount of isomers than traditional zeolite catalysts. Mildly acidic sites generated by post-syntheticmore » aluminum grafting were found to be the main reason for its high selectivity. The flexibility of the post-synthetic doping method enabled us to systematically explore the effect of the acid site density on the reaction rate and selectivity, which has been extremely difficult to achieve with zeolite catalysts. We found that a higher density of Brønsted acid sites leads to higher cracking of n-hexadecane presumably due to an increased surface residence time. Furthermore, regardless of pore size and microstructure, hydroisomerization turnover frequency linearly increased as a function of Brønsted acid site density. In addition to strength and density of acid sites, platinum nanoparticle size affected catalytic activity and selectivity. The smallest platinum nanoparticles produced the most effective bifunctional catalyst presumably because of higher percolation into aluminum doped mesoporous silica, generating more 'intimate' metallic and acidic sites. Finally, the aluminum doped silica catalyst was shown to retain its remarkable selectivity towards isomers even at increased reaction conversions.« less

Hydroisomerization of n-hexadecane: remarkable selectivity of mesoporous silica post-synthetically modified with aluminum

DOE PAGES

Sabyrov, Kairat; Musselwhite, Nathan; Melaet, Gérôme; ...

2017-01-01

As the impact of acids on catalytically driven chemical transformations is tremendous, fundamental understanding of catalytically relevant factors is essential for the design of more efficient solid acid catalysts. In this work, we employed a post-synthetic doping method to synthesize a highly selective hydroisomerization catalyst and to demonstrate the effect of acid strength and density, catalyst microstructure, and platinum nanoparticle size on the reaction rate and selectivity. Aluminum doped mesoporous silica catalyzed gas-phase n-hexadecane isomerization with remarkably high selectivity to monobranched isomers (~95%), producing a substantially higher amount of isomers than traditional zeolite catalysts. Mildly acidic sites generated by post-syntheticmore » aluminum grafting were found to be the main reason for its high selectivity. The flexibility of the post-synthetic doping method enabled us to systematically explore the effect of the acid site density on the reaction rate and selectivity, which has been extremely difficult to achieve with zeolite catalysts. We found that a higher density of Brønsted acid sites leads to higher cracking of n-hexadecane presumably due to an increased surface residence time. Furthermore, regardless of pore size and microstructure, hydroisomerization turnover frequency linearly increased as a function of Brønsted acid site density. In addition to strength and density of acid sites, platinum nanoparticle size affected catalytic activity and selectivity. The smallest platinum nanoparticles produced the most effective bifunctional catalyst presumably because of higher percolation into aluminum doped mesoporous silica, generating more 'intimate' metallic and acidic sites. Finally, the aluminum doped silica catalyst was shown to retain its remarkable selectivity towards isomers even at increased reaction conversions.« less

Single-atom gold catalysis in the context of developments in parahydrogen-induced polarization.

PubMed

Corma, Avelino; Salnikov, Oleg G; Barskiy, Danila A; Kovtunov, Kirill V; Koptyug, Igor V

2015-05-04

A highly isolated monoatomic gold catalyst, with single gold atoms dispersed on multiwalled carbon nanotubes (MWCNTs), has been synthesized, characterized, and tested in heterogeneous hydrogenation of 1,3-butadiene and 1-butyne with parahydrogen to maximize the polarization level and the contribution of the pairwise hydrogen addition route. The Au/MWCNTs catalyst was found to be active and efficient in pairwise hydrogen addition and the estimated contributions from the pairwise hydrogen addition route are at least an order of magnitude higher than those for supported metal nanoparticle catalysts. Therefore, the use of the highly isolated monoatomic catalysts is very promising for production of hyperpolarized fluids that can be used for the significant enhancement of NMR signals. A mechanism of 1,3-butadiene hydrogenation with parahydrogen over the highly isolated monoatomic Au/MWCNTs catalyst is also proposed. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Shear wave splitting and crustal anisotropy at the Mid-Atlantic Ridge, 35°N

NASA Astrophysics Data System (ADS)

Barclay, Andrew H.; Toomey, Douglas R.

2003-08-01

Shear wave splitting observed in microearthquake data at the axis of the Mid-Atlantic Ridge near 35°N has a fast polarization direction that is parallel to the trend of the axial valley. The time delays between fast and slow S wave arrivals range from 35 to 180 ms, with an average of 90 ms, and show no relationship with ray path length, source-to-receiver azimuth, or receiver location. The anisotropy is attributed to a shallow distribution of vertical, fluid-filled cracks, aligned parallel to the trend of the axial valley. Joint modeling of the shear wave anisotropy and coincident P wave anisotropy results, using recent theoretical models for the elasticity of a porous medium with aligned cracks, suggests that the crack distribution that causes the observed P wave anisotropy can account for at most 10 ms of the shear wave delay. Most of the shear wave delay thus likely accrues within the shallowmost 500 m (seismic layer 2A), and the percent S wave anisotropy within this highly fissured layer is 8-30%. Isolated, fluid-filled cracks at 500 m to 3 km depth that are too thin or too shallow to be detected by the P wave experiment may also contribute to the shear wave delays. The joint analysis of P and S wave anisotropy is an important approach for constraining the crack distributions in the upper oceanic crust and is especially suited for seismically active hydrothermal systems at slow and intermediate spreading mid-ocean ridges.

3D visualization of membrane failures in fuel cells

NASA Astrophysics Data System (ADS)

Singh, Yadvinder; Orfino, Francesco P.; Dutta, Monica; Kjeang, Erik

2017-03-01

Durability issues in fuel cells, due to chemical and mechanical degradation, are potential impediments in their commercialization. Hydrogen leak development across degraded fuel cell membranes is deemed a lifetime-limiting failure mode and potential safety issue that requires thorough characterization for devising effective mitigation strategies. The scope and depth of failure analysis has, however, been limited by the 2D nature of conventional imaging. In the present work, X-ray computed tomography is introduced as a novel, non-destructive technique for 3D failure analysis. Its capability to acquire true 3D images of membrane damage is demonstrated for the very first time. This approach has enabled unique and in-depth analysis resulting in novel findings regarding the membrane degradation mechanism; these are: significant, exclusive membrane fracture development independent of catalyst layers, localized thinning at crack sites, and demonstration of the critical impact of cracks on fuel cell durability. Evidence of crack initiation within the membrane is demonstrated, and a possible new failure mode different from typical mechanical crack development is identified. X-ray computed tomography is hereby established as a breakthrough approach for comprehensive 3D characterization and reliable failure analysis of fuel cell membranes, and could readily be extended to electrolyzers and flow batteries having similar structure.

Catalytic cracking of the top phase fraction of bio-oil into upgraded liquid oil

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sunarno; Chemical Engineering Department, Gadjah Mada University, Jalan Grafika No. 2 Bulaksumur,Yogyakarta 55281; Rochmadi,

The energy consumption is increasing, while oil reserves as a primary energy resource are decreasing, so that is the reason seeking alternative energy source is inevitable. Biomass especially oil palm empty fruit bunches (EFB) which is abundant in Indonesia can be processed into bio-oil by pyrolysis process. The potential for direct substitution of bio-oil for petroleum may be limited due to the high viscosity, high oxygen content, low heating value, and corrosiveness. Consequently, upgrading of the bio-oil before use is inevitable to give a wider variety of applications of its liquid product. Furthermore, upgrading process to improve the quality ofmore » bio-oil by reduction of oxygenates involves process such as catalytic cracking. The objective of this research is to study the effect of operation temperature on yield and composition of upgraded liquid oil and to determine physical properties. Bio-oil derived from EFB was upgraded through catalytic cracking using series tubular reactor under atmospheric pressure on a silica-alumina catalyst. Results show that increasing temperature from 450 to 600 °C, resulting in decreasing of upgraded liquid oil (ULO) yield, decreasing viscosity and density of ULO, but increasing in calorimetric value of ULO. The increasing temperature of cracking also will increase the concentration of gasoline and kerosene in ULO.« less

40 CFR 60.105a - Monitoring of emissions and operations for fluid catalytic cracking units (FCCU) and fluid coking...

Code of Federal Regulations, 2012 CFR

2012-07-01

... for air leaks, torn or broken bags or filter media, or any other condition that may cause an increase... Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) AIR PROGRAMS (CONTINUED) STANDARDS OF... nozzles must conduct a daily check of the air or water pressure to the spray nozzles and record the...

Surface property modification of silicon

NASA Technical Reports Server (NTRS)

Danyluk, S.

1984-01-01

The main emphasis of this work has been to determine the wear rate of silicon in fluid environments and the parameters that influence wear. Three tests were carried out on single crystal Czochralski silicon wafers: circular and linear multiple-scratch tests in fluids by a pyramidal diamond simulated fixed-particle abrasion; microhardness and three-point bend tests were used to determine the hardness and fracture toughness of abraded silicon and the extent of damage induced by abrasion. The wear rate of (100) and (111) n and p-type single crystal Cz silicon abraded by a pyramidal diamond in ethanol, methanol, acetone and de-ionized water was determined by measuring the cross-sectional areas of grooves of the circular and linear multiple-scratch tests. The wear rate depends on the loads on the diamond and is highest for ethanol and lowest for de-ionized water. The surface morphology of the grooves showed lateral and median cracks as well as a plastically deformed region. The hardness and fracture toughness are critical parameters that influence the wear rate. Microhardness tests were conducted to determine the hardness as influenced by fluids. Median cracks and the damage zone surrounding the indentations were also related to the fluid properties.

Initiation and propagation of a PKN hydraulic fracture in permeable rock: Toughness dominated regime

NASA Astrophysics Data System (ADS)

Sarvaramini, E.; Garagash, D.

2011-12-01

The present work investigates the injection of a low-viscosity fluid into a pre-existing fracture with constrained height (PKN), as in waterflooding or supercritical CO2 injection. Contrary to conventional hydraulic fracturing, where 'cake build up' limits diffusion to a small zone, the low viscosity fluid allows for diffusion over a wider range of scales. Over large injection times the pattern becomes 2 or 3-D, necessitating a full-space diffusion modeling. In addition, the dissipation of energy associated with fracturing of rock dominates the energy needed for the low-viscosity fluid flow into the propagating crack. As a result, the fracture toughness is important in evaluating both the initiation and the ensuing propagation of these fractures. Classical PKN hydraulic fracturing model, amended to account for full-space leak-off and the toughness [Garagash, unpublished 2009], is used to evaluate the pressure history and fluid leak-off volume during the injection of low viscosity fluid into a pre-existing and initially stationary. In order to find the pressure history, the stationary crack is first subject to a step pressure increase. The response of the porous medium to the step pressure increase in terms of fluid leak-off volume provides the fundamental solution, which then can be used to find the transient pressurization using Duhamel theorem [Detournay & Cheng, IJSS 1991]. For the step pressure increase an integral equation technique is used to find the leak-off rate history. For small time the solution must converge to short time asymptote, which corresponds to 1-D diffusion pattern. However, as the diffusion length in the zone around the fracture increases the assumption of a 1-D pattern is no longer valid and the diffusion follows a 2-D pattern. The solution to the corresponding integral equation gives the leak-off rate history, which is used to find the cumulative leak-off volume. The transient pressurization solution is obtained using global conservation of fluid injected into the fracture. With increasing pressure in the fracture due to the fluid injection, the energy release rate eventually becomes equal to the toughness and fracture propagates. The evolution of the fracture length is established using the method similar to the one employed for the stationary crack.

Time exposure studies on stress corrosion cracking of aluminum 2014-T6, 2219-T87, 2014-T651, 7075-T651, and titanium 6Al-4V

NASA Technical Reports Server (NTRS)

Terrell, J.

1973-01-01

The effect of a constant applied stress in crack initiation of aluminum 2014-T6, 2219-T87, 2014-T651, 7075-T651 and titanium 6Al-4V has been investigated. Aluminum c-ring specimens (1-inch diameter) and u-band titanium samples were exposed continuously to a 3.5% NaCl solution (pH 7) and organic fluids of ethyl, methyl, and iso-propyl alcohol (reagent purity), and demineralized distilled water. Corrosive action was observed to begin during the first and second day of constant exposure as evidenced by accumulation of hydrogen bubbles on the surface of stressed aluminum samples. However, titanium stressed specimens showed no reactions to its environment. Results of this investigation seems to suggest that aluminum 2014-T6, aluminum 7075-T651 and aluminum 2014-T651 are susceptible to stress corrosion cracking in chloride solution (NaCl), while aluminum 2219-T87 seem to resist stress corrosion cracking in sodium chloride at three levels of stress (25%, 50%, and 75% Y.S.). In organic fluids of methyl, ethyl, and iso-propyl alcohol, 2014-T6 and 7075-T651 did not fail by SCC; but 2014-T651 was susceptible to SCC in methly alcohol, but resistant in ethyl alcohol, iso-propyl alcohol and demineralized distilled water.

THE USE OF FRY (EMBALMING FLUID AND PCP-LACED CIGARETTES OR MARIJUANA STICKS) AMONG CRACK COCAINE SMOKERS

PubMed Central

PETERS, RONALD J.; WILLIAMS, MARK; ROSS, MICHAEL W.; ATKINSON, JOHN; McCURDY, SHERLY A.

2010-01-01

Statistics show that the prevalence of crack cocaine use and embalming fluid and phencyclidine (PCP)-laced cigarettes or marijuana sticks, commonly referred to on the street as “fry” or “wet” is a problem; however, the relationship between these substances of abuse and concurrent polydrug use is unknown. In the present study, a cross-sectional survey was conducted among 426 African-American crack users in Houston, Texas, to investigate the difference between those who concurrently reported lifetime (defined as at least one usage of fry in life) fry use and those who stated they never used fry. The data were analyzed using chi-square and logistic regression analyses. Fry users were significantly more likely than non-users to not have a casual sex partner (92% users vs. 84% non-users, p ≤ 0.05) and were more likely to have been diagnosed with gonorrhea in the past 12 months (9% users vs. 2% non-users, p ≤ 0.05). In addition fry users had significantly higher odds of currently trading sex for drugs (OR = 2.30, p ≤ 0.05), marijuana use (OR = 12.11, p ≤ 0.05), and codeine (syrup) use (OR = 8.10, p ≤ 0.05). These findings are important in determining the “cultural novelties” relative to crack and fry use among younger African Americans. PMID:19157045

Catalyst surfaces for the chromous/chromic redox couple

NASA Technical Reports Server (NTRS)

Giner, J. D.; Cahill, K. J. (Inventor)

1980-01-01

An electricity producing cell of the reduction-oxidation (REDOX) type is described. The cell is divided into two compartments by a membrane, each compartment containing a solid inert electrode. A ferrous/ferric couple in a chloride solution serves as a cathode fluid which is circulated through one of the compartments to produce a positive electric potential disposed therein. A chromic/chromous couple in a chloride solution serves as an anode fluid which is circulated through the second compartment to produce a negative potential on an electrode disposed therein. The electrode is an electrically conductive, inert material plated with copper, silver or gold. A thin layer of lead plates onto the copper, silver or gold layer when the cell is being charged, the lead ions being available from lead chloride which was added to the anode fluid. If the REDOX cell is then discharged, the current flows between the electrodes causing the lead to deplate from the negative electrode and the metal coating on the electrode will act as a catalyst to cause increased current density.

A review of shear wave splitting in the crack-critical crust

NASA Astrophysics Data System (ADS)

Crampin, Stuart; Chastin, Sebastien

2003-10-01

Over the last 15 years, it has become established that crack-induced stress-aligned shear wave splitting, with azimuthal anisotropy, is an inherent characteristic of almost all rocks in the crust. This means that most in situ rocks are pervaded by fluid-saturated microcracks and consequently are highly compliant. The evolution of such stress-aligned fluid-saturated grain-boundary cracks and pore throats in response to changing conditions can be calculated, in some cases with great accuracy, using anisotropic poro-elasticity (APE). APE is tightly constrained with no free parameters, yet dynamic modelling with APE currently matches a wide range of phenomena concerning anisotropy, stress, shear waves and cracks. In particular, APE has allowed the anisotropic response of a reservoir to injection to be calculated (predicted with hindsight), and the time and magnitude of an earthquake to be correctly stress-forecast. The reason for this calculability and predictability is that the microcracks in the crust are so closely spaced that they form critical systems. This crack-critical crust leads to a new style of geophysics that has profound implications for almost all aspects of pre-fracturing deformation of the crust and for solid-earth geophysics and geology. We review past, present and speculate about the future of shear wave splitting in the crack-critical crust. Shear wave splitting is seen to be a dynamic measure of the deformation of the rock mass. There is some good news and some bad news for conventional geophysics. Many accepted phenomena are no longer valid at high spatial and temporal resolution. A major effect is that the detailed crack geometry changes with time and varies from place to place in response to very small previously negligible changes. However, at least in some circumstances, the behaviour of the rock in the highly complex inhomogeneous Earth may be calculated and the response predicted, opening the way to possible control by feedback. The need is to devise ways to exploit these new opportunities in the crack-critical crust. Recent observations from the SMSITES Project at Húsavík in Northern Iceland, gathered while this review was being written, display the extraordinarily sensitivity of in situ rock to small changes at great distances. The effects are far too large to occur in a conventional elastic brittle crust, and their presence confirms the highly compliant nature of the crack-critical crust.

Surface coatings and catalyst production by electrodeposition

NASA Technical Reports Server (NTRS)

May, Chester B.; Riley, Clyde; Coble, H. Dwain; Loo, Boon H.

1987-01-01

Electrodeposition and electrocodeposition in low gravity are discussed. The goal is to provide a better understanding of the role of convection and buoyancy in the mechanisms of formation of some electrodeposited surfaces, fluid flow in the vicinity of electrodepositing surfaces, the influence of a moving medium upon codeposition, the effect of gravity upon the dispersion (coagulation) of neutral particles that are desired for codeposition and preparation of improved surface coatings and metal catalysts.

One-step hydroprocessing of fatty acids into renewable aromatic hydrocarbons over Ni/HZSM-5: insights into the major reaction pathways.

PubMed

Xing, Shiyou; Lv, Pengmei; Wang, Jiayan; Fu, Junying; Fan, Pei; Yang, Lingmei; Yang, Gaixiu; Yuan, Zhenhong; Chen, Yong

2017-01-25

For high caloricity and stability in bio-aviation fuels, a certain content of aromatic hydrocarbons (AHCs, 8-25 wt%) is crucial. Fatty acids, obtained from waste or inedible oils, are a renewable and economic feedstock for AHC production. Considerable amounts of AHCs, up to 64.61 wt%, were produced through the one-step hydroprocessing of fatty acids over Ni/HZSM-5 catalysts. Hydrogenation, hydrocracking, and aromatization constituted the principal AHC formation processes. At a lower temperature, fatty acids were first hydrosaturated and then hydrodeoxygenated at metal sites to form long-chain hydrocarbons. Alternatively, the unsaturated fatty acids could be directly deoxygenated at acid sites without first being saturated. The long-chain hydrocarbons were cracked into gases such as ethane, propane, and C 6 -C 8 olefins over the catalysts' Brønsted acid sites; these underwent Diels-Alder reactions on the catalysts' Lewis acid sites to form AHCs. C 6 -C 8 olefins were determined as critical intermediates for AHC formation. As the Ni content in the catalyst increased, the Brønsted-acid site density was reduced due to coverage by the metal nanoparticles. Good performance was achieved with a loading of 10 wt% Ni, where the Ni nanoparticles exhibited a polyhedral morphology which exposed more active sites for aromatization.

Optimizing catalysis conditions to decrease aromatic hydrocarbons and increase alkanes for improving jet biofuel quality.

PubMed

Cheng, Jun; Li, Tao; Huang, Rui; Zhou, Junhu; Cen, Kefa

2014-04-01

To produce quality jet biofuel with high amount of alkanes and low amount of aromatic hydrocarbons, two zeolites of HY and HZSM-5 supporting Ni and Mo were used as catalysts to convert soybean oil into jet fuel. Zeolite HY exhibited higher jet range alkane selectivity (40.3%) and lower jet range aromatic hydrocarbon selectivity (23.8%) than zeolite HZSM-5 (13.8% and 58.9%). When reaction temperature increased from 330 to 390°C, yield of jet fuel over Ni-Mo/HY catalyst at 4 MPa hydrogen pressure increased from 0% to 49.1% due to the shift of reaction pathway from oligomerization to cracking reaction. Further increase of reaction temperature from 390 to 410°C resulted in increased yield of jet range aromatic hydrocarbons from 18.7% to 30%, which decreased jet fuel quality. A high yield of jet fuel (48.2%) was obtained at 1 MPa low hydrogen pressure over Ni (8 wt.%)-Mo (12 wt.%)/HY catalyst. Copyright © 2014 Elsevier Ltd. All rights reserved.

Method for making monolithic metal oxide aerogels

DOEpatents

Droege, M.W.; Coronado, P.R.; Hair, L.M.

1995-03-07

Transparent, monolithic metal oxide aerogels of varying densities are produced using a method in which a metal alkoxide solution and a catalyst solution are prepared separately and reacted. The resulting hydrolyzed-condensed colloidal solution is gelled, and the wet gel is contained within a sealed, but gas permeable, containment vessel during supercritical extraction of the solvent. The present invention is especially advantageous for making metal oxides other than silica that are prone to forming opaque, cracked aerogels. 6 figs.

Method for making monolithic metal oxide aerogels

DOEpatents

Droege, Michael W.; Coronado, Paul R.; Hair, Lucy M.

1995-01-01

Transparent, monolithic metal oxide aerogels of varying densities are produced using a method in which a metal alkoxide solution and a catalyst solution are prepared separately and reacted. The resulting hydrolyzed-condensed colloidal solution is gelled, and the wet gel is contained within a sealed, but gas permeable, containment vessel during supercritical extraction of the solvent. The present invention is especially advantageous for making metal oxides other than silica that are prone to forming opaque, cracked aerogels.

Aviation Turbine Fuels from Tar Sands Bitumen and Heavy Oils. Part 3. Laboratory Sample Production.

DTIC Science & Technology

1987-12-01

FILD7 ar Sands, Heavy Ois Jet Fue - - - etF IE L D G R O U P S U B -G R O U P , u e -. IT - 3 seC m ) A s h l GROUP SB-RP Fue-i-T-33-A Reduced Crude...connec- tion with processes for heavy oil cracking and related catalysts. * program which allowed processing of bitumen stocks . The overall process flow

Temporal Variation in Oscillatory Characteristics of Long-period Tremor at Aso Volcano, Japan.

NASA Astrophysics Data System (ADS)

Yamamoto, M.; Ohkura, T.; Kaneshima, S.; Kawakatsu, H.

2017-12-01

At Aso volcano, Japan, various kinds of volcanic signals with broad frequency contents have been observed since 1930s. One of these signals is long-period tremor (LPT) with a dominant period of around 15 s, which is intermittently emitted from the volcano regardless of the surface activity. Our broadband seismic observations have revealed that LPTs are a kind of resonance oscillation of a crack-like conduit beneath the crater. In this study, aiming to detect a temporal variation of volcanic system, we analyze the long-term variation of LPTs from 1994 to the present.We first examine the temporal variation of dominant periods of LPTs (fundamental mode of around 15 s and the first overtone of around 7 s) using the continuous data recorded at broadband stations close to the active crater. The result shows a clear temporal change in the dominant periods of LPTs in 2003-2005 and 2014-2015. In 2003-2005, the periods of the two modes show correlated temporal change, and it can be interpreted as compositional and/or thermal change of hydrothermal fluids. On the other hand, in 2014-2015, the period of first overtone is almost constant at around 8 s, while that of the fundamental mode shows relatively large temporal fluctuations between 16 s and 12 s. To explain the different behavior among the two resonant modes, we examine the oscillatory characteristics of a fluid-filled crack having linearly varying thickness. With this model, we find that the ratio between resonance periods becomes smaller than that in the case of a flat crack having constant thickness. This behavior can be understood by considering the effective thickness of the crack depends on the wavelength of each resonant mode. Based on these results, the different temporal variation of dominant periods can be interpreted by depth-dependent thickness of the crack-like conduit which may be caused by pressurization and/or intrusion of magma at deeper portion of the conduit. These results suggest the importance of continuous observation, and at the same time, imply that the temporal variation of volcanic fluid systems beneath active volcanoes may be monitored by seismological means.

Effect of Chamber Pressurization Rate on Combustion and Propagation of Solid Propellant Cracks

NASA Astrophysics Data System (ADS)

Yuan, Wei-Lan; Wei, Shen; Yuan, Shu-Shen

2002-01-01

area of the propellant grain satisfies the designed value. But cracks in propellant grain can be generated during manufacture, storage, handing and so on. The cracks can provide additional surface area for combustion. The additional combustion may significantly deviate the performance of the rocket motor from the designed conditions, even lead to explosive catastrophe. Therefore a thorough study on the combustion, propagation and fracture of solid propellant cracks must be conducted. This paper takes an isolated propellant crack as the object and studies the effect of chamber pressurization rate on the combustion, propagation and fracture of the crack by experiment and theoretical calculation. deformable, the burning inside a solid propellant crack is a coupling of solid mechanics and combustion dynamics. In this paper, a theoretical model describing the combustion, propagation and fracture of the crack was formulated and solved numerically. The interaction of structural deformation and combustion process was included in the theoretical model. The conservation equations for compressible fluid flow, the equation of state for perfect gas, the heat conducting equation for the solid-phase, constitutive equation for propellant, J-integral fracture criterion and so on are used in the model. The convective burning inside the crack and the propagation and fracture of the crack were numerically studied by solving the set of nonlinear, inhomogeneous gas-phase governing equations and solid-phase equations. On the other hand, the combustion experiments for propellant specimens with a precut crack were conducted by RTR system. Predicted results are in good agreement with experimental data, which validates the reasonableness of the theoretical model. Both theoretical and experimental results indicate that the chamber pressurization rate has strong effects on the convective burning in the crack, crack fracture initiation and fracture pattern.

Effects of fracture and crack healing in sI methane and sII methane-ethane gas hydrate

NASA Astrophysics Data System (ADS)

Helgerud, M. B.; Waite, W. F.; Stern, L. A.; Kirby, S. H.

2005-12-01

Cracking within gas hydrate-bearing sediment can occur in the field at core-scales, due to unloading as material is brought to the surface during conventional coring, and at reservoir scales if the formation is fractured prior to production. Cracking can weaken hydrate-bearing sediment, but can also provide additional surface area for dissociation and permeability pathways for enhanced gas and fluid flow. In pulse-transmission wave speed measurements, we observe cracking in laboratory-formed pure sI methane and sII methane-ethane hydrates when samples are axially unloaded while being held under gas pressure to maintain hydrate stability. Cracking events are inferred from repeated, sharp decreases in shear wave speed occurring concurrently with abrupt increases in sample length. We also visually observe cracks in the solid samples after their recovery from the apparatus following each experiment. Following a cracking event, we observe evidence of rapid crack healing, or annealing expressed as nearly complete recovery of the shear wave speed within approximately 20 minutes. Gas hydrate recrystallization, grain growth, and annealing have also been observed in optical cell experiments and SEM imagery over a similar time frame. In a recovered hydrate-bearing core that is repressurized for storage or experimentation, rapid crack healing and recrystallization can partly restore lost mechanical strength and raise wave speeds. In a fractured portion of a hydrate-bearing reservoir, the rapid healing process can close permeable cracks and reduce the surface area available for dissociation.

Methods of cracking a crude product to produce additional crude products

DOEpatents

Mo, Weijian [Sugar Land, TX; Roes, Augustinus Wilhelmus Maria [Houston, TX; Nair, Vijay [Katy, TX

2009-09-08

A method for producing a crude product is disclosed. Formation fluid is produced from a subsurface in situ heat treatment process. The formation fluid is separated to produce a liquid stream and a first gas stream. The first gas stream includes olefins. The liquid stream is fractionated to produce one or more crude products. At least one of the crude products has a boiling range distribution from 38.degree. C. and 343.degree. C. as determined by ASTM Method D5307. The crude product having the boiling range distribution from 38.degree. C. and 343.degree. C. is catalytically cracked to produce one or more additional crude products. At least one of the additional crude products is a second gas stream. The second gas stream has a boiling point of at most 38.degree. C. at 0.101 MPa.

Time-dependent brittle deformation (creep) at Mt. Etna volcano

NASA Astrophysics Data System (ADS)

Heap, M. J.; Baud, P.; Meredith, P. G.; Vinciguerra, S.; Bell, A. F.; Main, I. G.

2009-04-01

Mt. Etna is the largest and most active volcano in Europe. Time-dependent weakening mechanisms, leading to slow fracturing, have been shown to act during pre-eruptive patterns of flank eruptions at Mt. Etna volcano. Due to the high permeability of its volcanic rocks, the volcanic edifice hosts one of the biggest hydrogeologic reservoirs of Sicily (Ogniben, 1966). The presence of a fluid phase in cracks within rock has been shown to dramatically affect both mechanical and chemical interactions. Chemically, it promotes time-dependent brittle deformation through such mechanisms as stress corrosion cracking that allows rocks to deform at stresses far below their short-term failure strength. Such crack growth is highly non-linear and accelerates towards dynamic failure over extended periods of time, even under constant applied stress; a phenomenon known as ‘brittle creep'. Here we report results from a study of time-dependent brittle creep in water-saturated samples of Etna basalt (EB) under triaxial stress conditions (confining pressure of 50 MPa and pore fluid pressure of 20 MPa). Samples of EB were loaded at a constant strain rate of 10-5 s-1 to a pre-determined percentage of the short-term strength and left to deform under constant stress until failure. Crack damage evolution was monitored throughout each experiment by measuring the independent damage proxies of axial strain, pore volume change and output of acoustic emission (AE) energy, during brittle creep of creep strain rates ranging over four orders of magnitude. Our data not only demonstrates that basalt creeps in the brittle regime but also that the applied differential stress exerts a crucial influence on both time-to-failure and creep strain rate in EB. Furthermore, stress corrosion is considered to be responsible for the acceleratory cracking and seismicity prior to volcanic eruptions and is invoked as an important mechanism in forecasting models. Stress-stepping creep experiments were then performed to allow the influence of the effective confining stress to be studied in detail. Experiments were performed under effective stress conditions of 10, 30 and 50 MPa (whilst maintaining a constant pore fluid pressure of 20 MPa). In addition to the purely mechanical influence of water, governed by the effective stress, which results in a shift of the creep strain rate curves to lower strain rates at higher effective stresses. Our results also demonstrate that the chemically-driven process of stress corrosion cracking appears to be inhibited at higher effective stress. This results in an increase in the gradient of the creep strain rate curves with increasing effective stress. We suggest that the most likely cause of this change is a decrease in water mobility due to a reduction in crack aperture and an increase in water viscosity at higher pressure. Finally, we show that a theoretical model based on mean-field damage mechanics creep laws is able to reproduce the experimental strain-time relations. Our results indicate that the local changes in the stress field and fluid circulation can have a profound impact in the time-to-failure properties of the basaltic volcanic pile.

Time-dependent Brittle Deformation in Etna Basalt

NASA Astrophysics Data System (ADS)

Heap, M. J.; Baud, P.; Meredith, P. G.; Vinciguerra, S.; Bell, A. F.; Main, I. G.

2008-12-01

Mt Etna is the largest and most active volcano in Europe. Due to the high permeability of its volcanic rocks, the volcanic edifice hosts one of the biggest hydrogeologic reservoirs of Sicily (Ogniben, 1966). Pre-eruptive patterns of flank eruptions, closely monitored by means of ground deformation and seismicity, revealed the slow development of fracture systems at different altitudes, marked by repeated bursts of seismicity and accelerating/decelerating deformation patterns acting over the scale of months to days. The presence of a fluid phase in cracks within rock has been shown to dramatically affect both mechanical and chemical interactions. Chemically, it promotes time-dependent brittle deformation through such mechanisms as stress corrosion cracking that allows rocks to deform at stresses far below their short-term failure strength. Such crack growth is highly non-linear and accelerates towards dynamic failure over extended periods of time, even under constant applied stress; a phenomenon known as 'brittle creep'. Stress corrosion is considered to be responsible for the acceleratory cracking and seismicity prior to volcanic eruptions and is invoked as an important mechanism in forecasting models. Here we report results from a study of time-dependent brittle creep in water-saturated samples of Etna basalt (EB) under triaxial stress conditions (confining pressure of 50 MPa and pore fluid pressure of 20 MPa). Samples of EB were loaded at a constant strain rate of 10-5 s-1 to a pre-determined percentage of the short- term strength and left to deform under constant stress until failure. Crack damage evolution was monitored throughout each experiment by measuring the independent damage proxies of axial strain, pore volume change and output of acoustic emission (AE) energy, during brittle creep of creep strain rates ranging over four orders of magnitude. Our data demonstrate that the applied differential stress exerts a crucial influence on both time-to-failure and creep strain rate in EB. Stress-stepping creep experiments were then performed to allow the influence of the effective confining stress to be studied in detail. Experiments were performed under effective stress conditions of 10, 30 and 50 MPa (whilst maintaining a constant pore fluid pressure of 20 MPa). In addition to the purely mechanical influence of water, governed by the effective stress, which results in a shift of the creep strain rate curves to lower strain rates at higher effective stresses. Our results also demonstrate that the chemically-driven process of stress corrosion cracking appears to be inhibited at higher effective stress. This results in an increase in the gradient of the creep strain rate curves with increasing effective stress. We suggest that the most likely cause of this change is a decrease in water mobility due to a reduction in crack aperture and an increase in water viscosity at higher pressure. Finally, we show that a theoretical model based on mean-field damage mechanics creep laws is able to reproduce the experimental strain-time relations. Our results indicate that the local changes in the stress field and fluid circulation can have a profound impact in the time- to-failure properties of the basaltic volcanic pile.

Time-dependent brittle deformation at Mt. Etna volcano

NASA Astrophysics Data System (ADS)

Baud, Patrick; Heap, Michael; Meredith, Philip; Vinciguerra, Sergio; Bell, Andrew; Main, Ian

2010-05-01

Time-dependent weakening mechanisms, leading to slow fracturing, are likely to act during the build up to flank eruptions at Mt. Etna volcano and are potentially a primary control on pre-eruptive patterns of seismicity and deformation. Due to the high permeability of its volcanic rocks, the volcanic edifice hosts a large water reservoir (Ogniben, 1966). The presence of a fluid phase in cracks within rock has been shown to dramatically affect both mechanical and chemical interactions. Chemically, it promotes time-dependent brittle deformation through such mechanisms as stress corrosion cracking that allows rocks to deform at stresses far below their short-term failure strength. Such crack growth is highly non-linear and accelerates towards dynamic failure over extended periods of time, even under constant applied stress; a phenomenon known as ‘brittle creep'. Here we report results from a study of time-dependent brittle creep in water-saturated samples of Etna basalt (EB) under triaxial stress conditions (confining pressure of 50 MPa and pore fluid pressure of 20 MPa). Samples of EB were loaded at a constant strain rate of 10-5 s-1 to a pre-determined percentage of the short-term strength and left to deform under constant stress until failure. Crack damage evolution was monitored throughout each experiment by measuring the independent damage proxies of axial strain, pore volume change and output of acoustic emission (AE) energy, during brittle creep of creep strain rates ranging over four orders of magnitude. Our data not only demonstrates that basalt creeps in the brittle regime but also that the applied differential stress exerts a crucial influence on both time-to-failure and creep strain rate in EB. Furthermore, stress corrosion is considered to be responsible for the acceleratory cracking and seismicity prior to volcanic eruptions and is invoked as an important mechanism in forecasting models. Stress-stepping creep experiments were then performed to allow the influence of the effective confining stress to be studied in detail. Experiments were performed under effective stress conditions of 10, 30 and 50 MPa (whilst maintaining a constant pore fluid pressure of 20 MPa). In addition to the purely mechanical influence of water, governed by the effective stress, which results in a shift of the creep strain rate curves to lower strain rates at higher effective stresses. Our results also demonstrate that the chemically-driven process of stress corrosion cracking appears to be inhibited at higher effective stress. This results in an increase in the gradient of the creep strain rate curves with increasing effective stress. We suggest that the most likely cause of this change is a decrease in water mobility due to a reduction in crack aperture and an increase in water viscosity at higher pressure. Finally, we show that a theoretical model based on mean-field damage mechanics creep laws is able to reproduce the experimental strain-time relations and inverse seismicity plots using our experimental AE data. Our results indicate that the local changes in the stress field and fluid circulation can have a profound impact in the time-to-failure properties of the basaltic volcanic pile.

Mathematical modelling of anisotropy of illite-rich shale

USGS Publications Warehouse

Chesnokov, E.M.; Tiwary, D.K.; Bayuk, I.O.; Sparkman, M.A.; Brown, R.L.

2009-01-01

The estimation of illite-rich shale anisotropy to account for the alignment of clays and gas- or brine-filled cracks is presented via mathematical modelling. Such estimation requires analysis to interpret the dominance of one effect over another. This knowledge can help to evaluate the permeability in the unconventional reservoir, stress orientation, and the seal capacity for the conventional reservoir. Effective media modelling is used to predict the elastic properties of the illite-rich shale and to identify the dominant contributions to the shale anisotropy. We consider two principal reasons of the shale anisotropy: orientation of clay platelets and orientation of fluid-filled cracks. In reality, both of these two factors affect the shale anisotropy. The goal of this study is, first, to separately analyse the effect of these two factors to reveal the specific features in P- and S-wave velocity behaviour typical of each of the factors, and, then, consider a combined effect of the factors when the cracks are horizontally or vertically aligned. To do this, we construct four models of shale. The behaviour of P- and S-wave velocities is analysed when gas- and water-filled cracks embedded in a host matrix are randomly oriented, or horizontally or vertically aligned. The host matrix can be either isotropic or anisotropic (of VTI symmetry). In such a modelling, we use published data on mineralogy and clay platelet alignment along with other micromechanical measurements. In the model, where the host matrix is isotropic, the presence of a singularity point (when the difference VS1 - VS2 changes its sign) in shear wave velocities is an indicator of brine-filled aligned cracks. In the model with the VTI host matrix and horizontally aligned cracks filled with gas, an increase in their volume concentration leads to that the azimuth at which the singularity is observed moves toward the symmetry axis. In this case, if the clay content is small (around 20 per cent), the singularity point may even vanish. The Thomsen parameters are helpful in fluid type indication in shale. An indicator of gas-filled aligned cracks is ?? > ??. If aligned cracks in illite-rich shale are brine-filled, ?? < ??. Negative value of ?? indicates brine-filled cracks in illite-rich shale. A shale with brine-filled cracks exhibits higher Vp/Vs ratio in the vertical direction as compared to the gas-filled shale. A disorientation of clay platelets and brine-filled cracks may lead to that the singularity point is absent for brine-saturated shale as well. In this case one can also observe ?? > ?? and decreased values of Vp/Vs in the vertical direction as in the case of gas-filled cracks. In the presence of vertically aligned cracks, shales exhibit distinctly revealed features of orthorhombic symmetry. The results have important applications where seismic measurements are applied to predict the maturity state of the shale. ?? 2009 The Authors Journal compilation ?? 2009 RAS.

Microstructures and Crystallographic Misorientation in Experimentally Deformed Natural Quartz Single Crystals

NASA Astrophysics Data System (ADS)

Thust, Anja; Heilbronner, Renée.; Stünitz, Holger

2010-05-01

Samples of natural milky quartz were deformed in a Griggs deformation apparatus at different confining pressures (700 MPa, 1000 MPa, 1500 MPa), with constant displacement rates of 1 * 10-6s-1, axial strains of 3 - 19%, and at a temperature of 900° C. The single crystal starting material contains a large number of H2O-rich fluid inclusions. Directly adjacent to the fluid inclusions the crystal is essentially dry (50-150H/106Si, determined by FTIR). The samples were cored from a narrow zone of constant 'milkyness' (i.e. same density of fluid inclusions) in a large single crystal in two different orientations (1) normal to one of the prism planes (⊥{m} orientation) and (2) 45° to and to (O+ orientation).During attaining of the experimental P and T conditions, numerous fluid inclusions decrepitate by cracking. Rapid crack healing produces regions of very small fluid inclusions ('wet' quartz domains). Only these regions are subsequently deformed by dislocation glide, dry quartz domains without cracking and decrepitation of fluid inclusions remain undeformed. Sample strain is not sufficient to cause recrystallization, so that deformation is restricted to dislocation glide. In experiments at lower temperatures (800, 700° C) or at lower strain rate (10-5s-1) there is abundant cracking and semi-brittle deformation, indicating that 900° C, (10-6s-1) represents the lower temperature end of crystal plastic deformation in these single crystals. Peak strengths (at 900° C) range between 150 and 250 MPa for most samples of both orientations. There is a trend of decreasing strength with increasing confining pressure, as described by Kronenberg and Tullis (1984) for quartzites, but the large variation in strength due to inhomogeneous sample strain precludes a definite analysis of the strength/pressure dependence in our single crystals. In the deformed samples, we can distinguish a number of microstructures and inferred different slip systems. In both orientations, deformation lamellae with a high optical relief appear in the usual sub-basal orientation; often they are associated with 'fluid inclusions trails', cracks or en echelon arrays. In ⊥{m} orientation, conjugate misorientation bands sub-parallel to the prism planes can be observed. The barreled shape of the samples can be explained by prism glide. Unfortunately, since prism glide does not affect the c-axis orientation it cannot be recognized on a c-axis orientation image. Nevertheless, changes in the c-axis orientation are observed locally, indicating either the activity of an additional slip system or a different deformation process (not specified yet). In O+ orientation, we observe the formation of internally kinked shear bands. They are up to 100 μm wide and oriented at α 90° w/r to the host c-axis, slightly oblique to the sense of shear. The width of the kinked domains is 20-40 μm and the average misorientation (β) is 5° . The dispersion of c-axis orientation with synthetic rotation of the c-axis is evidence of basal glide. References: Kronenberg, A.K. & Tullis, J. (1984): Flow strength of quartz aggregates: grain size and pressure effects due to hydrolytic weakening. JGR Vol. 89, 4281-4281.

Abyssal Sequestration of Nuclear Waste in Earth's Crust

NASA Astrophysics Data System (ADS)

Germanovich, L. N.; Garagash, D.; Murdoch, L. C.; Robinowitz, M.

2013-12-01

This work outlines a new method for disposing of hazardous (e.g., nuclear) waste. The technique is called Abyssal Sequestration, and it involves placing the waste at extreme depths in Earth's crust where it could achieve the geologically-long period of isolation. Abyssal Sequestration involves storing the waste in hydraulic fractures driven by gravity, a process we term gravity fracturing. In short, we suggest creating a dense fluid (slurry) containing waste, introducing the fluid into a fracture, and extending the fracture downward until it becomes long enough to propagate independently. The fracture will continue to propagate downward to great depth, permanently isolating the waste. Storing solid wastes by mixing them with fluids and injecting them into hydraulic fractures is a well-known technology. The essence of our idea differs from conventional hydraulic fracturing techniques only slightly in that it uses fracturing fluid heavier than the surrounding rock. This difference is fundamental, however, because it allows hydraulic fractures to propagate downward and carry wastes by gravity instead of or in addition to being injected by pumping. An example of similar gravity-driven fractures with positive buoyancy is given by magmatic dikes that may serve as an analog of Abyssal Sequestration occurring in nature. Mechanics of fracture propagation in conditions of positive (diking) and negative (heavy waste slurry) buoyancy is similar and considered in this work for both cases. Analog experiments in gelatin show that fracture breadth (horizontal dimension) remains nearly stationary when fracturing process in the fracture 'head' (where breadth is 'created') is dominated by solid toughness, as opposed to the viscous fluid dissipation dominant in the fracture tail. We model propagation of the resulting 'buoyant' or 'sinking' finger-like fracture of stationary breadth with slowly varying opening along the crack length. The elastic response of the crack to fluid loading in a horizontal cross-section is local and can be treated similar to the classical Perkins-Kern-Nordgren (PKN) model of hydraulic fracturing. The propagation condition for a finger-like crack is based on balancing the global energy release rate due to unit crack extension and the rock fracture toughness. It allows to relate the net fluid pressure at the tip to the fracture breadth and rock toughness. Unlike the PKN fracture, which breadth is known a priori, the final breadth of a finger-like fracture is a result of the fracturing process in the fracture head. To resolve the breadth, we relax the local elasticity assumption in the fracture head by neglecting viscous pressure drop there. The resulting fracture head model is a 3D analog of the Weertman's hydrostatic pulse, and yields expressions for the terminal breadth, b = 0.34 (K / Delta rho g))^(2/3), and for the head volume, V = 10.4 K b^(5/2) / E'. We then combine the finger crack solution for the viscous tail with the 3-D pulse solution for the fracture head. The obtained closed-form solution is compared to numerical simulations. Based on this solution, we analyzed the gravity fracture propagation in conditions of either continuous injection or finite volume release for sets of parameters representative of the heavy waste injection technique and low viscosity magma diking.

The Effect of Crack Orientation on the Nonlinear Interaction of a P-wave with an S-wave

DOE PAGES

TenCate, J. A.; Malcolm, A. E.; Feng, X.; ...

2016-06-06

Cracks, joints, fluids, and other pore-scale structures have long been hypothesized to be the cause of the large elastic nonlinearity observed in rocks. It is difficult to definitively say which pore-scale features are most important, however, because of the difficulty in isolating the source of the nonlinear interaction. In this work, we focus on the influence of cracks on the recorded nonlinear signal and in particular on how the orientation of microcracks changes the strength of the nonlinear interaction. We do this by studying the effect of orientation on the measurements in a rock with anisotropy correlated with the presencemore » and alignment of microcracks. We measure the nonlinear response via the traveltime delay induced in a low-amplitude P wave probe by a high-amplitude S wave pump. We find evidence that crack orientation has a significant effect on the nonlinear signal.« less

Formation of cycloidal features on Europa.

PubMed

Hoppa, G V; Tufts, B R; Greenberg, R; Geissler, P E

1999-09-17

Cycloidal patterns are widely distributed on the surface of Jupiter's moon Europa. Tensile cracks may have developed such a pattern in response to diurnal variations in tidal stress in Europa's outer ice shell. When the tensile strength of the ice is reached, a crack may occur. Propagating cracks would move across an ever-changing stress field, following a curving path to a place and time where the tensile stress was insufficient to continue the propagation. A few hours later, when the stress at the end of the crack again exceeded the strength, propagation would continue in a new direction. Thus, one arcuate segment of the cycloidal chain would be produced during each day on Europa. For this model to work, the tensile strength of Europa's ice crust must be less than 40 kilopascals, and there must be a thick fluid layer below the ice to allow sufficient tidal amplitude.

Stress-dependent permeability and wave dispersion in tight cracked rocks: Experimental validation of simple effective medium models

NASA Astrophysics Data System (ADS)

Sarout, Joel; Cazes, Emilie; Delle Piane, Claudio; Arena, Alessio; Esteban, Lionel

2017-08-01

We experimentally assess the impact of microstructure, pore fluid, and frequency on wave velocity, wave dispersion, and permeability in thermally cracked Carrara marble under effective pressure up to 50 MPa. The cracked rock is isotropic, and we observe that (1) P and S wave velocities at 500 kHz and the low-strain (<10-5) mechanical moduli at 0.01 Hz are pressure-dependent, (2) permeability decreases asymptotically toward a small value with increasing pressure, (3) wave dispersion between 0.01 Hz and 500 MHz in the water-saturated rock reaches a maximum of 26% for S waves and 9% for P waves at 1 MPa, and (4) wave dispersion virtually vanishes above 30 MPa. Assuming no interactions between the cracks, effective medium theory is used to model the rock's elastic response and its permeability. P and S wave velocity data are jointly inverted to recover the crack density and effective aspect ratio. The permeability data are inverted to recover the cracks' effective radius. These parameters lead to a good agreement between predicted and measured wave velocities, dispersion and permeability up to 50 MPa, and up to a crack density of 0.5. The evolution of the crack parameters suggests that three deformation regimes exist: (1) contact between cracks' surface asperities up to 10 MPa, (2) progressive crack closure between 10 and 30 MPa, and (3) crack closure effectively complete above 30 MPa. The derived crack parameters differ significantly from those obtained by analysis of 2-D electron microscope images of thin sections or 3-D X-ray microtomographic images of millimeter-size specimens.

Mathematical model of simple spalling formation during coal cutting with extracting machine

NASA Astrophysics Data System (ADS)

Gabov, V. V.; Zadkov, D. A.

2018-05-01

A single-mass model of a rotor shearer is analyzed. It is shown that rotor mining machines has large inertia moments and load dynamics. An extraction module model with selective movement of the cutting tool is represented. The peculiar feature of such extracting machines is fluid power drive cutter mechanism. They can steadily operate at large shear thickness, and locking modes are not an emergency for them. Comparing with shearers they have less inertional mass, but slower average cutting speed, and its momentary values depend on load. Basing on the equation of hydraulic fuel consumption balance the work of fluid power drive of extracting module cutter mechanism together with hydro pneumatic accumulator is analyzed. Spalling formation model during coal cutting with fluid power drive cutter mechanism and potential energy stores are suggested. Matching cutter speed with the speed of main crack expansion and amount of potential energy consumption, cutter load is determined only by ultimate stress at crack pole and friction. Tests of an extracting module cutter in real size model proved the stated theory.

Modeling of methanol decomposition on Pt/CeO2/ZrO2 catalyst in a packed bed microreactor

NASA Astrophysics Data System (ADS)

Pohar, Andrej; Belavič, Darko; Dolanc, Gregor; Hočevar, Stanko

2014-06-01

Methanol decomposition on Pt/CeO2/ZrO2 catalyst is studied inside a packed bed microreactor in the temperature range of 300-380 °C. The microreactor is fabricated using low-temperature co-fired ceramic (LTCC) technology, which is well suited for the production of relatively complex three-dimensional structures. It is packed with 2 wt% Pt-CeO2 catalyst, which is deposited onto ZrO2 spherical particles. A 1D mathematical model, which incorporates diffusion, convection and mass transfer through the boundary layer to the catalyst particles, as well as a 3D computational fluid dynamics model, are developed to describe the methanol decomposition process inside the packed bed. The microreactor exhibits reliable operation and no catalyst deactivation was observed during three months of experimentation. A comparison between the 1D mathematical model and the 3D model, considering the full 3D geometry of the microreactor is made and the differences between the models are identified and evaluated.

46 CFR 56.60-2 - Limitations on materials.

Code of Federal Regulations, 2014 CFR

2014-10-01

... with a maximum design temperature of 150 °F. The material must not be used for salt water service or other fluids that may cause dezincification or stress corrosion cracking. 6 [Reserved] 7 An ammonia...

46 CFR 56.60-2 - Limitations on materials.

Code of Federal Regulations, 2012 CFR

2012-10-01

... with a maximum design temperature of 150 °F. The material must not be used for salt water service or other fluids that may cause dezincification or stress corrosion cracking. 6 [Reserved] 7 An ammonia...

46 CFR 56.60-2 - Limitations on materials.

Code of Federal Regulations, 2013 CFR

2013-10-01

... with a maximum design temperature of 150 °F. The material must not be used for salt water service or other fluids that may cause dezincification or stress corrosion cracking. 6 [Reserved] 7 An ammonia...

Synthesis of high-temperature viscosity stabilizer used in drilling fluid

NASA Astrophysics Data System (ADS)

Zhang, Yanna; Luo, Huaidong; Shi, Libao; Huang, Hongjun

2018-02-01

Abstract For a well performance drilling fluid, when it operates in deep wells under high temperature, the most important property required is the thermal stability. The drilling fluid properties under high temperature can be controlled by proper selection of viscosity stabilizer, which can capture oxygen to protect polymer agent in the drilling fluid. In this paper a viscosity stabilizer PB-854 is described, which was synthesized by 4-phenoxybutyl bromide, paraformaldehyde, and phloroglucinol using etherification method and condensation reaction. We studied the effect of catalyst dosage, temperature, time, and stirring rate on the synthetic yield. Under this condition: molar ratio of 2-tert-Butylphenol, paraformaldehyde and phloroglucinol of 2:1:2.5, reacting temperature of 100 °C, stirring rate of 100 r min-1, and mass content of catalyst of 15 %, char yield of 5-bromine-3-tert-butyl salicylaldehyde reached 86 %. Under this condition: molar ratio of 5-bromine-3-tert-butyl salicylaldehyde and phloroglucinol of 4, reacting temperature of 60 °C, reacting time of 30 min, volume content of sulphuric acid of 80 %, char yield of the target product viscosity stabilizer PB-854 is 86%. Finally, in this paper, infrared spectroscopy is adopted to analyse the structure of the synthetic product PB-854.The improvement in the stability of drilling fluid was further shown after adding the viscosity stabilizer in the common polymer drilling fluid under high temperature conditions of 120 °C ˜ 180 °C. The results show significant change in terms of fluid stability in the presence of this new stabilizer as it provides better stability.

The ascent of kimberlite: Insights from olivine

NASA Astrophysics Data System (ADS)

Brett, R. C.; Russell, J. K.; Andrews, G. D. M.; Jones, T. J.

2015-08-01

Olivine xenocrysts are ubiquitous in kimberlite deposits worldwide and derive from the disaggregation of mantle-derived peridotitic xenoliths. Here, we provide descriptions of textural features in xenocrystic olivine from kimberlite deposits at the Diavik Diamond Mine, Canada and at Igwisi Hills volcano, Tanzania. We establish a relative sequence of textural events recorded by olivine during magma ascent through the cratonic mantle lithosphere, including: xenolith disaggregation, decompression fracturing expressed as mineral- and fluid-inclusion-rich sealed and healed cracks, grain size and shape modification by chemical dissolution and abrasion, late-stage crystallization of overgrowths on olivine xenocrysts, and lastly, mechanical milling and rounding of the olivine cargo prior to emplacement. Ascent through the lithosphere operates as a "kimberlite factory" wherein progressive upward dyke propagation of the initial carbonatitic melt fractures the overlying mantle to entrain and disaggregate mantle xenoliths. Preferential assimilation of orthopyroxene (Opx) xenocrysts by the silica-undersaturated carbonatitic melt leads to deep-seated exsolution of CO2-rich fluid generating buoyancy and supporting rapid ascent. Concomitant dissolution of olivine produces irregular-shaped relict grains preserved as cores to most kimberlitic olivine. Multiple generations of decompression cracks in olivine provide evidence for a progression in ambient fluid compositions (e.g., from carbonatitic to silicic) during ascent. Numerical modelling predicts tensile failure of xenoliths (disaggregation) and olivine (cracks) over ascent distances of 2-7 km and 15-25 km, respectively, at velocities of 0.1 to >4 m s-1. Efficient assimilation of Opx during ascent results in a silica-enriched, olivine-saturated kimberlitic melt (i.e. SiO2 >20 wt.%) that crystallizes overgrowths on partially digested and abraded olivine xenocrysts. Olivine saturation is constrained to occur at pressures <1 GPa; an absence of decompression cracks within olivine overgrowths suggests depths <25 km. Late stage (<25 km) resurfacing and reshaping of olivine by particle-particle milling is indicative of turbulent flow conditions within a fully fluidized, gas-charged, crystal-rich magma.

Methods and apparatus for carbon dioxide removal from a fluid stream

DOEpatents

Wei, Wei; Ruud, James Anthony; Ku, Anthony Yu-Chung; Ramaswamy, Vidya; Liu, Ke

2010-01-19

An apparatus for producing hydrogen gas wherein the apparatus includes a reactor. In one embodiment, the reactor includes at least two conversion-removal portions. Each conversion-removal portion comprises a catalyst section configured to convert CO in the stream to CO.sub.2 and a membrane section located downstream of and in flow communication with the catalyst section. The membrane section is configured to selectively remove the CO.sub.2 from the stream and to be in flow communication with a sweep gas.

Hierarchical Macro-meso-microporous ZSM-5 Zeolite Hollow Fibers With Highly Efficient Catalytic Cracking Capability

PubMed Central

Liu, Jia; Jiang, Guiyuan; Liu, Ying; Di, Jiancheng; Wang, Yajun; Zhao, Zhen; Sun, Qianyao; Xu, Chunming; Gao, Jinsen; Duan, Aijun; Liu, Jian; Wei, Yuechang; Zhao, Yong; Jiang, Lei

2014-01-01

Zeolite fibers have attracted growing interest for a range of new applications because of their structural particularity while maintaining the intrinsic performances of the building blocks of zeolites. The fabrication of uniform zeolite fibers with tunable hierarchical porosity and further exploration of their catalytic potential are of great importance. Here, we present a versatile and facile method for the fabrication of hierarchical ZSM-5 zeolite fibers with macro-meso-microporosity by coaxial electrospinning. Due to the synergistic integration of the suitable acidity and the hierarchical porosity, high yield of propylene and excellent anti-coking stability were demonstrated on the as-prepared ZSM-5 hollow fibers in the catalytic cracking reaction of iso-butane. This work may also provide good model catalysts with uniform wall thickness and tunable porosity for studying a series of important catalytic reactions. PMID:25450726

Health hazard evaluation report HETA 83-248-1515, Arco Philadelphia refinery, Philadelphia, Pennsylvania

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lewis, F.A.; Parrish, G.

1984-10-01

A bulk sample of fractionator residue was analyzed for polynuclear aromatic (PNA) compounds at the catalytic cracking unit of ARCO Philadelphia Refinery (SIC-2911), Philadelphia, Pennsylvania in May, 1983. The study was requested by the Atlantic Independent Union to determine if skin rashes and skin irritation occurring among refinery workers were caused by PNA in the fractionators. The authors conclude that a health hazard from exposure to chemicals at the cracking unit may exist. No specific chemical agent can be identified. Dust from the catalyst and oily residues that could contaminate workers shoes and clothing may have contributed to some ofmore » the dermatitis cases. Recommendations include laundering workers coveralls by dry cleaning to insure the removal of oily residues, providing workers with oil resistant or oil proof work boots, and repairing the ventilator in the sample preparation room adjacent to the block house.« less

Adhesion mechanisms of bituminous crack sealant to aggregate and laboratory test development

NASA Astrophysics Data System (ADS)

Hajialiakbari Fini, Elham

Crack sealing is a common pavement maintenance treatment because it extends pavement service life. However, crack sealant often fails prematurely due to a loss of adhesion. Since current test methods are mostly empirical and only provide a qualitative measure of bond strength, they cannot predict sealant adhesive failure accurately. Hence, there is an urgent need for test methods based on bituminous sealant rheology that can better predict sealant field performance. This study introduces three laboratory tests aimed to assess the bond property of hot-poured crack sealant to pavement crack walls. The three tests are designed to serve the respective needs of producers, engineers, and researchers. The first test implements the principle of surface energy to measure the thermodynamic work of adhesion, which is the energy spent in separating the two materials at the interface. The work of adhesion is reported as a measure of material compatibility at an interface. The second test is a direct adhesion test, a mechanical test which is designed to closely resemble both the installation process and the crack expansion due to thermal loading. This test uses the Direct Tension Test (DTT) device. The principle of the test is to apply a tensile force to detach the sealant from its aggregate counterpart. The maximum load, Pmax, and the energy to separation, E, are calculated and reported to indicate interface bonding. The third test implements the principles of fracture mechanics in a pressurized circular blister test. The apparatus is specifically designed to conduct the test for bituminous crack sealant, asphalt binder, or other bitumen-based materials. In this test, a fluid is injected at a constant rate at the interface between the substrate (aggregate or a standard material) and the adhesive (crack sealant) to create a blister. The fluid pressure and blister height are measured as functions of time; the data is used to calculate Interfacial Fracture Energy (IFE), which is a fundamental property that can be used to predict adhesion. The stable interface debonding process makes this test attractive. This test also may be used to estimate the optimum annealing time, and to quantify other interface characteristics, such as the moisture susceptibility of a bond. In addition, the elastic modulus of the sealant and its residual stresses can be determined analytically. While the direct adhesion test is proposed as part of newly-developed performance-based guidelines for the selection of hot-poured crack sealant, the blister test may be used to estimate the optimum annealing time, in addition to IFE determination.

Factors controlling the size of graphene oxide sheets produced via the graphite oxide route.

PubMed

Pan, Shuyang; Aksay, Ilhan A

2011-05-24

We have studied the effect of the oxidation path and the mechanical energy input on the size of graphene oxide sheets derived from graphite oxide. The cross-planar oxidation of graphite from the (0002) plane results in periodic cracking of the uppermost graphene oxide layer, limiting its lateral dimension to less than 30 μm. We use an energy balance between the elastic strain energy associated with the undulation of graphene oxide sheets at the hydroxyl and epoxy sites, the crack formation energy, and the interaction energy between graphene layers to determine the cell size of the cracks. As the effective crack propagation rate in the cross-planar direction is an order of magnitude smaller than the edge-to-center oxidation rate, graphene oxide single sheets larger than those defined by the periodic cracking cell size are produced depending on the aspect ratio of the graphite particles. We also demonstrate that external energy input from hydrodynamic drag created by fluid motion or sonication, further reduces the size of the graphene oxide sheets through tensile stress buildup in the sheets.

DEVELOPMENT OF ATTRITION RESISTANT IRON-BASED FISCHER-TROPSCH CATALYSTS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Adeyinka A. Adeyiga

2001-09-01

The Fischer-Tropsch (F-T) reaction provides a way of converting coal-derived synthesis gas (CO+H{sub 2}) to liquid fuels. Since the reaction is highly exothermic, one of the major problems in control of the reaction is heat removal. Recent work has shown that the use of slurry bubble column reactors (SBCRs) can largely solve this problem. The use of iron-based catalysts is attractive not only due to their low cost and ready availability, but also due to their high water-gas shift activity which makes it possible to use these catalysts with low H{sub 2}/CO ratios. However, a serious problem with use ofmore » Fe catalysts in a SBCR is their tendency to undergo attrition. This can cause fouling/plugging of downstream filters and equipment, makes the separation of catalyst from the oil/wax product very difficult if not impossible, and results in a steady loss of catalyst from the reactor. Recently, fundamental understanding of physical attrition is being addressed by incorporating suitable binders into the catalyst recipe. This has resulted in the preparation of a spray dried Fe-based catalyst having aps of 70 mm with high attrition resistance. This Fe-based attrition resistant, active and selective catalyst gave 95% CO conversion through 125 hours of testing in a fixed-bed at 270 C, 1.48 MPa, H{sub 2}/CO=0.67 and 2.0 NL/g-cat/h with C{sub 5}{sup +} selectivity of >78% and methane selectivity of <5%. However, further development of the catalyst is needed to address the chemical attrition due to phase changes that any Fe-catalyst goes through potentially causing internal stresses within the particle and resulting in weakening, spalling or cracking. The objective of this research is to develop robust iron-based Fischer-Tropsch catalysts that have suitable activity, selectivity and stability to be used in the slurry bubble column reactor. Specifically we aim to develop to: (i) improve the performance and preparation procedure of the high activity, high attrition resistant, high alpha iron-based catalysts synthesized at Hampton University, (ii) seek improvements in the catalyst performance through variations in process conditions, pretreatment procedures and/or modifications in catalyst preparation steps and (iii) investigate the performance in a slurry reactor. The effort during the reporting period has been devoted to attrition study of the iron-based catalysts. Precipitated silica appeared to decrease attrition resistance of spray-dried iron FT catalysts. It was found that the catalyst with precipitated silica content at around 12wt% showed the lowest attrition resistance. The results of net change in volume moment and catalyst morphology showed supporting evidences to the attrition results. Catalysts with low attrition resistance generated more fines loss, had higher net change in volume moment and showed more breakage of particles. BET surface area and pore volume of this catalyst series fluctuated; therefore no conclusion can be drawn from the data obtained. However, catalyst with no precipitated silica showed the lowest in BET surface area and pore volume, as expected. Addition of precipitated silica to the catalysts had no effect to the phase changes of iron that could have significant influence to catalyst attrition. The presence of precipitated silica is needed for enhancing catalyst surface area; however, the amount of silica added should be compromising with attrition resistance of catalysts.« less

High density Polyethylene plastic waste treatment with microwave heating pyrolysis method using coconut-shell activated carbon to produce alternative fuels

NASA Astrophysics Data System (ADS)

Juliastuti, S. R.; Hisbullah, M. I.; Abdillah, M.

2018-03-01

Pyrolysis is a technology that could crack polimer such as plastic waste into alternative fuels. This research uses microwave heating methode, which more efficient than conventional heating methode. The plastic waste used is 200 grams of HDPE, with feed to catalyst weight ratio are 1:1, 0.6:1, 0.4:1. Pyrolysis was run at temperatures of 250, 300, 350, & 400 °C for 15, 30 and 45 min. From the experimental result, the best variable of pyrolysis process with microwave method is at 45 minutes, at 400°C, and 1:1 feed to catalyst weight ratio. Result shows that yield of liquid and gas product is 99.22%; yield of residue is 0.78%; value of liquid product’s composition (cycloparaffin and n-paraffin) is 54.09% and concentration of methane gas is 10.2%.

Mesoporous Aluminosilicate Catalysts for the Selective Isomerization of n-Hexane: The Roles of Surface Acidity and Platinum Metal.

PubMed

Musselwhite, Nathan; Na, Kyungsu; Sabyrov, Kairat; Alayoglu, Selim; Somorjai, Gabor A

2015-08-19

Several types of mesoporous aluminosilicates were synthesized and evaluated in the catalytic isomerization of n-hexane, both with and without Pt nanoparticles loaded into the mesopores. The materials investigated included mesoporous MFI and BEA type zeolites, MCF-17 mesoporous silica, and an aluminum modified MCF-17. The acidity of the materials was investigated through pyridine adsorption and Fourier Transform-Infrared Spectroscopy (FT-IR). It was found that the strong Brönsted acid sites in the micropores of the zeolite catalysts facilitated the cracking of hexane. However, the medium strength acid sites on the Al modified MCF-17 mesoporous silica greatly enhanced the isomerization reaction. Through the loading of different amounts of Pt into the mesopores of the Al modified MCF-17, the relationship between the metal nanoparticles and acidic sites on the support was revealed.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gianetto, A.; Farag, H.I.; Blasetti, A.P.

Changes of the relative importance of intradiffusion on USY zeolite crystals were studied as a way of affecting selectivity of catalytic cracking reactions. Zeolite crystals were synthesized (Si/Al = 2.4), activated and stabilized using ion exchange and steam calcination to obtain USSY (Ultra Stable Submicron Y) zeolites. After the activation the zeolites were pelletized (45--60 [mu]m particles). USSYs were tested in a novel Riser Simulator. Results obtained show that total aromatics (BTX), benzene, C[sub 4] olefins, and coke were significantly affected with the change of zeolite crystal sizes. Gasolines produced with USSY zeolites contain less aromatics and particularly lower benzenemore » levels. Experimental results were analyzed with a model including several lumps: unconverted gas oil, gasoline, light gases, and coke. This model also accounts for catalyst deactivation as a function of coke on catalyst. Various kinetic parameters were determined with their corresponding spans for the 95% level of confidence.« less

Reactive-brittle dynamics in peridotite alteration

NASA Astrophysics Data System (ADS)

Evans, O.; Spiegelman, M. W.; Kelemen, P. B.

2017-12-01

The interactions between reactive fluids and brittle solids are critical in Earth dynamics. Implications of such processes are wide-ranging: from earthquake physics to geologic carbon sequestration and the cycling of fluids and volatiles through subduction zones. Peridotite alteration is a common feature in many of these processes, which - despite its obvious importance - is relatively poorly understood from a geodynamical perspective. In particular, alteration reactions are thought to be self-limiting in nature, contradicting observations of rocks that have undergone 100% hydration/carbonation. One potential explanation of this observation is the mechanism of "reaction-driven cracking": that volume changes associated with these reactions are large enough to fracture the surrounding rock, leading to a positive feedback where new reactive surfaces are exposed and fluid pathways are created. The purpose of this study is to investigate the relative roles of reaction, elastic stresses and surface tension in alteration reactions. In this regard we derive a system of equations describing reactive fluid flow in an elastically deformable porous media, and explore them via a combination of analytic and numerical solutions. Using this model we show that the final stress state of a dry peridotite that has undergone reaction depends strongly on the rates of reaction versus fluid transport: significant fluid flow driven by pressure and/or surface tension gradients implies higher fractions of serpentinization, leaving behind a highly stressed residuum of partially reacted material. Using a model set-up that mimics a cylindrical triaxial apparatus we predict that the resulting stresses would lead to tensile failure and the generation of radially oriented cracks.

Chemical Characterization and Thermal Stressing Studies of Perfluorohexane Fluids for Space-Based Applications

NASA Technical Reports Server (NTRS)

Arnold, William A.; Hartman, Thomas G.; McQuillen, John

2006-01-01

Perfluorohexane (PFH), C6F14, is a perfluorocarbon fluid. Several PFH fluids with different isomer concentrations were evaluated for use in an upcoming NASA space experiment. Samples tested included two commercially obtained high-purity n-perfluorohexane (n-PFH) fluids and a technical grade mixture of C6F14 branched and linear isomers (FC-72(TradeMark)). These fluids were evaluated for exact chemical composition, impurity purity and high temperature degradation behavior (pyrolysis). Our investigation involved simulated thermal stressing studies of PFH fluids under conditions likely to occur in the event of an atmospheric breach within the International Space Station (ISS) and subsequent exposure of the vapors to the high temperature and catalyst present in its Trace Contaminant Control Subsystem (TCCS). Exposure to temperatures in the temperature range of 200-450 C in an inert or oxidizing atmosphere, with and without the presence of catalyst was investigated. The most aggressive conditions studied were exposure of PFH vapors to 450 C in air and in the presence of TCCS (palladium) catalyst. Gas chromatography-mass spectrometry (GC-MS) and gas chromatography (GC) analyses were conducted on the perfluorohexane samples before and after pyrolysis. The FC-72 and n-PFH samples showed no significant degradation following pyrolysis even under the most aggressive study conditions. Some trace level impurities associated with the PFH samples such as linear perfluorocarbon monohydrides or monoiodides were destroyed by pyrolysis at the upper limit. Other trace level impurities such as olefinic or cycloolefinic perfluorocarbons were converted into oxidation products by pyrolysis. The purity of PFH following pyrolysis actually increased slightly as a consequence since these trace contaminants were effectively scrubbed from the samples. However, since the initial concentrations of the thermally-impacted impurities were so low, the net effect was trivial. A potential byproduct of exposure of perfluorohexane fluids to high temperatures is the production of perfluoroisobutene (PFiB), which is extremely toxic. An ultra-high sensitivity PFiB-specific analysis based on GC-MS with negative ion chemical ionization (NICI) detection was used to evaluate the samples following thermal stressing. The perfluorohexanes examined here under conditions reflective of the ISS TCCS environment showed no signs of PFiB production with an analytical detection limit of 10 part per billion (ppb v/v).

Chemicals from low temperature liquid-phase cracking of coals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sato, Y.; Kodera, Y.; Kamo, T.

1999-07-01

Mild gasification and low temperature pyrolysis are considered to be the most promising process for high-moisture subbituminous and lignite coal to produce upgraded solid fuel with high heating value and low sulfur, and to produce a useful liquid product. However effective technology to prevent spontaneous combustion of solid product and to utilize oxygen-rich liquid product has not yet been reported to enhance commercial feasibility of these process. In this study, liquid-phase cracking of low rank coal at 350--450 C under 2 MPa of initial nitrogen atmosphere has been studied to produce upgraded coal and value added liquid product. Liquid-phase crackingmore » of Wyoming subbituminous Buckskin coal using iron oxide catalyst in the presence of t-decalin at 440C gave 10 wt% of liquid product, 12 wt% of gases and 74 wt% of upgraded coal with small amount of water. Gaseous product consisted of mainly carbon dioxide (62wt%) and methane. Therefore, cracking of carboxylic function took place effectively in these conditions. Liquid product contains BTX, phenols and alkylphenols. Concentrated chemicals of BTX, phenol and cresols from the liquid products by hydrocracking and hydrotreating will be discussed.« less

Crack networks in damaged glass

NASA Astrophysics Data System (ADS)

Mallet, Celine; Fortin, Jerome; Gueguen, Yves

2013-04-01

We investigate how cracks develop and propagate in synthetic glass samples. Cracks are introduced in glass by a thermal shock of 300oC. Crack network is documented from optical and electronic microscopy on these samples that have been submitted to a thermal shock only. Samples are cylinder of 80 mm length and 40 mm diameter. Sections were cut along the cylinder axis and perpendicular to it. Using SEM, crack lengths and apertures can be measured. Optical microscopy allows to get the crack distribution over the entire sample. The sample average crack length is 3 mm. The average aperture is 6 ± 3μm. There is however a clear difference between the sample core, where the crack network has approximatively a transverse isotrope symmetry and the outer ring, where cracks are smaller and more numerous. By measuring before and after the thermal treatment the radial P and S wave velocities in room conditions, we can determine the total crack density which is 0.24. Thermally cracked samples, as described above, were submitted to creep tests. Constant axial stress and lateral stress were applied. Several experiments were performed at different stress values. Samples are saturated for 48 hours (to get an homogeneous pore fluid distribution), the axial stress is increased up to 80% of the sample strength. Stress step tests were performed in order to get creep data. The evolution of strain (axial and radial strain) is measured using strain gages, gap sensors (for the global axial strain) and pore volume change (for the volumetric strain). Creep data are interpreted as evidence of sub-critical crack growth in the cracked glass samples. The above microstructural observations are used, together with a crack propagation model, to account for the creep behavior. Assuming that (i) the observed volumetric strain rate is due to crack propagation and (ii) crack aspect ratio is constant we calculate the creep rate. We obtain some value on the crack propagation during a 24 hours of constant stress test. At each of these test, crack propagate of 0.3 to 0.4 mm. From the initial average crack length of 3 mm, the crack reach the size of 5.8 mm at the end of a complete creep test (with 8 constant stress step of 24 hours).

Monodisperse microbeads of hypercrosslinked polystyrene for liquid and supercritical fluid chromatography

NASA Astrophysics Data System (ADS)

Tsyurupa, M. P.; Blinnikova, Z. K.; Il'in, M. M.; Davankov, V. A.; Parenago, O. O.; Pokrovskii, O. I.; Usovich, O. I.

2015-11-01

Monodisperse styrene-divinylbenzene (1 wt %) copolymer microbeads are obtained via the elaborate method of high-productivity precipitation polymerization. The crosslinking of this copolymer with chloromethyl methyl ether in the presence of Friedel-Crafts catalyst yields porous hypercrosslinked polymers with degrees of crosslinking that range from 200 to 500%. Microbead sorbents are shown to be suited for selective stationary phases for high-performance liquid chromatography and supercritical fluid chromatography.

Effects of fluids on rock deformation and fault slip: From nature to societal impact (Louis Néel Medal Lecture)

NASA Astrophysics Data System (ADS)

Spiers, Christopher J.

2017-04-01

Understanding the effects of fluid-rock interaction on rock and fault mechanical behaviour is central not only to understanding natural tectonic and seismogenic processes, and phenomena such as resource trapping, but also to evaluating the impact of industrial operations in the Earth's crust. These include activities ranging from extraction of geo-energy to geological storage of fuels, CO2 and wastes. For the assessment of both natural and induced geohazards, a physics-based approach to quantifying rock mechanical behaviour is unmissable. Microstructural studies of rocks deformed naturally in the mid and upper crust, or at seismogenic depths in subduction zones, show widespread evidence for brittle deformation (cataclasis), dissolution-precipitation transfer, fluid-related reactions producing weak minerals, and dilatation/cementation of fractures, cracks and pores. In addition, experimental work on rocks and simulated fault gouges has shown that the presence of water strongly influences their mechanical and transport properties. This implies the operation of fluid-assisted deformation mechanisms, such as stress corrosion cracking and diffusive mass transfer (pressure solution). More recently, other fluid-coupled deformation processes have been recognised, in rocks from peridotites and granites to sandstones, limestones and shales. In this lecture, I will give an overview of progress in this area. I will address the physics of pressure solution and stress corrosion cracking and how they contribute to the deformation and compaction of sandstone, carbonate and evaporite rocks in the mid and upper crust, under natural conditions and in the context of deformation caused by geo-resources production and geo-storage. New results on how these processes are affected by pore fluid salinity, gas content and CO2 activity will also be considered, as will data on the effects of mineral-fluid reactions and associated volume changes on rock deformation, fracturing and transport. The effects of gas and CO2 sorption on the stress-strain behaviour and permeability of clay and shale caprocks, recently reported in relation to seal integrity, will be addressed too, and compared with similar phenomena familiar in seen in coal seams. Lastly, I will address the effects of fluid-rock interaction on the frictional behaviour of faults. Recent low velocity friction experiments (<100 μm/s) performed on simulated carbonate, evaporite and quartz gouges, with varying phyllosilicate content, indicate that pressure solution is key to determining whether frictional slip is velocity-strengthening (stable) or velocity weakening (potentially seismogenic). An important trend seen is a transition from velocity strengthening at low temperatures, to velocity weakening at intermediate temperatures, and back to velocity strengthening at high temperatures. This behaviour and the restrengthening observed when shearing is stopped are strongly influenced by water content. It is inferred that mechanistic models for the frictional behaviour of gouge-filled faults, under crustal conditions, must account for diffusion and stress corrosion cracking, and for slip on grain boundaries. First attempts to do this, assuming diffusive mass transfer as the fluid-assisted mechanism, successfully predict the steady state and transient behaviour seen in experiments and offer new perspectives for providing friction laws as for modelling earthquake rupture nucleation and evaluating seismic hazard, in the context of both natural and induced seismicity.

Sensing fluid pressure during plucking events in a natural bedrock channel and experimental flume

NASA Astrophysics Data System (ADS)

Wilkinson, C.; Harbor, D. J.; Keel, D.; Levy, S.; Kuehner, J. P.

2016-12-01

River channel erosion by plucking is believed to be the dominant erosional process in channels with fractured or jointed bedrock. However, despite its significance as an erosional mechanism, plucking is poorly studied in both laboratory and natural channels. In previous flume studies, model bedrock was plucked by fluid forces alone in nonuniform flow near jumps and waves even where blocks do not protrude into the flow. Here we develop sensor systems to test the hypothesis that bed fluid pressure gradients lift "pluckable" bedrock blocks in a natural field setting and a hydraulic flume. The field setting closely mimics the previous flume setup; the instrumented block is downstream of a roughly 1m step and exhibits no protrusion into the flow. The presence of the step promotes nonuniform flow which changes pressure in the bedrock crack network; slabs of bedrock that have slid downstream and sediment that has been pushed upstream 3-4 m under the bed and in the cracks suggest the influence of pressure differences throughout the crack network and below the bed. In this initial deployment, we evaluate a sensor that monitors movement and simultaneous pressure above and below the block. Sensors are emplaced in a 26kg, 45-cm-long, 20-cm-wide block broken from a 4.5-m-long, 11-cm-thick sandstone bed with a dense network of cracks nearly parallel to flow direction and include a tri-axial accelerometer/gyroscope and two fluid pressure sensors. The electronics are housed in a custom-designed 3D-printed ABS waterproof capsule that is mounted in a vertical hole through the rock. A concurrent flume study develops the sensors necessary to investigate the longitudinal pressure difference below a step using multiple analog sensors (0-1 psi gauge pressure) mounted flush to a false floor under the center of a 30x14-cm test zone. The 15-mm-wide sensors are aligned along the flow centerline and are placed under 25 1-cm-thick "pluckable" bedrock blocks constructed with a proprietary plaster cement. Measured mean pressure and transmission of pressure pulses under the test bed are compared to the visual record of plucking. In addition, conducting runs with blocks removed permits simulation of the mean and varying pressure conditions above the modeled "pluckable" layer as a hydraulic jump is moved downstream through the step.

The Influence of Deposition Methods of Support Layer on Cordierite Substrate on the Characteristics of a MnO2–NiO–Co3O4/Ce0.2Zr0.8O2/Cordierite Three Way Catalyst

PubMed Central

Pham, Phuong Thi Mai; Le, Minh Thang; Nguyen, Tien The; Bruneel, Els; Van Driessche, Isabel

2014-01-01

This paper compares different coating methods (in situ solid combustion, hybrid deposition, secondary growth on seed, suspension, double deposition of wet impregnation and suspension) to deposit Ce0.2Zr0.8O2 mixed oxides on cordierite substrates, for use as a three way catalyst. Among them, the double deposition was proven to be the most efficient one. The coated sample shows a BET (Brunauer–Emmett–Teller) surface area of 25 m2/g, combined with a dense and crack free surface. The catalyst with a layer of MnO2–NiO–Co3O4 mixed oxides on top of the Ce0.2Zr0.8O2/cordierite substrate prepared by this method exhibits good activity for the treatment of CO, NO and C3H6 in exhaust gases (CO conversion of 100% at 250 °C, C3H6 conversion of 100% at 400 °C and NO conversion of 40% at 400 °C). PMID:28788189

[Selective catalytic reduction of NOx over Pd/CeZr/TiO2/Al2O3 wire-mesh honeycomb catalysts].

PubMed

Sun, Hong; Quan, Xie; Zhang, Yao-bin; Zhao, Ya-zhi

2008-06-01

Pd/CeZr/TiO2/Al2O3 wire-mesh honeycomb catalyst was prepared by sol-gel and impregnation. Furthermore, selective catalytic reduction of NOx over Pd/CeZr/TiO2/Al2O3 wire-mesh honeycomb catalyst with propylene under lean burn condition was studied. The effects of the concentration of tetra-n-butyl titanate and dipcoat cycles on TiO2 washcoat were studied by SEM, and the effects of Pd concentration, O2 concentration and gas velocity on catalytic activity were investigated. The experimental results showed that the TiO2 washcoat on wire-mesh support is even and crack-free when the support is impregnated in 20.0% tetra- n-butyl titanate sol for 2 cycles. The NOx conversion decreases with Pd concentration increase. When Pd concentration is 0.23%, NOx conversion is highest. NOx conversion increases with oxygen concentration increase in the range of 1.5%-6.0%. However, when oxygen concentration is higher than 6.0%, NOx conversion decreases with increasing oxygen concentration. The NOx conversion decreases with gas velocity increase and its effect is severer at high temperature than low temperature.

Oxidative coupling of methane over a Sr-promoted La{sub 2}O{sub 3} catalyst supported on a low surface area porous catalyst carrier

DOE Office of Scientific and Technical Information (OSTI.GOV)

Choudhary, V.R.; Uphade, B.S.; Mulla, S.A.R.

1997-09-01

Oxidative coupling of methane (OCM) to higher hydrocarbons over Sr-promoted La{sub 2}O{sub 3} supported on commercial low surface area porous catalyst carriers at 800 and 850 C and a space velocity of 102,000 cm{sup 3}/g{center_dot}h has been thoroughly investigated. Effects of support, catalyst particle size, linear gas velocity, Sr/La ratio, CH{sub 4}/O{sub 2} ratio in the feed, and catalyst dilution by inert solid particles on the conversion, yield, or selectivity and product ratios (C{sub 2}H{sub 4}/C{sub 2}H{sub 6} and CO/CO{sub 2}) in the OCM process have been studied. The catalysts have been characterized for their basicity, acidity, and oxygen chemisorptionmore » by the TPD of CO{sub 2}, ammonia, and oxygen, respectively, from 50 to 950 C and also characterized for their surface area. The supported catalysts showed better performance than the unsupported one. The best OCM results (obtained over Sr-La{sub 2}O{sub 3}/SA-5205 with a Sr/La ratio of 0.3 at a space velocity of 102,000 cm{sup 3}/g{center_dot}h) are 30.1% CH{sub 4} conversion with 65.6% selectivity for C{sub 2+} (or 19.7% C{sub 2+}-yield) at 850 C (CH{sub 4}/O{sub 2} = 16.0). The basicity is strongly influenced by the Sr/La ratio; the supported catalysts showed the best performance for their Sr/La ratio of about 0.3. The methane/O{sub 2} ratio also showed a strong influence for their Sr/La ratio of about 0.3. The methane/O{sub 2} ratio also showed a strong influence on the OCM process. However, the influence of linear gas velocity and particle size is found to be small; it results mainly from the temperature gradient in the catalyst. The catalyst dilution has beneficial effects for achieving a higher C{sub 2}H{sub 4}/C{sub 2}H{sub 6} ratio and also for reducing the hazardous nature of the OCM process because of the coupling of the exothermic oxidative conversion reactions and the endothermic thermal cracking reactions and also due to the increased heat transfer area.« less

Liquid zone seal

DOEpatents

Klebanoff, Leonard E.

2001-01-01

A seal assembly that provides a means for establishing multiple pressure zones within a system. The seal assembly combines a plate extending from the inner wall of a housing or inner enclosure that intersects with and is immersed in the fluid contained in a well formed in a tray contained within the enclosure. The fluid is a low vapor pressure oil, chemically inert and oxidation resistant. The use of a fluid as the sealing component provides a seal that is self-healing and mechanically robust not subject to normal mechanical wear, breakage, and formation of cracks or pinholes and decouples external mechanical vibrations from internal structural members.

Fluid-driven Fractures and Backflow in a Multilayered Elastic Matrix

NASA Astrophysics Data System (ADS)

Smiddy, Samuel; Lai, Ching-Yao; Stone, Howard

2016-11-01

We study the dynamics when pressurized fluid is injected at a constant flow rate into a multi-layered elastic matrix. In particular, we report experiments of such crack propagation as a function of orientation and distance from the contact of the layers. Subsequently we study the shape and propagation of the fluid along the contact of layers as well as volume of fluid remaining in the matrix once the injection pressure is released and "flowback" occurs. The experiments presented here may mimic the interaction between hydraulic fractures and pre-existing fractures and the dynamics of flowback in hydraulic fracturing. Study made possible by the Andlinger Center for Energy and the Environment and the Fred Fox Fund.

Structure of mono- and bimetallic heterogeneous catalysts based on noble metals obtained by means of fluid technology and metal-vapor synthesis

NASA Astrophysics Data System (ADS)

Said-Galiev, E. E.; Vasil'kov, A. Yu.; Nikolaev, A. Yu.; Lisitsyn, A. I.; Naumkin, A. V.; Volkov, I. O.; Abramchuk, S. S.; Lependina, O. L.; Khokhlov, A. R.; Shtykova, E. V.; Dembo, K. A.; Erkey, C.

2012-10-01

Monometallic nanocomposites are obtained with the use of supercritical carbon dioxide (fluid technique) and metal-vapor synthesis (MVS), while bimetallic nanocomposites of Pt and Au noble metals and γ-Al2O3 oxide matrix are synthesized by a combination of these two methods. The structures, concentrations, and chemical states of metal atoms in composites are studied by means of small-angle X-ray scattering (SAXS), transparent electron microscopy (TEM), X-ray fluorescent analysis (XFA), and X-ray photoelectron spectroscopy (XPS). The neutral state of metal atoms in clusters is shown by XPS and their size distribution is found according to SAXS; as is shown, it is determined by the pore sizes of the oxide matrices and lies in the range of 1 to 50 nm. The obtained composites manifest themselves as effective catalysts in the oxidation of CO to CO2.

Seismic characteristics of tensile fracture growth induced by hydraulic fracturing

NASA Astrophysics Data System (ADS)

Eaton, D. W. S.; Van der Baan, M.; Boroumand, N.

2014-12-01

Hydraulic fracturing is a process of injecting high-pressure slurry into a rockmass to enhance its permeability. Variants of this process are used for unconventional oil and gas development, engineered geothermal systems and block-cave mining; similar processes occur within volcanic systems. Opening of hydraulic fractures is well documented by mineback trials and tiltmeter monitoring and is a physical requirement to accommodate the volume of injected fluid. Numerous microseismic monitoring investigations acquired in the audio-frequency band are interpreted to show a prevalence of shear-dominated failure mechanisms surrounding the tensile fracture. Moreover, the radiated seismic energy in the audio-frequency band appears to be a miniscule fraction (<< 1%) of the net injected energy, i.e., the integral of the product of fluid pressure and injection rate. We use a simple penny-shaped crack model as a predictive framework to describe seismic characteristics of tensile opening during hydraulic fracturing. This model provides a useful scaling relation that links seismic moment to effective fluid pressure within the crack. Based on downhole recordings corrected for attenuation, a significant fraction of observed microseismic events are characterized by S/P amplitude ratio < 5. Despite the relatively small aperture of the monitoring arrays, which precludes both full moment-tensor analysis and definitive identification of nodal planes or axes, this ratio provides a strong indication that observed microseismic source mechanisms have a component of tensile failure. In addition, we find some instances of periodic spectral notches that can be explained by an opening/closing failure mechanism, in which fracture propagation outpaces fluid velocity within the crack. Finally, aseismic growth of tensile fractures may be indicative of a scenario in which injected energy is consumed to create new fracture surfaces. Taken together, our observations and modeling provide evidence that failure mechanisms documented by passive monitoring of hydraulic fractures may contain a significant component of tensile failure, including fracture opening and closing, although creation of extensive new fracture surfaces may be a seismically inefficient process that radiates at sub-audio frequencies.

Computation of dynamic seismic responses to viscous fluid of digitized three-dimensional Berea sandstones with a coupled finite-difference method.

PubMed

Zhang, Yang; Toksöz, M Nafi

2012-08-01

The seismic response of saturated porous rocks is studied numerically using microtomographic images of three-dimensional digitized Berea sandstones. A stress-strain calculation is employed to compute the velocities and attenuations of rock samples whose sizes are much smaller than the seismic wavelength of interest. To compensate for the contributions of small cracks lost in the imaging process to the total velocity and attenuation, a hybrid method is developed to recover the crack distribution, in which the differential effective medium theory, the Kuster-Toksöz model, and a modified squirt-flow model are utilized in a two-step Monte Carlo inversion. In the inversion, the velocities of P- and S-waves measured for the dry and water-saturated cases, and the measured attenuation of P-waves for different fluids are used. By using such a hybrid method, both the velocities of saturated porous rocks and the attenuations are predicted accurately when compared to laboratory data. The hybrid method is a practical way to model numerically the seismic properties of saturated porous rocks until very high resolution digital data are available. Cracks lost in the imaging process are critical for accurately predicting velocities and attenuations of saturated porous rocks.

JSC Materials Laboratory Reproduction and Failure Analysis of Cracked Orbiter Reaction Control System Niobium Thruster Injectors

NASA Technical Reports Server (NTRS)

Castner, Willard L.; Jacobs, Jeremy B.

2006-01-01

In April 2004 a Space Shuttle Orbiter Reaction Control System (RCS) thruster was found to be cracked while undergoing a nozzle (niobium/C103 alloy) retrofit. As a failure resulting from an in-flight RCS thruster burn-through (initiated from a crack) could be catastrophic, an official Space Shuttle Program flight constraint was issued until flight safety could be adequately demonstrated. This paper describes the laboratory test program which was undertaken to reproduce the cracking in order to fully understand and bound the driving environments. The associated rationale developed to justify continued safe flight of the Orbiter RCS system is also described. The laboratory testing successfully reproduced the niobium cracking, and established specific bounding conditions necessary to cause cracking in the C103 thruster injectors. Each of the following conditions is necessary in combination together: 1) a mechanically disturbed / cold-worked free surface, 2) an externally applied sustained tensile stress near yield strength, 3) presence of fluorine-containing fluids on exposed tensile / cold-worked free surfaces, and 4) sustained exposure to temperatures greater than 400 F. As a result of this work, it was concluded that fluorine-containing materials (e.g. HF acid, Krytox , Brayco etc.) should be carefully controlled or altogether eliminated during processing of niobium and its alloys.

STS-133/ET-137 Tanking Test Photogrammetry Assessment

NASA Technical Reports Server (NTRS)

Oliver, Stanley T.

2012-01-01

Following the launch scrub of Space Shuttle mission STS-133 on November 5, 2010, an anomalous condition of cracked and raised thermal protection system (TPS) foam was observed on the External Tank (ET). Subsequent dissection of the affected TPS region revealed cracks in the feet of two Intertank (IT) metallic stringers. An extensive investigation into the cause(s) and corrective action(s) for the cracked stringers was initiated, involving a wide array of material and structural tests and nondestructive evaluations, with the intent to culminate into the development of flight rational. One such structural test was the instrumented tanking test performed on December 17, 2010. The tanking test incorporated two three-dimensional optical displacement measurement systems to measure full-field outer surface displacements of the TPS surrounding the affected region that contained the stringer cracks. The results showed that the radial displacement and rotation of the liquid oxygen (LO2) tank flange changed significantly as the fluid level of the LO2 approached and passed the LO2 tank flange.

Scientific bases of biomass processing into basic component of aviation fuel

NASA Astrophysics Data System (ADS)

Kachalov, V. V.; Lavrenov, V. A.; Lishchiner, I. I.; Malova, O. V.; Tarasov, A. L.; Zaichenko, V. M.

2016-11-01

A combination of feedstock pyrolysis and the cracking of the volatile pyrolysis products on the charcoal at 1000 °C allows to obtain a tarless synthesis gas which contains 90 vol% or more of carbon monoxide and hydrogen in approximately equal proportions. Basic component of aviation fuel was synthesized in a two-stage process from gas obtained by pyrolytic processing of biomass. Methanol and dimethyl ether can be efficiently produced in a two-layer loading of methanolic catalyst and γ-Al2O3. The total conversion of CO per pass was 38.2% using for the synthesis of oxygenates a synthesis gas with adverse ratio of H2/CO = 0.96. Conversion of CO to CH3OH was 15.3% and the conversion of CO to dimethyl ether was 20.9%. A high yield of basic component per oxygenates mass (44.6%) was obtained during conversion. The high selectivity of the synthesis process for liquid hydrocarbons was observed. An optimal recipe of aviation fuel B-92 based on a synthesized basic component was developed. The prototype of aviation fuel meets the requirements for B-92 when straight fractions of 50-100 °C (up to 35 wt%), isooctane (up to 10 wt%) and ethyl fluid (2.0 g/kg calculated as tetraethyl lead) is added to the basic component.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Seewald, Jeffrey, S.

Results of prior DOE supported research conducted at the Woods Hole Oceanographic Institution have demonstrated the participation of sedimentary minerals and water as reactants and catalysts in chemical transformations associated with the degradation of oil and the formation of low molecular weight organic compounds. The occurrence of such processes in natural environments can be difficult to recognize because the composition of organic alteration products may not be substantially different than those produced by thermal cracking. The goals of this study were the development of diagnostic tools based on hydrogen and carbon isotopes that can be used to identify geochemical processesmore » responsible for the formation of thermogenic natural gas. In addition, our activities were expanded to include experimental investigation of CO2 reduction in aqueous systems at elevated temperature and pressures and an assessment of microbial activity in relatively low temperature (<70°C) natural gas reservoirs in southeastern Oklahoma. Specific objectives included: A laboratory investigation of geochemical processes that regulate the hydrogen isotope composition of low molecular weight hydrocarbons in natural gas at elevated temperatures and pressures. A laboratory investigation of factors that regulate the carbon isotope composition of organic acids in basinal brines. A laboratory assessment of the role of methanol during reduction of CO2 to CH4 under hydrothermal conditions. Characterization of microbial ecosystems in coproduced fluids from the Potato Hills gas field to assess the role of microbes in the generation of natural gas.« less

Water pumping in mantle shear zones

PubMed Central

Précigout, Jacques; Prigent, Cécile; Palasse, Laurie; Pochon, Anthony

2017-01-01

Water plays an important role in geological processes. Providing constraints on what may influence the distribution of aqueous fluids is thus crucial to understanding how water impacts Earth's geodynamics. Here we demonstrate that ductile flow exerts a dynamic control on water-rich fluid circulation in mantle shear zones. Based on amphibole distribution and using dislocation slip-systems as a proxy for syn-tectonic water content in olivine, we highlight fluid accumulation around fine-grained layers dominated by grain-size-sensitive creep. This fluid aggregation correlates with dislocation creep-accommodated strain that localizes in water-rich layers. We also give evidence of cracking induced by fluid pressure where the highest amount of water is expected. These results emphasize long-term fluid pumping attributed to creep cavitation and associated phase nucleation during grain size reduction. Considering the ubiquitous process of grain size reduction during strain localization, our findings shed light on multiple fluid reservoirs in the crust and mantle. PMID:28593947

SPH modeling of fluid-solid interaction for dynamic failure analysis of fluid-filled thin shells

NASA Astrophysics Data System (ADS)

Caleyron, F.; Combescure, A.; Faucher, V.; Potapov, S.

2013-05-01

This work concerns the prediction of failure of a fluid-filled tank under impact loading, including the resulting fluid leakage. A water-filled steel cylinder associated with a piston is impacted by a mass falling at a prescribed velocity. The cylinder is closed at its base by an aluminum plate whose characteristics are allowed to vary. The impact on the piston creates a pressure wave in the fluid which is responsible for the deformation of the plate and, possibly, the propagation of cracks. The structural part of the problem is modeled using Mindlin-Reissner finite elements (FE) and Smoothed Particle Hydrodynamics (SPH) shells. The modeling of the fluid is also based on an SPH formulation. The problem involves significant fluid-structure interactions (FSI) which are handled through a master-slave-based method and the pinballs method. Numerical results are compared to experimental data.

Three-dimensional analysis of flow-chemical interaction within a single square channel of a lean NO x trap catalyst.

PubMed

Fornarelli, Francesco; Dadduzio, Ruggiero; Torresi, Marco; Camporeale, Sergio Mario; Fortunato, Bernardo

2018-02-01

A fully 3D unsteady Computational Fluid Dynamics (CFD) approach coupled with heterogeneous reaction chemistry is presented in order to study the behavior of a single square channel as part of a Lean [Formula: see text] Traps. The reliability of the numerical tool has been validated against literature data considering only active BaO site. Even though the input/output performance of such catalyst has been well known, here the spatial distribution within a single channel is investigated in details. The square channel geometry influences the flow field and the catalyst performance being the flow velocity distribution on the cross section non homogeneous. The mutual interaction between the flow and the active catalyst walls influences the spatial distribution of the volumetric species. Low velocity regions near the square corners and transversal secondary flows are shown in several cross-sections along the streamwise direction at different instants. The results shed light on the three-dimensional characteristic of both the flow field and species distribution within a single square channel of the catalyst with respect to 0-1D approaches.

Seismic anisotropy and its precursory change before eruptions at Piton de la Fournaise volcano, La Réunion

NASA Astrophysics Data System (ADS)

Savage, M. K.; Ferrazzini, V.; Peltier, A.; Rivemale, E.; Mayor, J.; Schmid, A.; Brenguier, F.; Massin, F.; Got, J.-L.; Battaglia, J.; DiMuro, A.; Staudacher, T.; Rivet, D.; Taisne, B.; Shelley, A.

2015-05-01

The Piton de la Fournaise volcano exhibits frequent eruptions preceded by seismic swarms and is a good target to test hypotheses about magmatically induced variations in seismic wave properties. We use a permanent station network and a portable broadband network to compare seismic anisotropy measured via shear wave splitting with geodetic displacements, ratios of compressional to shear velocity (Vp/Vs), earthquake focal mechanisms, and ambient noise correlation analysis of surface wave velocities and to examine velocity and stress changes from 2000 through 2012. Fast directions align radially to the central cone and parallel to surface cracks and fissures, suggesting stress-controlled cracks. High Vp/Vs ratios under the summit compared with low ratios under the flank suggest spatial variations in the proportion of fluid-filled versus gas-filled cracks. Secular variations of fast directions (ϕ) and delay times (dt) between split shear waves are interpreted to sense changing crack densities and pressure. Delay times tend to increase while surface wave velocity decreases before eruptions. Rotations of ϕ may be caused by changes in either stress direction or fluid pressure. These changes usually correlate with GPS baseline changes. Changes in shear wave splitting measurements made on multiplets yield several populations with characteristic delay times, measured incoming polarizations, and fast directions, which change their proportion as a function of time. An eruption sequence on 14 October 2010 yielded over 2000 shear wave splitting measurements in a 14 h period, allowing high time resolution measurements to characterize the sequence. Stress directions from a propagating dike model qualitatively fit the temporal change in splitting.

A review of wave celerity in frictionless and axisymmetrical steel-lined pressure tunnels

NASA Astrophysics Data System (ADS)

Hachem, F. E.; Schleiss, A. J.

2011-02-01

Generally applicable approaches for estimating the “quasi-static”, which means without fluid-structure interaction and frequency-dependent water-hammer wave speed in steel-lined pressure tunnels are analyzed. The external constraints and assumptions of these approaches are discussed in detail. The reformulated formulas are then compared to commonly used expressions. Some special cases of wave speed calculation such as unlined pressure tunnels and open-air penstocks are investigated. The quasi-static wave speed is significantly influenced by the state of the backfill concrete and the near-field rock zone (cracked or uncracked). In the case when these two layers are cracked, the quasi-static wave speed is overestimated in between 1% and 8% compared to uncracked concrete and near-field rock layers. Depending on the stiffness of steel liner and penstock, the fluid-structure interaction leads to significant difference in wave speeds values. Compared to the quasi-static case, the fluid-structure interaction approach, applied to steel-lined tunnels, results up to 13% higher wave speed values in the high-frequency range (higher than 600 Hz) and up to 150% lower values for frequencies between 150 and 300 Hz in the considered test case.

Light-Toned Bedrock Along Cracks as Evidence of Fluid Alteration

NASA Image and Video Library

2007-02-15

This enhanced-color image from the HiRISE camera on NASA Mars Reconnaissance Orbiter shows a landscape of sand dunes and buttes among a background of light-toned bands and dark-toned bands in the Candor Chasma region

Adsorption of n-hexane and intermediate molecular weight aromatic hydrocarbons on LaY zeolite

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ruthven, D.M.; Kaul, B.K.

Experimental equilibrium isotherms, Henry`s law constants, and heats of sorption are reported for n-hexane, benzene, toluene, p-xylene, mesitylene, naphthalene, trimethylbenzene (TMP), and hexamethylbenzene (HMB) in La-exchanged zeolite Y (Si/Al = 1.8). Henry`s law constants and energies of adsorption are substantially smaller than those for NaX zeolite, reflecting the absence of accessible cations in LaY. These data provide a basis for the estimation of adsorbed phase concentrations of the relevant hydrocarbons on REY cracking catalysts under reaction conditions.

Effects of self-healing microcapsules on bending performance in composite brake pads

NASA Astrophysics Data System (ADS)

Zhang, Li; Dong, Xiu-ping; Wang, Hui

2009-07-01

For the purpose of reducing self-weight, friction noise and cost, improving shock absorption, enhancing corrosion and wear resistance, brake pads made of composite materials with self-healing function are prepared to substitute metal ones by designing ingredients and applying optimized production technology. As self-healing capsules are chosen, new method with technology of self-healing microcapsules, dicyclpentadiene (DCPD) microcapsules coated with poly (urea-formaldehyde), is put forward in this paper. In the crack's extending process, the stress is concentrated at the crack end, where the microcapsule is designed to be located. When the stress goes through the microcapsules and causes them to break, the self-healing liquid runs out to fill the crack by the capillary and it will poly-react with catalyst in the composite. As a result, the crack is healed. In this paper, polymer matrix composite brake pads with 6 prescriptions are prepared and studied. Three-point bending tests are carried out according to standards in GB/T 3356-1999 and the elastic constants of these polymer matrix composites are obtained by experiments. In accordance with the law of the continuous fiber composite, elastic constants of the short-fiber composite can be calculated by proportions of each ingredient. Results show that the theoretical expected results and the experimental values are consistent. 0.3-1.2 % mass proportion of microcapsules has little effects on the composite's bending intensity and modulus of elasticity. These studies also show that self-healing microcapsules used in composite brake pads is feasible.

Water redistribution in experimentally deformed natural milky quartz single crystals—Implications for H2O-weakening processes

NASA Astrophysics Data System (ADS)

Stünitz, H.; Thust, A.; Heilbronner, R.; Behrens, H.; Kilian, R.; Tarantola, A.; Fitz Gerald, J. D.

2017-02-01

Natural quartz single crystals were experimentally deformed in two orientations: (1) ⊥ to one prism plane and (2) in O+ orientation at 900 and 1000°C, 1.0 and 1.5 GPa, and strain rates of 1 × 10-6 s-1. In addition, hydrostatic and annealing experiments were performed. The starting material was milky quartz, which consisted of dry quartz with a large number of fluid inclusions of variable size up to several 100 µm. During pressurization fluid inclusions decrepitated producing much smaller fluid inclusions. Deformation on the sample scale is anisotropic due to dislocation glide on selected slip systems and inhomogeneous due to an inhomogeneous distribution of fluid inclusions. Dislocation glide is accompanied by minor dynamic recovery. Strongly deformed regions show a pointed broad absorption band in the 3400 cm-1 region consisting of a superposition of bands of molecular H2O and three discrete absorption bands (at 3367, 3400, and 3434 cm-1). In addition, there is a discrete absorption band at 3585 cm-1, which only occurs in deformed regions and reduces or disappears after annealing, so that this band appears to be associated with dislocations. H2O weakening in inclusion-bearing natural quartz crystals is assigned to the H2O-assisted dislocation generation and multiplication. Processes in these crystals represent recycling of H2O between fluid inclusions, cracking and crack healing, incorporation of structurally bound H in dislocations, release of H2O from dislocations during recovery, and dislocation generation at very small fluid inclusions. The H2O weakening by this process is of disequilibrium nature because it depends on the amount of H2O available.

Action of a Local Time-Periodic Load on an Ice Sheet with a Crack

NASA Astrophysics Data System (ADS)

Tkacheva, L. A.

2017-11-01

The problem of vibrations of an ice sheet with a rectilinear crack on the surface of an ideal incompressible fluid of finite depth under the action of a time-periodic local load is solved analytically using the Wiener-Hopf technique. Ice cover is simulated by two thin elastic semi-infinite plates of constant thickness. The thickness of the plates may be different on the opposite sides of the crack. Various boundary conditions on the edges of the plates are considered. For the case of contact of plates of the same thickness, a solution in explicit form is obtained. The asymptotics of the deflection of the plates in the far field is studied. It is shown that in the case of contact of two plates of different thickness, predominant directions of wave propagation at an angle to the crack can be identified in the far field. In the case of contact of plates of the same thickness with free edges and with free overlap, an edge waveguide mode propagating along the crack is excited. It is shown that the edge mode propagates with maximum amplitude if the vertical wall is in contact with the plate. Examples of calculations are given.

Damage and cracking of synthetic and natural glasses subjected to triaxial deformation

NASA Astrophysics Data System (ADS)

Ougier-Simonin, Audrey; Fortin, Jérôme; Guéguen, Yves; Schubnel, Alexandre; Bouyer, Frédéric

2010-05-01

Glass is an ideal elastic-brittle material. Although cracking in glass has been much investigated, going back to the pioneer work of Griffith, investigations under confining pressure have not been done so far. Besides, as glass results of the solidification of variable fused silicate mix, the impact of thermal cracking in this material cannot be neglected. Our study aims at investigating thermo-mechanical cracking effects on elastic wave velocities and mechanical strength, both under pressure, to document damage evolution on glass. We performed the experiments on a triaxial cell at room temperature, with and without pore fluid pressure, on borosilicate glass. The crack evolution has been monitored with: (i) elastic wave velocity measurements and (ii) acoustic emissions (MiniRichter system). We also measured the global mechanical behavior of our synthetic glass samples with strain gages. The original glass, produced in ideal conditions of slow cooling that prevent from any crack formation, exhibits a linear and reversible mechanical behavior and isotropic elastic velocities, as expected. It also presents a high strength as it fails at about 700 MPa of deviatoric stress for a confining pressure of 15 MPa. The damage develops progressively, with increasing acoustic emission rate, parallel to the deviatoric stress orientation and probably starts on the rare air bubbles trapped in the amorphous matrix. We choose to apply to some original glass samples a reproducible method (thermal treatment with a thermal shock of ?T = 100, 200 and 300°C) which creates cracks with a homogeneous distribution. The impact of the thermal treatment is clearly visible through the elastic wave velocity measurements as we observe crack closure under hydrostatic conditions (at about 30 MPa). Anisotropy is also observed for increasing deviatoric stress. For ?T higher than 200°C, the glass mechanical behavior becomes non linear and records an irreversible damage. The total damage observed with the acoustic emissions in these samples underlines the combination of the thermal and the mechanical cracks which drive to the sample failure. The preliminary results obtained with pore fluid pressure show a very small permeability even for a high damage level (10-21 ≤ φ ≤ 10-17). However, the glass amorphous structure makes it very different from any rock structure. In order to quantify these differences and to compare glass to rock, we managed to find a micro-crystallized basalt (Seljadur basalt, Iceland) with very low porosity (k ≤ 2%) and close chemical composition, and studied its behavior in the same experimental conditions. We show that a micro-crystallized rock remains different from a glass in terms of mechanical behavior but exhibits dynamical elastic parameters close from the glass ones.

A Hydrous Seismogenic Fault Rock Indicating A Coupled Lubrication Mechanism

NASA Astrophysics Data System (ADS)

Okamoto, S.; Kimura, G.; Takizawa, S.; Yamaguchi, H.

2005-12-01

In the seismogenic subduction zone, the predominant mechanisms have been considered to be fluid induced weakening mechanisms without frictional melting because the subduction zone is fundamentally quite hydrous under low temperature conditions. However, recently geological evidence of frictional melting has been increasingly reported from several ancient accretionary prisms uplifted from seismogenic depths of subduction zones (Ikesawa et al., 2003; Austrheim and Andersen, 2004; Rowe et al., 2004; Kitamura et al., 2005) but relationship between conflicting mechanisms; e.g. thermal pressurization of fluid and frictional melting is still unclear. We found a new exposure of pseudotachylyte from a fossilized out-of-sequence thrust (OOST) , Nobeoka thrust in the accretionary complex, Kyushu, southwest Japan. Hanging-wall and foot-wall are experienced heating up to maximum temperature of about 320/deg and about 250/deg, respectively. Hanging-wall rocks of the thrust are composed of shales and sandstones deformed plastically. Foot-wall rocks are composed of shale matrix melange with sandstone and basaltic blocks deformed in a brittle fashion (Kondo et al, 2005). The psudotachylyte was found from one of the subsidiary faults in the hanging wall at about 10 m above the fault core of the Nobeoka thrust. The fault is about 1mm in width, and planer rupture surface. The fault maintains only one-time slip event because several slip surfaces and overlapped slip textures are not identified. The fault shows three deformation stages: The first is plastic deformation of phyllitic host rocks; the second is asymmetric cracking formed especially in the foot-wall of the fault. The cracks are filled by implosion breccia hosted by fine carbonate minerals; the third is frictional melting producing pseudotachylyte. Implosion breccia with cracking suggests that thermal pressurization of fluid and hydro-fracturing proceeded frictional melting.

Fundamental studies of catalytic processing of synthetic liquids. Final report

DOE Office of Scientific and Technical Information (OSTI.GOV)

Watson, P.R.

1994-06-15

Liquids derived from coal contain relatively high amounts of oxygenated organic compounds, mainly in the form of phenols and furans that are deleterious to the stability and quality of these liquids as fuels. Hydrodeoxygenation (HDO) using Mo/W sulfide catalysts is a promising method to accomplish this removal, but our understanding of the reactions occurring on the catalyst surface during HDO is very limited. Rather than attempting to examine the complexities of real liquids and catalysts we have adopted an approach here using model systems amenable to surface-sensitive techniques that enable us to probe in detail the fundamental processes occurring duringmore » HDO at the surfaces of well-defined model catalysts. The results of this work may lead to the development of more efficient, selective and stable catalysts. Above a S/Mo ratio of about 0.5 ML, furan does not adsorb on sulfided Mo surfaces; as the sulfur coverage is lowered increasing amounts of furan can be adsorbed. Temperature-programmed reaction spectroscopy (TPRS) reveals that C-H, C-C and C-O bond scission occurs on these surfaces. Auger spectra show characteristic changes in the nature and amount of surface carbon. Comparisons with experiments carried out with CO, H{sub 2} and alkenes show that reaction pathways include -- direct abstraction of CO at low temperatures; cracking and release of hydrogen below its normal desorption temperature; dehydrogenatin of adsorbed hydrocarbon fragments; recombination of C and O atoms and dissolution of carbon into the bulk at high temperatures. Performing the adsorption or thermal reaction in 10{sup {minus}5} torr of hydrogen does not change the mode of reaction significantly.« less

Reaction pathways for the deoxygenation of vegetable oils and related model compounds.

PubMed

Gosselink, Robert W; Hollak, Stefan A W; Chang, Shu-Wei; van Haveren, Jacco; de Jong, Krijn P; Bitter, Johannes H; van Es, Daan S

2013-09-01

Vegetable oil-based feeds are regarded as an alternative source for the production of fuels and chemicals. Paraffins and olefins can be produced from these feeds through catalytic deoxygenation. The fundamentals of this process are mostly studied by using model compounds such as fatty acids, fatty acid esters, and specific triglycerides because of their structural similarity to vegetable oils. In this Review we discuss the impact of feedstock, reaction conditions, and nature of the catalyst on the reaction pathways of the deoxygenation of vegetable oils and its derivatives. As such, we conclude on the suitability of model compounds for this reaction. It is shown that the type of catalyst has a significant effect on the deoxygenation pathway, that is, group 10 metal catalysts are active in decarbonylation/decarboxylation whereas metal sulfide catalysts are more selective to hydrodeoxygenation. Deoxygenation studies performed under H2 showed similar pathways for fatty acids, fatty acid esters, triglycerides, and vegetable oils, as mostly deoxygenation occurs indirectly via the formation of fatty acids. Deoxygenation in the absence of H2 results in significant differences in reaction pathways and selectivities depending on the feedstock. Additionally, using unsaturated feedstocks under inert gas results in a high selectivity to undesired reactions such as cracking and the formation of heavies. Therefore, addition of H2 is proposed to be essential for the catalytic deoxygenation of vegetable oil feeds. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Release of hydrogen sulfide during microwave pyrolysis of sewage sludge: Effect of operating parameters and mechanism.

PubMed

Zhang, Jun; Zuo, Wei; Tian, Yu; Yin, Linlin; Gong, Zhenlong; Zhang, Jie

2017-06-05

The effects of sludge characteristics, pyrolysis temperature, heating rate and catalysts on the release of H 2 S and mechanism of H 2 S formation during sludge pyrolysis were investigated in a microwave heating reactor (MHR). The evolution of sulfur-containing compounds in the pyrolysis chars obtained at temperature range of 400-800°C was characterized by XPS. For a given temperature, the maximum concentration of H 2 S appeared at moisture content of 80%. Compared to the influence of heating rate on the H 2 S yields, pyrolysis temperature and catalyst played a more significant role on the release of H 2 S during microwave pyrolysis process. The H 2 S concentration increased with increasing temperature from 400°C to 800°C while decreased with increasing heating rate. Both the Nickel-based catalyst and Dolomite displayed significant desulfurization effect and Ni-based catalyst exhibited the larger desulfurization capability than that of Dolomite. The organic sulfur compounds accounted for about 60% of the total sulfur in the sludge which was the main reason for the formation of H 2 S. The mechanism analysis indicated that the cleavage reactions of mercaptan and aromatic-S compounds at temperatures below 600°C and the cracking reaction of sulfate above 700°C respectively were responsible for the H 2 S release during sludge pyrolysis. Copyright © 2017 Elsevier B.V. All rights reserved.

Octadecyl ferulate behavior in 1,2-dioleoylphosphocholine liposomes

USDA-ARS?s Scientific Manuscript database

Octadecyl ferulate, a lipophilic derivative of ferulic acid having antioxidant properties, is found throughout the plant and fungi kingdoms. Octadecyl ferulate was prepared using solid acid catalyst, monitored using supercritical fluid chromatograph and purified to a 42% yield. Differential scanning...

Percolation in a Proton Exchange Membrane Fuel Cell Catalyst Layer

DOE Office of Scientific and Technical Information (OSTI.GOV)

Stacy, Stephen; Allen, Jeffrey

Water management in the catalyst layers of proton exchange membrane fuel cells (PEMFC) is confronted by two issues, flooding and dry out, both of which result in improper functioning of the fuel cell and lead to poor performance and degradation. At the present time, the data that has been reported about water percolation and wettability within a fuel cell catalyst layer is limited. A method and apparatus for measuring the percolation pressure in the catalyst layer has been developed based upon an experimental apparatus used to test water percolation in porous transport layers (PTL). The experimental setup uses a pseudomore » Hele-Shaw type testing where samples are compressed and a fluid is injected into the sample. Testing the samples gives percolation pressure plots which show trends in increasing percolation pressure with an increase in flow rate. A decrease in pressure was seen as percolation occurred in one sample, however the pressure only had a rising effect in the other sample.« less

Titanium compounds as catalysts of higher alpha-olefin-based super-high-molecular polymers synthesis

NASA Astrophysics Data System (ADS)

Konovalov, K. B.; Kazaryan, M. A.; Manzhay, V. N.; Vetrova, O. V.

2016-01-01

The synthesis of polymers of 10 million or more molecular weight is a difficult task even in a chemical lab. Higher α-olefin-based polymer agents of such kind have found a narrow but quite important niche, the reduction of drag in the turbulent flow of hydrocarbon fluids such as oil and oil-products. In its turn, searching for a catalytic system capable to produce molecules of such a high length and to synthesize polymers of a low molecular-mass distribution is part of a global task of obtaining a high-quality product. In this paper we had observed a number of industrial catalysts with respect to their suitability for higher poly-α- olefins synthesis. A number samples representing copolymers of 1-hexene with 1-decene obtained on a previous generation catalyst, a microsphere titanium chloride catalytic agent had been compared to samples synthesized using a titanium-magnesium catalyst both in solution and in a polymer medium.

Application of green chemistry techniques to prepare electrocatalysts for direct methanol fuel cells.

PubMed

Shimizu, Kenichi; Wang, Joanna S; Wai, Chien M

2010-03-25

A series of green techniques for synthesizing carbon nanotube-supported platinum nanoparticles and their high electrocatalytic activity toward methanol fuel cell applications are reported. The techniques utilize either the supercritical fluid carbon dioxide or water as a medium for depositing platinum nanoparticles on surfaces of multiwalled or single-walled carbon nanotubes. The catalytic properties of the carbon nanotubes-supported Pt nanoparticle catalysts prepared by four different techniques are compared for anodic oxidation of methanol and cathodic reduction of oxygen using cyclic voltammetry. One technique using galvanic exchange of Pt(2+) in water with zerovalent iron present on the surfaces of as-grown single-walled carbon nanotubes produces a Pt catalyst that shows an unusually high catalytic activity for reduction of oxygen but a negligible activity for oxidation of methanol. This fuel-selective catalyst may have a unique application as a cathode catalyst in methanol fuel cells to alleviate the problems caused by crossover of methanol through the polymer electrolyte membrane.

Counting Active Sites on Titanium Oxide-Silica Catalysts for Hydrogen Peroxide Activation through In Situ Poisoning with Phenylphosphonic Acid

DOE Office of Scientific and Technical Information (OSTI.GOV)

Eaton, Todd R.; Boston, Andrew M.; Thompson, Anthony B.

2015-06-04

Quantifying specific active sites in supported catalysts improves our understanding and assists in rational design. Supported oxides can undergo significant structural changes as surface densities increase from site-isolated cations to monolayers and crystallites, which changes the number of kinetically relevant sites. Herein, TiO x domains are titrated on TiO x–SiO 2 selectively with phenylphosphonic acid (PPA). An ex situ method quantifies all fluid-accessible TiO x, whereas an in situ titration during cis-cyclooctene epoxidation provides previously unavailable values for the number of tetrahedral Ti sites on which H 2O 2 activation occurs. We use this method to determine the active sitemore » densities of 22 different catalysts with different synthesis methods, loadings, and characteristic spectra and find a single intrinsic turnover frequency for cis-cyclooctene epoxidation of (40±7) h -1. This simple method gives molecular-level insight into catalyst structure that is otherwise hidden when bulk techniques are used.« less

Understanding of catalyst deactivation caused by sulfur poisoning and carbon deposition in steam reforming of liquid hydrocarbon fuels

NASA Astrophysics Data System (ADS)

Xie, Chao

2011-12-01

The present work was conducted to develop a better understanding on the catalyst deactivation in steam reforming of sulfur-containing liquid hydrocarbon fuels for hydrogen production. Steam reforming of Norpar13 (a liquid hydrocarbon fuel from Exxon Mobile) without and with sulfur was performed on various metal catalysts (Rh, Ru, Pt, Pd, and Ni) supported on different materials (Al2O3, CeO2, SiO2, MgO, and CeO2- Al2O3). A number of characterization techniques were applied to study the physicochemical properties of these catalysts before and after the reactions. Especially, X-ray absorption near edge structure (XANES) spectroscopy was intensively used to investigate the nature of sulfur and carbon species in the used catalysts to reveal the catalyst deactivation mechanism. Among the tested noble metal catalysts (Rh, Ru, Pt, and Pd), Rh catalyst is the most sulfur tolerant. Al2O3 and CeO2 are much better than SiO2 and MgO as the supports for the Rh catalyst to reform sulfur-containing hydrocarbons. The good sulfur tolerance of Rh/Al2O3 can be attributed to the acidic nature of the Al2O3 support and its small Rh crystallites (1-3 nm) as these characteristics facilitate the formation of electron-deficient Rh particles with high sulfur tolerance. The good catalytic performance of Rh/CeO2 in the presence of sulfur can be ascribed to the promotion effect of CeO2 on carbon gasification, which significantly reduced the carbon deposition on the Rh/CeO2catalyst. Steam reforming of Norpar13 in the absence and presence of sulfur was further carried out over CeO2-Al2O3 supported monometallic Ni and Rh and bimetallic Rh-Ni catalysts at 550 and 800 °C. Both monometallic catalysts rapidly deactivated at 550 °C, iv and showed poor sulfur tolerance. Although ineffective for the Ni catalyst, increasing the temperature to 800 °C dramatically improved the sulfur tolerance of the Rh catalyst. Sulfur K-edge XANES revealed that metal sulfide and organic sulfide are the dominant sulfur species on the used Ni catalyst, while sulfonate and sulfate predominate on the used Rh catalyst. The superior sulfur tolerance of the Rh/CeO2-Al2O3 catalyst at 800 °C may be associated with its capability in sulfur oxidation. It is very likely that the oxygenshielded sulfur structure of sulfonate and sulfate can suppress the poisoning impact of sulfur on Rh through inhibiting direct rhodium-sulfur interaction. Although the Rh-Ni catalyst exhibited better sulfur tolerance than the monometallic ones at 550 °C, its catalytic performance was inferior compared with the Rh catalyst in the sulfur-containing reaction at 800 °C probably due to the severe carbon deposition on the bimetallic catalyst. The last part of this work focuses on the influence of sulfur on the carbon deposition in steam reforming of liquid hydrocarbon fuels over CeO2-Al2O3 supported monometallic Ni and Rh catalysts at 800 ºC. Though abundant carbon deposits can accumulate on the pure CeO2-Al2O3 support due to fuel thermal cracking, the metal addition substantially mitigated the carbon deposition in the sulfur-free reaction. The presence of sulfur increased the carbon deposition on both catalysts, which has a much more significant impact for the Ni catalyst. Our results indicate that (I) the presence of sulfur can suppress carbon gasification and promote the formation of graphitic carbon on reforming catalysts, and (II) the Rh catalyst possesses stronger capability to maintain carbon gasification activity than the Ni catalyst in the presence of sulfur.

Bioleaching of rare earth elements from waste phosphors and cracking catalysts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Reed, David W.; Fujita, Yoshiko; Daubaras, Dayna L.

Four microbial cultures were evaluated for organic acid production and their potential utility for leaching of rare earth elements (REE) from retorted phosphor powder (RPP) and spent fluidized cracking catalyst (FCC). Three of the cultures (2 bacterial, 1 fungal) were isolated from environmental and industrial materials known to contain rare earth elements. The other was the well-known and industrially important bacterium Gluconobacter oxydans. Gluconic acid was the predominant identified organic acid produced by all of the cultures; citric and acetic acid were among the other acids detected. There was also maximum REE leaching by cell free culture supernatants obtained withmore » Gluconobacter and the FCC; 49% of total REE was recovered, with preferential recovery of lanthanum over cerium. The phosphor powder was more difficult to leach; only ~2 % total REE was leached from RPP with Gluconobacter. Tests with the RPP indicated that the extent of REE solubilization was similar whether whole cell cultures or cell-free supernatants were used. However, Gluconobacter cell-free culture supernatants with 10-15 mM gluconic acid outperformed abiotically prepared leaching solutions with 30 mM gluconic acid concentrations. Abiotic tests showed that increasing gluconic acid concentrations increased leaching efficiency; for example, total REE leaching from FCC increased from 24 to 36 to 45% when gluconic acid was increased from 10 to 30 to 90 mM. Our research shows that utilizing microorganisms that produce gluconic acid can result in effective leaching of REE from waste materials, and optimizing gluconic acid production will improve recovery.« less

Bioleaching of rare earth elements from waste phosphors and cracking catalysts

DOE PAGES

Reed, David W.; Fujita, Yoshiko; Daubaras, Dayna L.; ...

2016-08-22

Four microbial cultures were evaluated for organic acid production and their potential utility for leaching of rare earth elements (REE) from retorted phosphor powder (RPP) and spent fluidized cracking catalyst (FCC). Three of the cultures (2 bacterial, 1 fungal) were isolated from environmental and industrial materials known to contain rare earth elements. The other was the well-known and industrially important bacterium Gluconobacter oxydans. Gluconic acid was the predominant identified organic acid produced by all of the cultures; citric and acetic acid were among the other acids detected. There was also maximum REE leaching by cell free culture supernatants obtained withmore » Gluconobacter and the FCC; 49% of total REE was recovered, with preferential recovery of lanthanum over cerium. The phosphor powder was more difficult to leach; only ~2 % total REE was leached from RPP with Gluconobacter. Tests with the RPP indicated that the extent of REE solubilization was similar whether whole cell cultures or cell-free supernatants were used. However, Gluconobacter cell-free culture supernatants with 10-15 mM gluconic acid outperformed abiotically prepared leaching solutions with 30 mM gluconic acid concentrations. Abiotic tests showed that increasing gluconic acid concentrations increased leaching efficiency; for example, total REE leaching from FCC increased from 24 to 36 to 45% when gluconic acid was increased from 10 to 30 to 90 mM. Our research shows that utilizing microorganisms that produce gluconic acid can result in effective leaching of REE from waste materials, and optimizing gluconic acid production will improve recovery.« less

Microwave-induced cracking of pyrolytic tars coupled to microwave pyrolysis for syngas production.

PubMed

Beneroso, D; Bermúdez, J M; Montes-Morán, M A; Arenillas, A; Menéndez, J A

2016-10-01

Herein a new process is proposed to produce a syngas-rich gas fraction (>80vol% H2+CO) from biowaste based on microwave heating within two differentiated steps in order to avoid tars production. The first step consists of the microwave pyrolysis of biowaste induced by a char-based susceptor at 400-800°C; tars, char and syngas-rich gas fractions being produced. The tars are then fed into the second step where a portion of the char from the first step is used as a bed material in a 0.3:1wt% ratio. This bed is heated up by microwaves up to 800°C, allowing thermal cracking of tars and additional syngas (>90vol% H2+CO) being then produced. This new concept arises as an alternative technology to the gasification of biowastes for producing syngas with no need for catalysts or gasifying reagents to minimise tars production. Copyright © 2016 Elsevier Ltd. All rights reserved.

Failure analysis of fuel cell electrodes using three-dimensional multi-length scale X-ray computed tomography

NASA Astrophysics Data System (ADS)

Pokhrel, A.; El Hannach, M.; Orfino, F. P.; Dutta, M.; Kjeang, E.

2016-10-01

X-ray computed tomography (XCT), a non-destructive technique, is proposed for three-dimensional, multi-length scale characterization of complex failure modes in fuel cell electrodes. Comparative tomography data sets are acquired for a conditioned beginning of life (BOL) and a degraded end of life (EOL) membrane electrode assembly subjected to cathode degradation by voltage cycling. Micro length scale analysis shows a five-fold increase in crack size and 57% thickness reduction in the EOL cathode catalyst layer, indicating widespread action of carbon corrosion. Complementary nano length scale analysis shows a significant reduction in porosity, increased pore size, and dramatically reduced effective diffusivity within the remaining porous structure of the catalyst layer at EOL. Collapsing of the structure is evident from the combination of thinning and reduced porosity, as uniquely determined by the multi-length scale approach. Additionally, a novel image processing based technique developed for nano scale segregation of pore, ionomer, and Pt/C dominated voxels shows an increase in ionomer volume fraction, Pt/C agglomerates, and severe carbon corrosion at the catalyst layer/membrane interface at EOL. In summary, XCT based multi-length scale analysis enables detailed information needed for comprehensive understanding of the complex failure modes observed in fuel cell electrodes.

Ni nanoparticles and the Kirkendall effect in dry reforming of methane

NASA Astrophysics Data System (ADS)

Pegios, N.; Bliznuk, V.; Theofanidis, S. A.; Galvita, V. V.; Marin, G. B.; Palkovits, R.; Simeonov, K.

2018-09-01

In this study we report a simple preparation technique for Ni/γ-Al2O3 catalysts for the dry reforming of methane (DRM) at 800 °C to produce CO and H2 (synthesis gas). Hard-templating with low and high surface area activated carbon was applied. The produced synthesis gas exhibited a low product ratio of H2:CO [0.04-0.12], due to reverse water-gas shift. After 75 h time on stream (TOS) minimal deactivation of the catalyst could be observed. A rather unusual activity evolution was found involving a sequence of minimum-maximum-plateau. A scheme was suggested, explaining the activity evolution based on the Ni-nanoparticle positioning from being bare or encapsulated by Al2O3. The Al2O3 shell cracks and undergoes restructuring during reaction making more active sites available for the reaction. Superior metal dispersion was achieved with average nickel nanoparticle size at 4.9 ± 1.3 nm. The sintering mechanism was also investigated. Surprisingly, hollow nickel nanoparticles were observed at 25 h TOS due to the nanoscale Kirkendall effect. This diffusion phenomenon between the core, Ni0, and the outer shell, NiO, (Ni2+) lead to pronounced structural and morphological changes of the catalyst.

Advances in catalysts for internal reforming in high temperature fuel cells

NASA Astrophysics Data System (ADS)

Dicks, A. L.

Catalytic steam reforming of natural gas is an attractive method of producing the hydrogen required by the present generation of fuel cells. The molten carbonate (MCFC) and solid oxide (SOFC) fuel cells operate at high enough temperatures for the endothermic steam reforming reaction to be carried out within the stack. For the MCFC, the conventional anodes have insufficient activity to catalyse the steam reforming of natural gas. For these cells, internal reforming can be achieved only with the addition of a separate catalyst, preferably located in close proximity to the anode. However, in the so-called `Direct Internal Reforming' configuration, attack from alkali in the MCFC may severely limit catalyst lifetime. In the case of the state-of-the-art SOFC, natural gas can be reformed directly on the nickel cermet anode. However, in the SOFC, temperature variations in the cell caused by the reforming reaction may limit the amount of internal reforming that can be allowed in practice. In addition, some external pre-reforming may be desirable to remove high molecular weight hydrocarbons from the fuel gas, which would otherwise crack to produce elemental carbon. Degradation of the SOFC anode may also be a problem when internal reforming is carried out. This has prompted several research groups to investigate the use of alternative anode materials.

A numerical investigation of the scale-up effects on flow, heat transfer, and kinetics processes of FCC units.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chang, S. L.

1998-08-25

Fluid Catalytic Cracking (FCC) technology is the most important process used by the refinery industry to convert crude oil to valuable lighter products such as gasoline. Process development is generally very time consuming especially when a small pilot unit is being scaled-up to a large commercial unit because of the lack of information to aide in the design of scaled-up units. Such information can now be obtained by analysis based on the pilot scale measurements and computer simulation that includes controlling physics of the FCC system. A Computational fluid dynamic (CFD) code, ICRKFLO, has been developed at Argonne National Laboratorymore » (ANL) and has been successfully applied to the simulation of catalytic petroleum cracking risers. It employs hybrid hydrodynamic-chemical kinetic coupling techniques, enabling the analysis of an FCC unit with complex chemical reaction sets containing tens or hundreds of subspecies. The code has been continuously validated based on pilot-scale experimental data. It is now being used to investigate the effects of scaled-up FCC units. Among FCC operating conditions, the feed injection conditions are found to have a strong impact on the product yields of scaled-up FCC units. The feed injection conditions appear to affect flow and heat transfer patterns and the interaction of hydrodynamics and cracking kinetics causes the product yields to change accordingly.« less

MICROBIALLY MEDIATED LEACHING OF RARE EARTH ELEMENTS FROM RECYCLABLE MATERIALS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Reed, D. W.; Fujita, Y.; Daubaras, D. L.

2016-09-01

Bioleaching offers a potential approach for recovery of rare earth elements (REE) from recyclable materials, such as fluorescent lamp phosphors or degraded industrial catalysts. Microorganisms were enriched from REE-containing ores and recyclable materials with the goal of identifying strains capable of extracting REE from solid materials. Over 100 heterotrophic microorganisms were isolated and screened for their ability to produce organic acids capable of leaching REE. The ten most promising isolates were most closely related to Pseudomonas, Acinetobacter and Talaromyces. Of the acids produced, gluconic acid appeared to be the most effective at leaching REE (yttrium, lanthanum, cerium, europium, and terbium)more » from retorted phosphor powders (RPP), fluidized cracking catalyst (FCC), and europium-doped yttrium oxide (YOEu). We found that an Acinetobacter isolates, BH1, was the most capable strain and able to leach 33% of the total REE content from the FCC material. These results support the continuing evaluation of gluconic acid-producing microbes for large-scale REE recovery from recyclable materials.« less

Pretreatment of Miscanthus stalk with organic alkali guanidine and amino-guanidine.

PubMed

Li, Wei; Wang, Wei; Xu, Piaopiao; Xu, Pingping; Zhao, Xiaoli; Wang, Yun

2015-03-01

Organic alkali guanidine and amino-guanidine were used as catalysts to pretreat Miscanthus stalks. The effects of catalyst loadings, pretreatment temperature and time, on pretreatment results were studied. Between guanidines and amino-guanidines, guanidines were of benefit to produce hexose and amino-guanidines were in favor of producing pentose in stalk enzymolysis process. SEM images showed that the stalk surface after pretreatment were porous, cracked, and corroded. XRD data showed that the relative crystallinity index of cellulose after pretreatment was increased. FTIR spectra illustrated that both guanidine and amino-guanidine were effective to remove lignin and degrade hydrogen bonds of cellulose. TG data indicated that the initial temperature of rapid weight loss of Miscanthus stalks pretreated by the guanidine was higher than that by the amino-guanidine. The maximum sugar yields of Miscanthus stalks pretreated by the guanidine and the amino-guanidine after enzymolysis for 24 h were 350 and 370 mg/g stalks, respectively. Copyright © 2014 Elsevier Ltd. All rights reserved.

In situ generation of Ni nanoparticles from metal-organic framework precursors and their use for biomass hydrodeoxygenation.

PubMed

Čelič, Tadeja Birsa; Grilc, Miha; Likozar, Blaž; Tušar, Nataša Novak

2015-05-22

So far, in situ-generated Ni nanoparticles have been reported to be efficient catalysts for tar cracking during wood liquefaction by pyrolysis. Herein, their performance in further bio-oil conversion steps is evaluated. Nanoparticles were generated for the first time from a Ni-containing metal-organic framework, MIL-77, during the hydrotreatment of glycerol-solvolyzed lignocellulosic (LC) biomass. Reactions were conducted at 300 °C and the H2 pressure was 8 MPa in a slurry reactor. The catalytic activity and selectivity of the deoxygenation and hydrocracking reactions for real biomass-derived feedstock using in situ-generated nanoparticles was compared with Ni nanoparticles dispersed on a silica-alumina support (commercial Ni/SiO2 -Al2 O3 catalyst). The mass activity of the in situ-generated nanoparticles for hydrogenolysis was more than ten times higher in comparison to their commercial analogues, and their potential for the use in LC biorefinery is discussed. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hydrogen and syngas production by catalytic gasification of algal biomass (Cladophora glomerata L.) using alkali and alkaline-earth metals compounds.

PubMed

Ebadi, Abdol Ghaffar; Hisoriev, Hikmat; Zarnegar, Mohammad; Ahmadi, Hamed

2018-01-02

The steam gasification of algal biomass (Cladophora glomerata L.) in presence of alkali and alkaline-earth metal compounds catalysts was studied to enhance the yield of syngas and reduce its tar content through cracking and reforming of condensable fractions. The commercial catalysts used include NaOH, KHCO 3 , Na 3 PO 4 and MgO. The gasification runs carried out with a research scale, biomass gasification unit, show that the NaOH has a strong potential for production of hydrogen, along with the added advantages of char converting and tar destruction, allowing enhancement of produced syngas caloric value. When the temperature increased from 700°C to 900°C, the tar content in the gas sharply decreased, while the hydrogen yield increased. Increasing steam/biomass ratio significantly increased hydrogen yield and tar destruction; however, the particle size in the range of 0.5-2.5 mm played a minor role in the process.

Catalytic Fast Pyrolysis of Cellulose by Integrating Dispersed Nickel Catalyst with HZSM-5 Zeolite

NASA Astrophysics Data System (ADS)

Lei, Xiaojuan; Bi, Yadong; Zhou, Wei; Chen, Hui; Hu, Jianli

2018-01-01

The effect of integrating dispersed nickel catalyst with HZSM-5 zeolite on upgrading of vapors produced from pyrolysis of lignocellulosic biomass was investigated. The active component nickel nitrate was introduced onto the cellulose substrate by impregnation technique. Based on TGA experimental results, we discovered that nickel nitrate first released crystallization water, and then successively decomposed into nickel oxide which was reduced in-situ to metallic nickel through carbothermal reduction reaction. In-situ generated nickel nanoparticles were found highly dispersed over carbon substrate, which were responsible for catalyzing reforming and cracking of tars. In catalytic fast pyrolysis of cellulose, the addition of nickel nitrate caused more char formation at the expense of the yield of the condensable liquid products. In addition, the selectivity of linear oxygenates was increased whereas the yield of laevoglucose was reduced. Oxygen-containing compounds in pyrolysis vapors were deoxygenated into aromatics using HZSM-5. Moreover, the amount of condensable liquid products was decreased with the addition of HZSM-5.

Methodology for extracting local constants from petroleum cracking flows

DOEpatents

Chang, Shen-Lin; Lottes, Steven A.; Zhou, Chenn Q.

2000-01-01

A methodology provides for the extraction of local chemical kinetic model constants for use in a reacting flow computational fluid dynamics (CFD) computer code with chemical kinetic computations to optimize the operating conditions or design of the system, including retrofit design improvements to existing systems. The coupled CFD and kinetic computer code are used in combination with data obtained from a matrix of experimental tests to extract the kinetic constants. Local fluid dynamic effects are implicitly included in the extracted local kinetic constants for each particular application system to which the methodology is applied. The extracted local kinetic model constants work well over a fairly broad range of operating conditions for specific and complex reaction sets in specific and complex reactor systems. While disclosed in terms of use in a Fluid Catalytic Cracking (FCC) riser, the inventive methodology has application in virtually any reaction set to extract constants for any particular application and reaction set formulation. The methodology includes the step of: (1) selecting the test data sets for various conditions; (2) establishing the general trend of the parametric effect on the measured product yields; (3) calculating product yields for the selected test conditions using coupled computational fluid dynamics and chemical kinetics; (4) adjusting the local kinetic constants to match calculated product yields with experimental data; and (5) validating the determined set of local kinetic constants by comparing the calculated results with experimental data from additional test runs at different operating conditions.

Injection-Sensitive Mechanics of Hydraulic Fracture Interaction with Discontinuities

NASA Astrophysics Data System (ADS)

Chuprakov, D.; Melchaeva, O.; Prioul, R.

2014-09-01

We develop a new analytical model, called OpenT, that solves the elasticity problem of a hydraulic fracture (HF) contact with a pre-existing discontinuity natural fracture (NF) and the condition for HF re-initiation at the NF. The model also accounts for fluid penetration into the permeable NFs. For any angle of fracture intersection, the elastic problem of a blunted dislocation discontinuity is solved for the opening and sliding generated at the discontinuity. The sites and orientations of a new tensile crack nucleation are determined based on a mixed stress- and energy-criterion. In the case of tilted fracture intersection, the finite offset of the new crack initiation point along the discontinuity is computed. We show that aside from known controlling parameters such stress contrast, cohesional and frictional properties of the NFs and angle of intersection, the fluid injection parameters such as the injection rate and the fluid viscosity are of first-order in the crossing behavior. The model is compared to three independent laboratory experiments, analytical criteria of Blanton, extended Renshaw-Pollard, as well as fully coupled numerical simulations. The relative computational efficiency of OpenT model (compared to the numerical models) makes the model attractive for implementation in modern engineering tools simulating hydraulic fracture propagation in naturally fractured environments.

The mechanics and physics of fracturing: application to thermal aspects of crack propagation and to fracking.

PubMed

Cherepanov, Genady P

2015-03-28

By way of introduction, the general invariant integral (GI) based on the energy conservation law is presented, with mention of cosmic, gravitational, mass, elastic, thermal and electromagnetic energy of matter application to demonstrate the approach, including Coulomb's Law generalized for moving electric charges, Newton's Law generalized for coupled gravitational/cosmic field, the new Archimedes' Law accounting for gravitational and surface energy, and others. Then using this approach the temperature track behind a moving crack is found, and the coupling of elastic and thermal energies is set up in fracturing. For porous materials saturated with a fluid or gas, the notion of binary continuum is used to introduce the corresponding GIs. As applied to the horizontal drilling and fracturing of boreholes, the field of pressure and flow rate as well as the fluid output from both a horizontal borehole and a fracture are derived in the fluid extraction regime. The theory of fracking in shale gas reservoirs is suggested for three basic regimes of the drill mud permeation, with calculating the shape and volume of the local region of the multiply fractured rock in terms of the pressures of rock, drill mud and shale gas. © 2015 The Author(s) Published by the Royal Society. All rights reserved.

Centrifugation-assisted Assembly of Colloidal Silica into Crack-Free and Transferrable Films with Tunable Crystalline Structures

PubMed Central

Fan, Wen; Chen, Min; Yang, Shu; Wu, Limin

2015-01-01

Self-assembly of colloidal particles into colloidal films has many actual and potential applications. While various strategies have been developed to direct the assembly of colloidal particles, fabrication of crack-free and transferrable colloidal film with controllable crystal structures still remains a major challenge. Here we show a centrifugation-assisted assembly of colloidal silica spheres into free-standing colloidal film by using the liquid/liquid interfaces of three immiscible phases. Through independent control of centrifugal force and interparticle electrostatic repulsion, polycrystalline, single-crystalline and quasi-amorphous structures can be readily obtained. More importantly, by dehydration of silica particles during centrifugation, the spontaneous formation of capillary water bridges between particles enables the binding and pre-shrinkage of the assembled array at the fluid interface. Thus the assembled colloidal films are not only crack-free, but also robust and flexible enough to be easily transferred on various planar and curved substrates. PMID:26159121

Surface Waves and Flow-Induced Oscillations along an Underground Elliptic Cylinder Filled with a Viscous Fluid

NASA Astrophysics Data System (ADS)

Sakuraba, A.

2015-12-01

I made a linear analysis of flow-induced oscillations along an underground cylindrical conduit with an elliptical cross section on the basis of the hypothesis that volcanic tremor is a result of magma movement through a conduit. As a first step to understand how the self oscillation occurs because of magma flow, I investigated surface wave propagation and attenuation along an infinitely long fluid-filled elliptic cylinder in an elastic medium. The boundary element method is used to obtain the two-dimensional wave field around the ellipse in the frequency-wavenumber domain. When the major axis is much greater than the minor axis of the ellipse, we obtain the analytic form of the dispersion relation of both the crack-wave mode (Korneev 2008, Lipovsky & Dunham 2015) and the Rayleigh-wave mode with flexural deformation. The crack-wave mode generally has a slower phase speed and a higher attenuation than the Rayleigh-wave mode. In the long-wavelength limit, the crack-wave mode disappears because of fluid viscosity, but the Rayleigh-wave mode exists with a constant Q-value that depends on viscosity. When the aspect ratio of the ellipse is finite, the surface waves can basically be understood as those propagating along a fluid pipe. The flexural mode does exist even when the wavelength is much longer than the major axis, but its phase speed coincides with that of the surrounding S-wave (Randall 1991). As its attenuation is zero in the long-wavelength limit, the flexural mode differs in nature from surface wave. I also obtain a result on linear stability of viscous flow through an elliptic cylinder. In this analysis, I made an assumption that the fluid inertia is so small that the Stokes equation can be used. As suggested by the author's previous study (Sakuraba & Yamauchi 2014), the flexural (Rayleigh-wave) mode is destabilized at a critical flow speed that decreases with the wavelength. However, when the wavelength is much greater than the major axis of the ellipse, the unstable solution does exist, but its linear growth rate in amplitude becomes almost zero. Therefore, the unstable solution effectively disappears in the long-wavelength limit, suggesting that the aspect ratio of the conduit is needed to be sufficiently large if the flow-induced oscillation caused by a moderate magma speed is an origin of volcanic tremor.

Modeling the Impact of Fracture Growth on Fluid Displacements in Deformable Porous Media

NASA Astrophysics Data System (ADS)

Santillán, D.; Cueto-Felgueroso, L.; Juanes, R.

2015-12-01

Coupled flow and geomechanics is a critical research challenge in engineering and the geosciences. The flow of a fluid through a deformable porous media is present in manyenvironmental, industrial, and biological processes,such as the removal of pollutants from underground water bodies, enhanced geothermal systems, unconventional hydrocarbon resources or enhanced oil recovery techniques. However, the injection of a fluid can generate or propagate fractures, which are preferential flow paths. Using numerical simulation, we study the interplay between injection and rock mechanics, and elucidate fracture propagation as a function of injection rate, initial crack topology and mechanical rock properties. Finally, we discuss the role of fracture growth on fluid displacements in porous media. Figure: An example of fracture (in red) propagated in a porous media (in blue)

Failure Analysis of Space Shuttle Orbiter Valve Poppet

NASA Technical Reports Server (NTRS)

Russell, Rick

2010-01-01

The poppet failed during STS-126 due to fatigue cracking that most likely was initiated during MDC ground-testing. This failure ultimately led to the discovery that the cracking problem was a generic issue effecting numerous poppets throughout the Shuttle program's history. This presentation has focused on the laboratory analysis of the failed hardware, but this analysis was only one aspect of a comprehensive failure investigation. One critical aspect of the overall investigation was modeling of the fluid flow through this valve to determine the possible sources of cyclic loading. This work has led to the conclusion that the poppets are failing due to flow-induced vibration.

Fracture Flow Characterization from Seismic and Electric Properties: Insight from Experimental and Numerical Approaches

NASA Astrophysics Data System (ADS)

Sawayama, K.; Kitamura, K.; Tsuji, T.; Fujimitsu, Y.

2017-12-01

The estimation of fluid flow and its distribution in the fracture is essential to evaluate subsurface fluid (e.g., geothermal water, ground water, oil and gas). Recently, fluid flow in the geothermal reservoir has been attracting attention to develop EGS (enhanced geothermal system) technique. To detect the fluid distribution under the ground, geophysical exploration such as seismic and electromagnetic methods have been broadly applied. For better interpretation of these exploration data, more detailed investigation about the effect of fluid on seismic and electric properties of fracture is required. In this study, we measured and calculated seismic and electric properties of a cracked rock to discuss the effect of water distribution and saturation on them as well as fluid flow. For the experimental observation, we developed the technique to measure electrical impedance, P-wave velocity and water saturation simultaneously during the fluid-flow test. The test has been conducted as follows; a cracked andesite core sample was filled with nitrogen gas (Pp = 10 MPa) under 20 MPa of confining pressure and then, brine (1wt.%-KCl, 1.75 S/m) was injected into the sample to replace the gas. During the test, water saturation, permeability, electrical impedance and P-wave velocity were measured. As a result of this experimental study, electrical impedance dramatically decreased from 105 to 103 Ω and P-wave velocity increased by 2% due to the brine injection. This remarkable change of the electrical impedance could be due to the replacement of pre-filled nitrogen gas to the brine in the broad fracture. After the brine injection, electrical impedance decreased with injection pressure by up to 40% while P-wave velocity was almost constant. This decrease of electrical impedance could be related to the flow to the narrow path (microcrack) which cannot be detected by P-wave velocity. These two types of fluid flow mechanism were also suggested from other parameters such as permeability, water saturation and saturation exponent of Archie's law. To quantify the fluid flow and its distribution in the fracture, we applied fluid flow simulation by LBM (Lattice Boltzmann Method). From this result, we calculate physical parameters by FEM and FDM and then discuss effect of fluid on them as well as their comparison with experimental results.

Understanding and Mitigating Reservoir Compaction: an Experimental Study on Sand Aggregates

NASA Astrophysics Data System (ADS)

Schimmel, M.; Hangx, S.; Spiers, C. J.

2016-12-01

Fossil fuels continue to provide a source for energy, fuels for transport and chemicals for everyday items. However, adverse effects of decades of hydrocarbons production are increasingly impacting society and the environment. Production-driven reduction in reservoir pore pressure leads to a poro-elastic response of the reservoir, and in many occasions to time-dependent compaction (creep) of the reservoir. In turn, reservoir compaction may lead to surface subsidence and could potentially result in induced (micro)seismicity. To predict and mitigate the impact of fluid extraction, we need to understand production-driven reservoir compaction in highly porous siliciclastic rocks and explore potential mitigation strategies, for example, by using compaction-inhibiting injection fluids. As a first step, we investigate the effect of chemical environment on the compaction behaviour of sand aggregates, comparable to poorly consolidated, highly porous sandstones. The sand samples consist of loose aggregates of Beaujean quartz sand, sieved into a grainsize fraction of 180-212 µm. Uniaxial compaction experiments are performed at an axial stress of 35 MPa and temperature of 80°C, mimicking conditions of reservoirs buried at three kilometres depth. The chemical environment during creep is either vacuum-dry or CO2-dry, or fluid-saturated, with fluids consisting of distilled water, acid solution (CO2-saturated water), alkaline solution (pH 9), aluminium solution (pH 3) and solution with surfactants (i.e., AMP). Preliminary results show that compaction of quartz sand aggregates is promoted in a wet environment compared to a dry environment. It is inferred that deformation is controlled by subcritical crack growth when dry and stress corrosion cracking when wet, both resulting in grain failure and subsequent grain rearrangement. Fluids inhibiting these processes, have the potential to inhibit aggregate compaction.

Gravity-Driven Hydraulic Fractures

NASA Astrophysics Data System (ADS)

Germanovich, L. N.; Garagash, D.; Murdoch, L. C.; Robinowitz, M.

2014-12-01

This study is motived by a new method for disposing of nuclear waste by injecting it as a dense slurry into a hydraulic fracture that grows downward to great enough depth to permanently isolate the waste. Disposing of nuclear waste using gravity-driven hydraulic fractures is mechanically similar to the upward growth of dikes filled with low density magma. A fundamental question in both applications is how the injected fluid controls the propagation dynamics and fracture geometry (depth and breadth) in three dimensions. Analog experiments in gelatin [e.g., Heimpel and Olson, 1994; Taisne and Tait, 2009] show that fracture breadth (the short horizontal dimension) remains nearly stationary when the process in the fracture "head" (where breadth is controlled) is dominated by solid toughness, whereas viscous fluid dissipation is dominant in the fracture tail. We model propagation of the resulting gravity-driven (buoyant or sinking), finger-like fracture of stationary breadth with slowly varying opening along the crack length. The elastic response to fluid loading in a horizontal cross-section is local and can be treated similar to the classical Perkins-Kern-Nordgren (PKN) model of hydraulic fracturing. The propagation condition for a finger-like crack is based on balancing the global energy release rate due to a unit crack extension with the rock fracture toughness. It allows us to relate the net fluid pressure at the tip to the fracture breadth and rock toughness. Unlike the PKN fracture, where breadth is known a priori, the final breadth of a finger-like fracture is a result of processes in the fracture head. Because the head is much more open than the tail, viscous pressure drop in the head can be neglected leading to a 3D analog of Weertman's hydrostatic pulse. This requires relaxing the local elasticity assumption of the PKN model in the fracture head. As a result, we resolve the breadth, and then match the viscosity-dominated tail with the 3-D, toughness-dominated head to obtain a complete closed-form solution. We then analyze the gravity fracture propagation in conditions of either continuous injection or finite volume release for sets of parameters representative of dense waste injection technique and low viscosity magma diking.

A new perspective on the generation of the 2016 M6.4 Meilung earthquake, southwestern Taiwan

NASA Astrophysics Data System (ADS)

Wang, Z.

2017-12-01

In order to investigate the likely generation mechanism of the 2016 M6.4 Meilung earthquake, a large number of high-quality travel times from P- and S-wave source-receiver pairs are used jointly in this study to invert three-dimensional (3-D) seismic velocity (Vp, Vs) and Poisson's ratio structures at high resolution. We also calculated crack density, saturate fracture, and bulk-sound velocity from our inverted Vp, Vs, and s models. In this way, multi-geophysical parameter imaging revealed that the 2016 Meilung earthquake occurred along a distinctive edge portion exhibiting high-to-low variations in these parameters in both horizontal and vertical directions across the hypocenter. We consider that a slow velocity and high-Poisson ratio body that has high-crack density and somewhat high-saturate fracture anomalies above the hypocenter under the coastal plain represents fluids contained in the young fold-and-thrust belt relative to the passive Asian continental margin in southwestern Taiwan. Intriguing, a continuous low Vp and Vs zone with high Poisson ratio, crack density and saturate fracture anomalies across the Laonung and Chishan faults is also clearly imaged in the northwestern upper crust beneath the coastal plain and western foothills as far as the southeastern lower crust under the central range. We therefore propose that this southeastern extending weakened zone was mainly the result of a fluid intrusion either from the young fold-and-thrust belt associated with the passive Asian continental margin in the shallow crust or the subducted Eurasian continental (EC) plate in the lower crust and uppermost mantle. We suggest that fluid intrusion into the upper Oligocene to Pleistocene shallow marine and clastic shelf units of the Eurasian continental crust and/or the relatively thin uppermost part of the transitional Pleistocene-Holocene foreland due to the subduction of the EC plate along the deformation front played a key role in earthquake generation in southwestern Taiwan. Such fluid penetration would reduce Vp, and Vs while increasing Poisson ratio and saturate fracture across the source area, leading to mechanical strength failure of the rock matrix in the relative weakened and brittle seismogenic layer and triggering the 2016 earthquake.

The chemo-mechanical effect of cutting fluid on material removal in diamond scribing of silicon

NASA Astrophysics Data System (ADS)

Kumar, Arkadeep; Melkote, Shreyes N.

2017-07-01

The mechanical integrity of silicon wafers cut by diamond wire sawing depends on the damage (e.g., micro-cracks) caused by the cutting process. The damage type and extent depends on the material removal mode, i.e., ductile or brittle. This paper investigates the effect of cutting fluid on the mode of material removal in diamond scribing of single crystal silicon, which simulates the material removal process in diamond wire sawing of silicon wafers. We conducted scribing experiments with a diamond tipped indenter in the absence (dry) and in the presence of a water-based cutting fluid. We found that the cutting mode is more ductile when scribing in the presence of cutting fluid compared to dry scribing. We explain the experimental observations by the chemo-mechanical effect of the cutting fluid on silicon, which lowers its hardness and promotes ductile mode material removal.

Experimental advances and preliminary mathematical modeling of the Swiss-roll mixed-reactant direct borohydride fuel cell

NASA Astrophysics Data System (ADS)

Aziznia, Amin; Oloman, Colin W.; Gyenge, Előd L.

2014-11-01

The Swiss-roll single-cell mixed reactant (SR-MRFC) borohydride - oxygen fuel cell equipped with Pt/carbon cloth 3D anode and either MnO2 or Ag gas-diffusion cathodes is investigated by a combination of experimental studies and preliminary mathematical modeling of the polarization curve. We investigate the effects of four variables: cathode side metallic mesh fluid distributor, separator type (Nafion 112® vs. Viledon®), cathode catalyst (MnO2 vs. Ag), and the hydrophilic pore volume fraction of the gas-diffusion cathode. Using a two-phase feed of alkaline borohydride solution (1 M NaBH4 - 2 M NaOH) and O2 gas in an SR-MRFC equipped with Pt/C 3D anode, MnO2 gas diffusion cathode, Viledon® porous diaphragm, expanded mesh cathode-side fluid distributor, the maximum superficial power density is 2230 W m-2 at 323 K and 105 kPa(abs). The latter superficial power density is almost 3.5 times higher than our previously reported superficial power density for the same catalyst combinations. Furthermore, with a Pt anode and Ag cathode catalyst combination, a superficial power density of 2500 W m-2 is achieved with superior performance durability compared to the MnO2 cathode. The fuel cell results are substantiated by impedance spectroscopy analysis and preliminary mathematical model predictions based on mixed potential theory.

Modeling Outburst Flooding as a Turbulent Hydraulic Fracture Parallel to a Nearby Free Surface

NASA Astrophysics Data System (ADS)

Tsai, V. C.; Rice, J. R.

2009-12-01

Meltwater generated at the surface and base of glaciers and ice sheets is known to have a large impact on how ice masses behave dynamically, but much is still unknown about the physical processes responsible for how this meltwater drains out of the glacier. For example, little attention has been paid to short-timescale processes like turbulent hydraulic fracture, which is likely an important mechanism by which drainage channels initially form when water pressures are high. In recent work (Tsai and Rice [Fall AGU, 2008; JGR subm., 2009]), we have constructed a model of this turbulent hydraulic fracture process in which over-pressurized water is assumed to flow turbulently through a crack, leading to crack growth. However, one important limitation of this prior work is that it only strictly applies in the limit of short crack length 2L compared to glacier height H, whereas relevant observations of supraglacial lake drainage, jokulhlaups and sub-glacial lake-to-lake transport episodes do not fall in this regime. Here, we improve somewhat upon this model by explicitly accounting for a nearby free surface. We accomplish this by applying the approach of Erdogan et al. [Meth. Anal. Sol. Crack Prob., 1973] to numerically calculate elastic displacements consistent with crack pressure distribution for a crack near a free surface, and use these results as before to simultaneously satisfy the governing fluid, elastic and fracture equations. Our results are analogous to the zero fracture toughness results of Zhang et al. [Int. J. Numer. Anal. Meth. Geomech., 2005], but applied to the case of turbulent flow rather than laminar flow of a Newtonian viscous fluid. Our new results clarify the importance of the free surface and potentially explain discrepancies between our previous modeling results and observations of supraglacial lake drainage by Das et al. [Science, 2008]. However, the numerical challenges increase as 2L becomes comparable to or much larger than H. We hope to ultimately develop simpler analyses for that range which make use of (visco)elastic plate theory at positions along the uplifted ice sheet that are remote from the fracturing front. This approach may also be of interest for tidal interactions with the ice-shelf grounding line location.

Modeling Outburst Flooding as a Turbulent Hydraulic Fracture Parallel to a Nearby Free Surface

NASA Astrophysics Data System (ADS)

Tsai, Victor; Rice, James

2010-05-01

Meltwater generated at the surface and base of glaciers and ice sheets is known to have a large impact on how ice masses behave dynamically, but much is still unknown about the physical processes responsible for how this meltwater drains out of the glacier. For example, little attention has been paid to short-timescale processes like turbulent hydraulic fracture, which is likely an important mechanism by which drainage channels initially form when water pressures are high. In recent work (Tsai and Rice [Fall AGU, 2008; JGR subm., 2009]), we have constructed a model of this turbulent hydraulic fracture process in which over-pressurized water is assumed to flow turbulently through a crack, leading to crack growth. However, one important limitation of this prior work is that it only strictly applies in the limit of short crack length, 2L, compared to glacier height, H, whereas relevant observations of supraglacial lake drainage, jokulhlaups and sub-glacial lake-to-lake transport episodes do not fall in this regime. Here, we improve somewhat upon this model by explicitly accounting for a nearby free surface. We accomplish this by applying the approach of Erdogan et al. [Meth. Anal. Sol. Crack Prob., 1973] to numerically calculate elastic displacements consistent with crack pressure distribution for a crack near a free surface, and use these results as before to simultaneously satisfy the governing fluid, elastic and fracture equations. Our results are analogous to the zero fracture toughness results of Zhang et al. [Int. J. Numer. Anal. Meth. Geomech., 2005], but applied to the case of turbulent flow rather than laminar flow of a Newtonian viscous fluid. Our new results clarify the importance of the free surface and potentially explain discrepancies between our previous modeling results and observations of supraglacial lake drainage by Das et al. [Science, 2008]. However, the numerical challenges increase as 2L becomes comparable to or much larger than H. We hope to ultimately develop simpler analyses for that range which make use of (visco)elastic plate theory at positions along the uplifted ice sheet that are remote from the fracturing front. This approach may also be of interest for tidal interactions with the ice-shelf grounding line location.

Effects of fluid-rock interaction on friction and slip stability of gouge-filled faults (Invited)

NASA Astrophysics Data System (ADS)

Spiers, C. J.

2013-12-01

Understanding the effects of fluid-rock interaction on fault friction is central not only to understanding natural seismogenesis but also to evaluating the risks of fault reactivation and induced seismicity posed by subsurface resources production and by geological storage of CO2. Microstructural studies on natural fault rocks deformed in the mid and upper crust, including those sampled in fault drilling projects, frequently show evidence for i) fluid-related reactions forming an anastomosing phyllosilicate network, ii) pressure solution and cataclasis of clast phases, and iii) dilatation and cementation of fractures, cracks and pores. Moreover, decades of friction experiments on simulated granitic, gabroic, quartz and more recently calcite and phyllosilicate-quartz gouges, have shown that the presence of an aqueous pore fluid, or even water vapour, strongly influences the frictional behaviour of these materials. This has long been recognised to point to the operation of fluid-assisted deformation mechanisms, such as stress corrosion cracking or pressure solution. Indeed, recent low velocity friction experiments performed at Utrecht on evaporite and quartz gouges, with varying amounts of phyllosilicate, indicate that fluid-assisted deformation of the clast phases is a requirement for velocity-weakening slip capable of causing stick-slip. Supercritical carbon dioxide, on the other hand, has little effect on the frictional behaviour of either dry or wet gouges. An important trend emerging from all gouges containing quartz, and tested at hydrothermal conditions and sliding velocities below 100 μm/s, is a transition from velocity strengthening at low temperatures, to velocity weakening at intermediate temperatures, and back to velocity strengthening at high temperatures, delineating three regimes of steady state frictional behaviour. Where dilation has been measured or estimated, the velocity weakening regime is further characterised by porosity development. This all leads to the conclusion that a micromechanism-based description of the frictional behaviour of gouge-filled faults, under mid and upper crustal conditions, needs to account for pressure solution and stress corrosion cracking of clast phases, and for both dilatant and non-dilatant slip on intervening, weak phyllosilicates. First attempts to do this, assuming pressure solution as the fluid-assisted clast deformation mechanism, successfully predict the three-regime behaviour seen in experiments on phyllosilicate-quartz gouges, as well as other key observations. Both steady state and transient frictional behaviour similar to that seen in experiments can be predicted. The key factor here controlling both frictional response (i.e a, b, a-b and Dc in the terminology of RSF modelling) and porosity turns out to be competition between dilatation due to intergranular slip on phyllosillicates versus flow and compaction by pressure solution. In particular, velocity-weakening slip, hence rupture nucleation, are predicted to be caused by the effects of the fluid phase in promoting compaction by pressure solution during dilatant shear.

Vascularized networks with two optimized channel sizes

NASA Astrophysics Data System (ADS)

Wang, K.-M.; Lorente, S.; Bejan, A.

2006-07-01

This paper reports the development of optimal vascularization for supplying self-healing smart materials with liquid that fills and seals the cracks that may occur throughout their volume. The vascularization consists of two-dimensional grids of interconnected orthogonal channels with two hydraulic diameters (D1, D2). The smallest square loop is designed to match the size (d) of the smallest crack. The network is sealed with respect to the outside and is filled with pressurized liquid. In this work, the crack site is modelled as a small spherical volume of diameter d. When a crack is formed, fluid flows from neighbouring channels to the crack site. This volume-to-point flow is optimized using two formulations: (1) incompressible liquid from steady constant-strength sources located in every node of the grid and from sources located equidistantly on the perimeter of the vascularized body of length scale L and (2) slightly compressible liquid from an initially pressurized grid discharging in time-dependent fashion into one crack site. The flow in every channel is laminar and fully developed. The objectives are (a) to minimize the global resistance to the flow from the grid to the crack site and (b) to minimize the time of discharge from the pressurized grid to the crack site. It is shown that methods (a) and (b) yield similar results. There is an optimal ratio of channel diameters D2/D1 < 1, and it decreases as the grid fineness (L/d) increases. The global flow resistance of the grid with optimized ratio of diameters is approximately half of the resistance of the corresponding grid with one channel size (D1 = D2). The optimized ratio of diameters and the minimized global resistance depend on how the grid intersects the crack site: this effect is minor and stresses the robustness of the vascularized design.

Bio-oil production from biomass via supercritical fluid extraction

DOE Office of Scientific and Technical Information (OSTI.GOV)

Durak, Halil, E-mail: halildurak@yyu.edu.tr

2016-04-18

Supercritical fluid extraction is used for producing bio-fuel from biomass. Supercritical fluid extraction process under supercritical conditions is the thermally disruption process of the lignocellulose or other organic materials at 250-400 °C temperature range under high pressure (4-5 MPa). Supercritical fluid extraction trials were performed in a cylindrical reactor (75 mL) in organic solvents (acetone, ethanol) under supercritical conditions with (calcium hydroxide, sodium carbonate) and without catalyst at the temperatures of 250, 275 and 300 °C. The produced liquids at 300 °C in supercritical liquefaction were analyzed and characterized by elemental, GC-MS and FT-IR. 36 and 37 different types of compounds weremore » identified by GC-MS obtained in acetone and ethanol respectively.« less

Effect of nanoscale flows on the surface structure of nanoporous catalysts.

PubMed

Montemore, Matthew M; Montessori, Andrea; Succi, Sauro; Barroo, Cédric; Falcucci, Giacomo; Bell, David C; Kaxiras, Efthimios

2017-06-07

The surface structure and composition of a multi-component catalyst are critical factors in determining its catalytic performance. The surface composition can depend on the local pressure of the reacting species, leading to the possibility that the flow through a nanoporous catalyst can affect its structure and reactivity. Here, we explore this possibility for oxidation reactions on nanoporous gold, an AgAu bimetallic catalyst. We use microscopy and digital reconstruction to obtain the morphology of a two-dimensional slice of a nanoporous gold sample. Using lattice Boltzmann fluid dynamics simulations along with thermodynamic models based on first-principles total-energy calculations, we show that some sections of this sample have low local O 2 partial pressures when exposed to reaction conditions, which leads to a pure Au surface in these regions, instead of the active bimetallic AgAu phase. We also explore the effect of temperature on the surface structure and find that moderate temperatures (≈300-450 K) should result in the highest intrinsic catalytic performance, in apparent agreement with experimental results.

Improved perfluoroalkyl ether fluid development

NASA Technical Reports Server (NTRS)

Jones, William R., Jr.; Paciorek, Kazimiera J. L.; Nakahara, James H.; Smythe, Mark E.; Kratzer, Reinhold H.

1987-01-01

The feasibility of transforming a commercial linear perfluoroalkylether fluid into a material stable in the presence of metals and metal alloys in oxidizing atmospheres at 300 C without the loss of the desirable viscosity temperature characteristics was determined. The approach consisted of thermal oxidative treatment in the presence of catalyst to remove weak links, followed by transformation of the created functional groups into phospha-s-triazine linkages. It is found that the experimental material obtained in 66 percent yield from the commercial fluid exhibits, over an 8 hr period at 300 C in the presence of Ti(4Al, 4Mn) alloy, thermal oxidative stability better by a factor of 2.6 x 1000 based on volatiles evolved than the commercial product. The viscosity and molecular weight of the developed fluid are unchanged and are essentially identical with the commercial material. No metal corrosion occurs with the experimental fluid at 300 C.

3D Simulation of Multiple Simultaneous Hydraulic Fractures with Different Initial Lengths in Rock

NASA Astrophysics Data System (ADS)

Tang, X.; Rayudu, N. M.; Singh, G.

2017-12-01

Hydraulic fracturing is widely used technique for extracting shale gas. During this process, fractures with various initial lengths are induced in rock mass with hydraulic pressure. Understanding the mechanism of propagation and interaction between these induced hydraulic cracks is critical for optimizing the fracking process. In this work, numerical results are presented for investigating the effect of in-situ parameters and fluid properties on growth and interaction of multi simultaneous hydraulic fractures. A fully coupled 3D fracture simulator, TOUGH- GFEM is used for simulating the effect of different vital parameters, including in-situ stress, initial fracture length, fracture spacing, fluid viscosity and flow rate on induced hydraulic fractures growth. This TOUGH-GFEM simulator is based on 3D finite volume method (FVM) and partition of unity element method (PUM). Displacement correlation method (DCM) is used for calculating multi - mode (Mode I, II, III) stress intensity factors. Maximum principal stress criteria is used for crack propagation. Key words: hydraulic fracturing, TOUGH, partition of unity element method , displacement correlation method, 3D fracturing simulator

Understanding fluid transport through the multiscale pore network of a natural shale

NASA Astrophysics Data System (ADS)

Davy, Catherine A.; Nguyen Kim, Thang; Song, Yang; Troadec, David; Blanchenet, Anne-Marie; Adler, Pierre M.

2017-06-01

The pore structure of a natural shale is obtained by three imaging means. Micro-tomography results are extended to provide the spatial arrangement of the minerals and pores present at a voxel size of 700 nm (the macroscopic scale). FIB/SEM provides a 3D representation of the porous clay matrix on the so-called mesoscopic scale (10-20 nm); a connected pore network, devoid of cracks, is obtained for two samples out of five, while the pore network is connected through cracks for two other samples out of five. Transmission Electron Microscopy (TEM) is used to visualize the pore space with a typical pixel size of less than 1 nm and a porosity ranging from 0.12 to 0.25. On this scale, in the absence of 3D images, the pore structure is reconstructed by using a classical technique, which is based on truncated Gaussian fields. Permeability calculations are performed with the Lattice Boltzmann Method on the nanoscale, on the mesoscale, and on the combination of the two. Upscaling is finally done (by a finite volume approach) on the bigger macroscopic scale. Calculations show that, in the absence of cracks, the contribution of the nanoscale pore structure on the overall permeability is similar to that of the mesoscale. Complementarily, the macroscopic permeability is measured on a centimetric sample with a neutral fluid (ethanol). The upscaled permeability on the macroscopic scale is in good agreement with the experimental results.

Who cares about Mid-Ocean Ridge Earthquakes? And Why?

NASA Astrophysics Data System (ADS)

Tolstoy, M.

2004-12-01

Every day the surface of our planet is being slowly ripped apart by the forces of plate tectonics. Much of this activity occurs underwater and goes unnoticed except for by a few marine seismologists who avidly follow the creaks and groans of the ocean floor in an attempt to understand the spreading and formation of oceanic crust. Are marine seismologists really the only ones that care? As it turns out, deep beneath the ocean surface, earthquakes play a fundamental role in a myriad of activity centered on mid-ocean ridges where new crust forms and breaks on a regular basis. This activity takes the form of exotic geological structures hosting roasting hot fluids and bizarre chemosynthetic life forms. One of the fundamental drivers for this other world on the seafloor is earthquakes. Earthquakes provide cracks that allow seawater to penetrate the rocks, heat up, and resurface as hydrothermal vent fluids, thus providing chemicals to feed a thriving biological community. Earthquakes can cause pressure changes along cracks that can fundamentally alter fluid flow rates and paths. Thus earthquakes can both cut off existing communities from their nutrient source and provide new oases on the seafloor around which life can thrive. This poster will present some of the fundamental physical principals of how earthquakes can impact fluid flow, and hence life on the seafloor. Using these other-wordly landscapes and alien-like life forms to woe the unsuspecting passerby, we will sneak geophysics into the picture and tell the story of why earthquakes are so fundamental to life on the seafloor, and perhaps life elsewhere in the universe.

Calculation of elastic properties in lower part of the Kola borehole from bulk chemical compositions of core samples

DOE Office of Scientific and Technical Information (OSTI.GOV)

Babeyko, A.Yu.; Sobolev, S.V.; Sinelnikov, E.D.

1994-09-01

In-situ elastic properties in deep boreholes are controlled by several factors, mainly by lithology, petrofabric, fluid-filled cracks and pores. In order to separate the effects of different factors it is useful to extract lithology-controlled part from observed in-situ velocities. For that purpose we calculated mineralogical composition and isotropic crack-free elastic properties in the lower part of the Kola borehole from bulk chemical compositions of core samples. We use a new technique of petrophysical modeling based on thermodynamic approach. The reasonable accuracy of the modeling is confirmed by comparison with the observations of mineralogical composition and laboratory measurements of density andmore » elastic wave velocities in upper crustal crystalline rocks at high confining pressure. Calculations were carried out for 896 core samples from the depth segment of 6840-10535m. Using these results we estimate density and crack-free isotropic elastic properties of 554 lithology-defined layers composing this depth segment. Average synthetic P-wave velocity appears to be 2.7% higher than the velocity from Vertical Seismic Profiling (VSP), and 5% higher than sonic log velocity. Average synthetic S-wave velocity is 1.4% higher than that from VSP. These differences can be explained by superposition of effects of fabric-related anisotropy, cracks aligned parallel to the foliation plain, and randomly oriented cracks, with the effects of cracks being the predominant control. Low sonic log velocities are likely caused by drilling-induced cracking (hydrofractures) in the borehole walls. The calculated synthetic density and velocity cross-sections can be used for much more detailed interpretations, for which, however, new, more detailed and reliable seismic data are required.« less

Preparation of Carbon-Platinum-Ceria and Carbon-Platinum-Cerium catalysts and its application in Polymer Electrolyte Fuel Cell: Hydrogen, Methanol, and Ethanol

NASA Astrophysics Data System (ADS)

Guzman Blas, Rolando Pedro

This thesis is focused on fuel cells using hydrogen, methanol and ethanol as fuel. Also, in the method of preparation of catalytic material for the anode: Supercritical Fluid Deposition (SFD) and impregnation method using ethylenediaminetetraacetic acid (EDTA) as a chelating agent. The first part of the thesis describes the general knowledge about Hydrogen Polymer Exchange Membrane Fuel Cell (HPEMFC),Direct Methanol Fuel Cell (DMFC) and Direct Ethanol Fuel Cell (DEFC), as well as the properties of Cerium and CeO2 (Ceria). The second part of the thesis describes the preparation of catalytic material by Supercritical Fluid Deposition (SFD). SFD was utilized to deposit Pt and ceria simultaneously onto gas diffusion layers. The Pt-ceria catalyst deposited by SFD exhibited higher methanol oxidation activity compared to the platinum catalyst alone. The linear sweep traces of the cathode made for the methanol cross over study indicate that Pt-Ceria/C as the anode catalyst, due to its better activity for methanol, improves the fuel utilization, minimizing the methanol permeation from anode to cathode compartment. The third and fourth parts of the thesis describe the preparation of material catalytic material Carbon-Platinum-Cerium by a simple and cheap impregnation method using EDTA as a chelating agent to form a complex with cerium (III). This preparation method allows the mass production of the material catalysts without additional significant cost. Fuel cell polarization and power curves experiments showed that the Carbon-Platinum-Cerium anode materials exhibited better catalytic activity than the only Vulcan-Pt catalysts for DMFC, DEFC and HPEMFC. In the case of Vulcan-20%Pt-5%w Cerium, this material exhibits better catalytic activity than the Vulcan-20%Pt in DMFC. In the case of Vulcan-40% Pt-doped Cerium, this material exhibits better catalytic activity than the Vulcan-40% Pt in DMFC, DEFC and HPEMFC. Finally, I propose a theory that explains the reason why the carbon-platinum-cerium has better catalytic activity than platinum-carbon. Due to the hybridization behavior of C and Ce could arise charge transfer, both carbon and cerium to the Platinum. Ce-C→Pt charge transfer could occur at the Ce-C/Pt interface. Thus, results in an increase in the catalytic activity of platinum-cerium-carbon when compared with carbon-platinum.

Cracking mechanism of shale cracks during fracturing

NASA Astrophysics Data System (ADS)

Zhao, X. J.; Zhan, Q.; Fan, H.; Zhao, H. B.; An, F. J.

2018-06-01

In this paper, we set up a model for calculating the shale fracture pressure on the basis of Huang’s model by the theory of elastic-plastic mechanics, rock mechanics and the application of the maximum tensile stress criterion, which takes into account such factors as the crustal stress field, chemical field, temperature field, tectonic stress field, the porosity of shale and seepage of drilling fluid and so on. Combined with the experimental data of field fracturing and the experimental results of three axis compression of shale core with different water contents, the results show that the error between the present study and the measured value is 3.85%, so the present study can provide technical support for drilling engineering.

Characteristics of microearthquakes accompanying hydraulic fracturing as determined from studies of spectra of seismic waveforms

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fehler, M.; Bame, D.

1985-03-01

A study of the spectral properties of the waveforms recorded during hydraulic fracturing earthquakes has been carried out to obtain information about the physical dimensions of the earthquakes. We find two types of events. The first type has waveforms with clear P and S arrivals and spectra that are very similar to earthquakes occurring in tectonic regions. These events are interpreted as being due to shear slip along fault planes. The second type of event has waveforms that are similar in many ways to long period earthquakes observed at volcanoes and is called long period. Many waveforms of these eventsmore » are identical, which implies that these events represent repeated activation of a given source. We propose that the source of these long period events is the sudden opening of a channel that connects two cracks filled with fluid at different pressures. The sizes of the two cracks differ, which causes two or more peaks to appear in the spectra, each peak being associated with one physical dimension of the crack. From the frequencies at which spectral peaks occur, we estimate crack dimensions of between 3 and 22m. 13 refs., 8 figs.« less

Chemical activation of commercial CNTs with simultaneous surface deposition of manganese oxide nano flakes for the creation of CNTs-graphene supported oxygen reduction ternary composite catalysts applied in air fuel cell

NASA Astrophysics Data System (ADS)

Sun, Ling; Liu, Danxian

2018-07-01

To elevate power performance is crucial for commercally potential metal air fuel cells. Non-precious metal oxide-based oxygen reduction catalytic electrode is much desirable. Rational combination with low-dimension nanomaterials are greatly expected as the supports. Herein, carbon nanotubes (CNTs)-graphene supported manganese oxides composite catalysts (CMnCs) were obtained through activating commercial CNTs, namely, immersing them in acidic KMnO4 solution at room condition. It avoided conventional hydrothermal process and template surfactants. CMnCs-based air cathodes were made via pilot manufacture technology and equipped in fuel cells. Through characterizations, CNTs was found structurally defective and their outer walls suffered cracking into graphene nano pieces during processing, which further enhanced oxygen reduction reaction (ORR). Nano sized manganese oxide flakes were simulataneously grown on the CNTs-graphene surfaces, identified as the manganite. The areal distribution was found closely related to the additive amount of KMnO4 with regard to CNTs, somewhat influencing catalytic performance. The ORR activities of these CMnCs exceeded raw CNTs and referred manganese catalysts under identical conditions, and also the CMnCs air fuel cells were capable of outputting ∼15% more power at 100 mA/cm2. This reseach provided an inspiring pilot evidence for updating air fuel cell power from economical carbon as well as industrialization.

Assessment of Composite Delamination Self-Healing Via Micro-Encapsulation

NASA Technical Reports Server (NTRS)

O'Brien, T. Kevin; White, Scott R.

2008-01-01

Composite skin/stringer flange debond specimens manufactured from composite prepreg containing interleaf layers with a polymer based healing agent encapsulated in thin walled spheres were tested. As a crack develops and grows in the base polymer, the spheres fracture releasing the healing agent. The agent reacts with catalyst and polymerizes healing the crack. In addition, through-thickness reinforcement, in the form of pultruded carbon z-pins were included near the flange tips to improve the resistance to debonding. Specimens were manufactured with 14 plies in the skin and 10 plies in the stiffener flange. Three-point bend tests were performed to measure the skin/stiffener debonding strength and the recovered strength after healing. The first three tests performed indicated no healing following unloading and reloading. Micrographs showed that delaminations could migrate to the top of the interleaf layer due to the asymmetric loading, and hence, bypass most of the embedded capsules. For two subsequent tests, specimens were clamped in reverse bending before reloading. In one case, healing was observed as evidenced by healing agent that leaked to the specimen edge forming a visible "scar". The residual strength measured upon reloading was 96% of the original strength indicating healing had occurred. Hence, self-healing is possible in fiber reinforced composite material under controlled conditions, i.e., given enough time and contact with pressure on the crack surfaces. The micro-encapsulation technique may prove more robust when capsule sizes can be produced that are small enough to be embedded in the matrix resin without the need for using an interleaf layer. However, in either configuration, the amount of healing that can occur may be limited to the volume of healing agent available relative to the crack volume that must be filled.

Stress corrosion-controlled rates of mode I fracture propagation in calcareous bedrock

NASA Astrophysics Data System (ADS)

Voigtlaender, Anne; Leith, Kerry; Krautblatter, Michael

2014-05-01

Surface bedrock on natural rock slopes is subject to constant and cyclic environmental stresses (wind, water, wave, ice, seismic or gravitational). Studies indicate that these stresses range up to several hundred kPa, generally too low to cause macroscopic changes in intact rock, although clear evidence of fracture generation, crack propagation and weathering of bedrock illustrates the effect of environmental stresses at the Earth's surface. We suggest that material degradation and its extent, is likely to be controlled by the rate of stress corrosion cracking (SCC). Stress corrosion is a fluid-material reaction, where fluids preferentially react with strained atomic bonds at the tip of developing fractures. Stress corrosion in ferrous and siliceous materials is often accepted as the fracture propagation and degradation rate-controlling process where materials are subject to stresses and fluids. Although evidence for chemical weathering in propagating bedrock fractures is clear in natural environments, the physical system and quantification of stress corrosion in natural rocks is yet to be addressed. Here, we present preliminary data on the relationship between stresses at levels commonly present on natural rock slopes, and material damage resulting from stress corrosion under constant or cyclic tensile loading. We undertake single notch three-point bending tests (SNBT) on fresh calcareous bedrock specimens (1100x100x100mm) over a two-month period. Two beams containing an artificial notch are stressed to 75% of their ultimate strength, and a constant supply of weak acid is applied at the notch tip to enhance chemical reactions. A third, unloaded, beam is also exposed to weak acid in order to elucidate the contribution of stress corrosion cracking to the material degradation. Stresses at the tip of propagating cracks affect the kinetics of the chemical reaction in the specimen exposed to both loading and corrosion, leading to an increase in degradation, and greater stress relaxation. These changes in material properties are monitored using strain gauges, acoustic emission sensors, changes in P-wave velocity, and records of time to failure where appropriate. Our preliminary studies indicate changes in material properties are concentrated in the region of predicted tensile stress intensification. Reactions seem to favourably occur at the stressed bonds around the crack tip. The rate of chemical dissolution and further propagation of the fracture at the notch tip appears to be enhanced by the level of stress applied to the specimen. This provides the foundation for a suite of repeated experiments in which we plan to test corrosion-controlled rates of degradation across a range of loading conditions. The improved understanding into micro-mechanical controls, will contribute to the assessment of rock fall production rates and erosion processes in natural environments as well as natural building stones.

Sand consolidation method

DOE Office of Scientific and Technical Information (OSTI.GOV)

Young, B.M.

1965-10-05

This is a new and improved sand consolidation method wherein an in-situ curing of a resinous fluid is undertaken. This method does not require that the resinous fluids be catalyzed at the surface of the well or well bore as is the case in previous methods. This method consists of, first, pumping an acid-curable consolidating fluid into the unconsolidated sand or earth formation and, secondly, pumping an oil overflush solution containing a halogenated organic or other organic acid or delayed acid-producing chemical. A small quantity of diesel oilspacer may be used between the plastic catalyst solution. The overflush functions tomore » remove permeability, and its acid or acid producing component promotes subsequent hardening of the remaining film of consolidating fluid. Trichloroacetic acid and benzotrichloride are satisfactory to add to the overflush solution for curing the resins. (17 claims)« less

An experimental study of catalytic and non-catalytic reaction in heat recirculating reactors and applications to power generation

NASA Astrophysics Data System (ADS)

Ahn, Jeongmin

An experimental study of the performance of a Swiss roll heat exchanger and reactor was conducted, with emphasis on the extinction limits and comparison of results with and without Pt catalyst. At Re<40, the catalyst was required to sustain reaction; with the catalyst self-sustaining reaction could be obtained at Re less than 1. Both lean and rich extinction limits were extended with the catalyst, though rich limits were extended much further. At low Re, the lean extinction limit was rich of stoichiometric and rich limit had equivalence ratios 80 in some cases. Non-catalytic reaction generally occurred in a flameless mode near the center of the reactor. With or without catalyst, for sufficiently robust conditions, a visible flame would propagate out of the center, but this flame could only be re-centered with catalyst. Gas chromatography indicated that at low Re, CO and non-C3 H8 hydrocarbons did not form. For higher Re, catalytic limits were slightly broader but had much lower limit temperatures. At sufficiently high Re, catalytic and gas-phase limits merged. Experiments with titanium Swiss rolls have demonstrated reducing wall thermal conductivity and thickness leads to lower heat losses and therefore increases operating temperatures and extends flammability limits. By use of Pt catalysts, reaction of propane-air mixtures at temperatures 54°C was sustained. Such low temperatures suggest that polymers may be employed as a reactor material. A polyimide reactor was built and survived prolonged testing at temperatures up to 500°C. Polymer reactors may prove more practical for microscale devices due to their lower thermal conductivity and ease of manufacturing. Since the ultimate goal of current efforts is to develop combustion driven power generation devices at MEMS like scales, a thermally self-sustaining miniature power generation device was developed utilizing a single-chamber solid-oxide-fuel-cell (SOFC) placed in a Swiss roll. With the single-chamber design, fuel/oxygen crossover due to cracking of seals via thermal cycling is irrelevant and coking on the anode is practically eliminated. SOFC power densities up to 420mW/cm2 were observed at low Re. These results suggest that single-chamber SOFC's integrated with heat-recirculating reactors may be a viable approach for small-scale power generation devices.

Stress and Pore Fluid Pressure Cycles Beneath the Seismogenic Layer Recorded by Veins

NASA Astrophysics Data System (ADS)

Nüchter, J. A.; Stöckhert, B.

2006-12-01

Metamorphic rocks approaching the crustal scale brittle-ductile transition (BDT) during exhumation are expected to become increasingly affected by short term stress fluctuations related to seismic activity in the overlying seismogenic layer, while still residing in a long-term viscous environment. The (micro-)structural record of monogenetic syntaxial quartz veins in metamorphic rocks from southern Evia, Greece, yields insight into the processes and conditions just beneath the long-term BDT at temperatures of about 300 to 350° C. The following features are characteristic: 1) The veins crosscut the foliation and all syn-metamorphic structures; 2) the veins have formed from tensile fractures, with a typical length on the order of 10-1 to 101 m; 3) some veins branch symmetrically with an aperture angle of 30°, which is interpreted to indicate high crack propagation rates similar to Raleigh wave speed; 4) the veins formed during a single sealing stage by mineral precipitation in open cavities; 5) the veins show a low aspect ratio of about 10 to 100 and a characteristic lenticular shape, controlled by distributed ductile deformation of the host rock, with vein-parallel shortening by typically less than 1 %; 6) the intensity of crystal plastic deformation in the vein quartz decreases from the vein walls towards the center; 7) fluid inclusions trapped in the vein quartz record a time series of pore fluid pressure (Pf) evolution during progressive sealing, with low Pf at the vein walls (early stage) to high Pf in the vein core (final stage). These features indicate: Opening of the fractures commenced immediately after crack arrest, controlled by ductile deformation of the host rock at temperatures between about 300 and 350° C. The crack opening rate exceeded the rate of sealing, so that the quartz crystals grew into an open cavity. For opening of cracks, the effective stress on the fracture walls must be tensile and the fluid pressure must be similar to that of the magnitude of the least principal stress Pf ≍ σ3. The evolution of Pf recorded by the fluid inclusions reflects the relaxation of stress during progressive opening and sealing of the vein. This is supported by the fact that the quartz crystals grown at the fracture walls, hence early in the opening and sealing history, record a more intense deformation compared to the crystals grown lately in the centre of the vein. The structural and microstructural record of these monogenetic veins reflects an isothermal switch from brittle failure to decelerating viscous creep. The total strain accumulated is low. The following scenario is inferred: Fracturing is proposed to be a consequence of co-seismic loading related to fault slip in the overlying upper crust. Within the underlying damage zone, fractures develop and dilation causes a drop in Pf. Subsequently, the fractures open controlled by viscous creep of the host rock with a concomitant rise in Pf during stress relaxation. Sealing of the fissures to become veins takes place continuously by precipitation of minerals from the pore fluid streaming through the evolving cavity. The lenticular monogenetic veins are therefore interpreted to record a short-term and episodic process. Such type of record of exhumed rocks provides insight into earthquake-related damage beneath the seismogenic layer and into the nature of transient crustal properties in the earthquake cycle.

Zirconium carbide as an electrocatalyst for the chromous-chromic redox couple

NASA Technical Reports Server (NTRS)

Gahn, R. F.; Reid, M. A.; Yang, C. Y. (Inventor)

1981-01-01

Zirconium carbide is used as a catalyst in a REDOX cell for the oxidation of chromous ions to chromic ions and for the reduction of chromic ions to chromous ions. The zirconium carbide is coated on an inert electronically conductive electrode which is present in the anode fluid of the cell.

Polyfunctional fluorosilicone composition, method for making, and use

NASA Technical Reports Server (NTRS)

Singh, Navjot (Inventor); Leman, John Thomas (Inventor); Whitney, John M. (Inventor)

2002-01-01

A fluorosilicone crosslinker and method for making is provided. Reaction is effected between a silanol terminated polyfluoroalkyl silicone fluid and a polyalkoxysilane in the presence of a Platinum Group Metal catalyst. The fluorosilicone crosslinker can be used in combination with a silanol terminated fluoroalkyl substituted polydiorganosiloxane to formulate a neutral, condensation curable, solvent resistant sealant.

Assessments of fluid friction factors for use in leak rate calculations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chivers, T.C.

1997-04-01

Leak before Break procedures require estimates of leakage, and these in turn need fluid friction to be assessed. In this paper available data on flow rates through idealized and real crack geometries are reviewed in terms of a single friction factor k It is shown that for {lambda} < 1 flow rates can be bounded using correlations in terms of surface R{sub a} values. For {lambda} > 1 the database is less precise, but {lambda} {approx} 4 is an upper bound, hence in this region flow calculations can be assessed using 1 < {lambda} < 4.

A Novel Methodology for the Synthesis of Acyloxy Castor Polyol Esters: Low Pour Point Lubricant Base Stocks.

PubMed

Kamalakar, Kotte; Mahesh, Goli; Prasad, Rachapudi B N; Karuna, Mallampalli S L

2015-01-01

Castor oil, a non-edible oil containing hydroxyl fatty acid, ricinoleic acid (89.3 %) was chemically modified employing a two step procedure. The first step involved acylation (C(2)-C(6) alkanoic anhydrides) of -OH functionality employing a green catalyst, Kieselguhr-G and solvent free medium. The catalyst after reaction was filtered and reused several times without loss in activity. The second step is esterification of acylated castor fatty acids with branched mono alcohol, 2-ethylhexanol and polyols namely neopentyl glycol (NPG), trimethylolpropane (TMP) and pentaerythritol (PE) to obtain 16 novel base stocks. The base stocks when evaluated for different lubricant properties have shown very low pour points (-30 to -45°C) and broad viscosity ranges 20.27 cSt to 370.73 cSt, higher viscosity indices (144-171), good thermal and oxidative stabilities, and high weld load capacities suitable for multi-range industrial applications such as hydraulic fluids, metal working fluids, gear oil, forging and aviation applications. The study revealed that acylated branched mono- and polyol esters rich in monounsaturation is desirable for developing low pour point base stocks.

Enhancement mechanisms of graphene in nano-58S bioactive glass scaffold: mechanical and biological performance.

PubMed

Gao, Chengde; Liu, Tingting; Shuai, Cijun; Peng, Shuping

2014-04-16

Graphene is a novel material and currently popular as an enabler for the next-generation nanocomposites. Here, we report the use of graphene to improve the mechanical properties of nano-58S bioactive glass for bone repair and regeneration. And the composite scaffolds were fabricated by a homemade selective laser sintering system. Qualitative and quantitative analysis demonstrated the successful incorporation of graphene into the scaffold without obvious structural damage and weight loss. The optimum compressive strength and fracture toughness reached 48.65 ± 3.19 MPa and 1.94 ± 0.10 MPa · m(1/2) with graphene content of 0.5 wt%, indicating significant improvements by 105% and 38% respectively. The mechanisms of pull-out, crack bridging, crack deflection and crack tip shielding were found to be responsible for the mechanical enhancement. Simulated body fluid and cell culture tests indicated favorable bioactivity and biocompatibility of the composite scaffold. The results suggest a great potential of graphene/nano-58S composite scaffold for bone tissue engineering applications.

A magnetic method for determining the geometry of hydraulic fractures

USGS Publications Warehouse

Byerlee, J.D.; Johnston, M.J.S.

1976-01-01

We propose a method that may be used to determine the spatial orientation of the fracture plane developed during hydraulic fracture. In the method, magnetic particles are injected into the crack with the fracturing fluid so as to generate a sheet of magnetized material. Since the magnetization of a body with extreme dimension ratios, such as a crack, exceeds that of an equidimensional body and since this magnetization is sensitive both to orientation and geometry, this could be used to obtain information about the crack. By measuring the vertical and horizontal components of the magnetic field and field gradients at the earth's surface surrounding the injection well with superconducting magnetometers having 10-4 gamma sensitivity and also by measuring field direction within the well itself, it should be possible to calculate the orientation and perhaps infer the approximate geometry of the fracture surface. Experiments on electric field potential operated in conjunction with this experiment could further constrain estimates of shape and orientation. ?? 1976 Birkha??user Verlag.

Control of serpentinisation rate by reaction-induced cracking

NASA Astrophysics Data System (ADS)

Malvoisin, Benjamin; Brantut, Nicolas; Kaczmarek, Mary-Alix

2017-10-01

Serpentinisation of mantle rocks requires the generation and maintenance of transport pathways for water. The solid volume increase during serpentinisation can lead to stress build-up and trigger cracking, which ease fluid penetration into the rock. The quantitative effect of this reaction-induced cracking mechanism on reactive surface generation is poorly constrained, thus hampering our ability to predict serpentinisation rate in geological environments. Here we use a combined approach with numerical modelling and observations in natural samples to provide estimates of serpentinisation rate at mid-ocean ridges. We develop a micromechanical model to quantify the propagation of serpentinisation-induced cracks in olivine. The maximum crystallisation pressure deduced from thermodynamic calculations reaches several hundreds of megapascals but does not necessary lead to crack propagation if the olivine grain is subjected to high compressive stresses. The micromechanical model is then coupled to a simple geometrical model to predict reactive surface area formation during grain splitting, and thus bulk reaction rate. Our model reproduces quantitatively experimental kinetic data and the typical mesh texture formed during serpentinisation. We also compare the model results with olivine grain size distribution data obtained on natural serpentinised peridotites from the Marum ophiolite and the Papuan ultramafic belt (Papua New Guinea). The natural serpentinised peridotites show an increase of the number of olivine grains for a decrease of the mean grain size by one order of magnitude as reaction progresses from 5 to 40%. These results are in agreement with our model predictions, suggesting that reaction-induced cracking controls the serpentinisation rate. We use our model to estimate that, at mid-ocean ridges, serpentinisation occurs up to 12 km depth and reaction-induced cracking reduces the characteristic time of serpentinisation by one order of magnitude, down to values comprised between 10 and 1000 yr. The increase of effective pressure with depth also prevents cracking, which positions the peak in serpentinisation rate at shallower depths, 4 km above previous predictions.

Making ultrafine and highly-dispersive multimetallic nanoparticles in three-dimensional graphene with supercritical fluid as excellent electrocatalyst for oxygen reduction reaction

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhou, Yazhou; Yen, Clive H.; Hu, Yun Hang

2016-01-01

Three-dimensional (3D) graphene showed an advanced support for designing porous electrode materials due to its high specific surface area, large pore volume, and excellent electronic property. However, the electrochemical properties of reported porous electrode materials still need to be improved further. The current challenge is how to deposit desirable nanoparticles (NPs) with controllable structure, loading and composition in 3D graphene while maintaining the high dispersion. Herein, we demonstrate a modified supercritical fluid (SCF) technique to address this issue by controlling the SCF system. Using this superior method, a series of Pt-based/3D graphene materials with the ultrafine-sized, highly dispersive and controllablemore » composition multimetallic NPs were successfully synthesized. Specifically, the resultant Pt40Fe60/3D graphene showed a significant enhancement in electrocatalytic performance for the oxygen reduction reaction (ORR), including a factor of 14.2 enhancement in mass activity (1.70 A mgPt 1), a factor of 11.9 enhancement in specific activity (1.55 mA cm 2), and higher durability compared with that of Pt/C catalyst. After careful comparison, the Pt40Fe60/3D graphene catalyst shows the higher ORR activity than most of the reported similar 3D graphene-based catalysts. The successful synthesis of such attractive materials by this method also paves the way to develop 3D graphene in widespread applications.« less

Self-healing in single and multiple fiber(s) reinforced polymer composites

NASA Astrophysics Data System (ADS)

Woldesenbet, E.

2010-06-01

You Polymer composites have been attractive medium to introduce the autonomic healing concept into modern day engineering materials. To date, there has been significant research in self-healing polymeric materials including several studies specifically in fiber reinforced polymers. Even though several methods have been suggested in autonomic healing materials, the concept of repair by bleeding of enclosed functional agents has garnered wide attention by the scientific community. A self-healing fiber reinforced polymer composite has been developed. Tensile tests are carried out on specimens that are fabricated by using the following components: hollow and solid glass fibers, healing agent, catalysts, multi-walled carbon nanotubes, and a polymer resin matrix. The test results have demonstrated that single fiber polymer composites and multiple fiber reinforced polymer matrix composites with healing agents and catalysts have provided 90.7% and 76.55% restoration of the original tensile strength, respectively. Incorporation of functionalized multi-walled carbon nanotubes in the healing medium of the single fiber polymer composite has provided additional efficiency. Healing is found to be localized, allowing multiple healing in the presence of several cracks.

Coupling of exothermic and endothermic reactions in oxidative conversion of natural gas into ethylene/olefins over diluted SrO/La{sub 2}O{sub 3}/SA5205 catalyst

DOE Office of Scientific and Technical Information (OSTI.GOV)

Choudhary, V.R.; Mulla, S.A.R.

1997-09-01

In the oxidative conversion of natural gas to ethylene/lower olefins over SrO (17.3 wt.%)/La{sub 2}O{sub 3} (17.9 wt.%)/SA5205 catalyst diluted with inert solid particles (inerts/catalyst(w/w) = 2.0) in the presence of limited O{sub 2}, the exothermic oxidative conversion reactions of natural gas are coupled with the endothermic C{sub 2+} hydrocarbon thermal cracking reactions for avoiding hot spot formation and eliminating heat removal problems. Because of this, the process is operated in the most energy-efficient and safe manner. The influence of various process variables (viz. temperature, NG/O{sub 2} and steam/NG ratios in feed, and space velocity) on the conversion of carbonmore » and also of the individual hydrocarbons in natural gas, the selectivity for C{sub 2}-C{sub 4} olefins, and also on the net heat of reactions in the process has been thoroughly investigated. By carrying out the process at 800--850 C in the presence of steam (H{sub 2}O/NG {le} 0.2) and using limited O{sub 2} in the feed (NG/O{sub 2} = 12--18), high selectivity for ethylene (about 60%) or C{sub 2}-C{sub 4} olefins (above 80%) at the carbon conversion (>15%) of practical interest could be achieved at high space velocity ({ge}34,000 cm{sup 3}/g (catalyst) h), requiring no external energy and also without forming coke or tar-like products. The net heat of reactions can be controlled and the process can be made mildly exothermic or even close to thermoneutral by manipulating the O{sub 2} concentration in the feed.« less

DOE-GO-14154-1 OHIO FINAL report Velocys 30Sept08

DOE Office of Scientific and Technical Information (OSTI.GOV)

Terry J. Mazanec

2008-09-30

The overall goal of the OHIO project was to develop a commercially viable high intensity process to produce ethylene by controlled catalytic reaction of ethane with oxygen in a microchannel reactor. Microchannel technology provides a breakthrough solution to the challenges identified in earlier development work on catalytic ethane oxidation. Heat and mass transfer limitations at the catalyst surface create destructively high temperatures that are responsible for increased production of waste products (CO, CO2, and CH4). The OHIO project focused on microscale energy and mass transfer management, designed to alleviate these transport limitations, thereby improving catalyst selectivity and saving energy-rich feedstock.more » The OHIO project evaluated ethane oxidation in small scale microchannel laboratory reactors including catalyst test units, and full commercial length single- and multi-channel reactors. Small scale catalyst and single channel results met target values for ethylene yields, demonstrating that the microchannel concept improves mass and heat transport compared to conventional reactors and results in improved ethylene yield. Earlier economic sensitivity studies of ethane oxidation processes suggested that only modest improvements were necessary to provide a system that provides significant feedstock, energy, and capital benefits compared to conventional steam ethane cracking. The key benefit derived from the OHIO process is energy savings. Ethylene production consumes more energy than any other U.S. chemical process.1 The OHIO process offers improved feedstock utilization and substantial energy savings due to a novel reaction pathway and the unique abilities of microchannel process technology to control the reaction temperature and other critical process parameters. Based on projected economic benefits of the process, the potential energy savings could reach 150 trillion Btu/yr by the year 2020, which is the equivalent of over 25 million barrels of oil.« less

Geopressured-geothermal test of the EDNA Delcambre No. 1 well, Tigre Lagoon Field, Vermilion Parish, Louisiana: geology of the Tigre Lagoon Field, Planulina Basin. Final report

DOE Office of Scientific and Technical Information (OSTI.GOV)

Not Available

1978-10-01

The geology and hydrology of the Tigre Lagoon Gas Field and the structural and depositional basin in which it occurs, as described, define a hydrodynamic system which has been in operation for millions of years. Fluid entrapment and geopressuring of the deposits has resulted in steepened geothermal gradients, accelerated maturation and thermal degradation (cracking) of fluid hydrocarbons, thermal diagenesis of certain clay minerals with release of much bound and intracrystalline water as free pore water, and a systematic fluid migration history controlled by the sand-bed aquifers in the basin, and by upward leakage at growth faults wherever fluid pressures approachedmore » or exceeded rock pressures. Observed geotemperature, geopressure, water salinity, and natural gas occurrence in the study area conform with the conceptual model developed.« less

Effect of hydrofracking fluid on colloid transport in the unsaturated zone.

PubMed

Sang, Wenjing; Stoof, Cathelijne R; Zhang, Wei; Morales, Verónica L; Gao, Bin; Kay, Robert W; Liu, Lin; Zhang, Yalei; Steenhuis, Tammo S

2014-07-15

Hydraulic fracturing is expanding rapidly in the US to meet increasing energy demand and requires high volumes of hydrofracking fluid to displace natural gas from shale. Accidental spills and deliberate land application of hydrofracking fluids, which return to the surface during hydrofracking, are common causes of environmental contamination. Since the chemistry of hydrofracking fluids favors transport of colloids and mineral particles through rock cracks, it may also facilitate transport of in situ colloids and associated pollutants in unsaturated soils. We investigated this by subsequently injecting deionized water and flowback fluid at increasing flow rates into unsaturated sand columns containing colloids. Colloid retention and mobilization was measured in the column effluent and visualized in situ with bright field microscopy. While <5% of initial colloids were released by flushing with deionized water, 32-36% were released by flushing with flowback fluid in two distinct breakthrough peaks. These peaks resulted from 1) surface tension reduction and steric repulsion and 2) slow kinetic disaggregation of colloid flocs. Increasing the flow rate of the flowback fluid mobilized an additional 36% of colloids, due to the expansion of water filled pore space. This study suggests that hydrofracking fluid may also indirectly contaminate groundwater by remobilizing existing colloidal pollutants.

A fault constitutive relation accounting for thermal pressurization of pore fluid

USGS Publications Warehouse

Andrews, D.J.

2002-01-01

The heat generated in a slip zone during an earthquake can raise fluid pressure and thereby reduce frictional resistance to slip. The amount of fluid pressure rise depends on the associated fluid flow. The heat generated at a given time produces fluid pressure that decreases inversely with the square root of hydraulic diffusivity times the elapsed time. If the slip velocity function is crack-like, there is a prompt fluid pressure rise at the onset of slip, followed by a slower increase. The stress drop associated with the prompt fluid pressure rise increases with rupture propagation distance. The threshold propagation distance at which thermally induced stress drop starts to dominate over frictionally induced stress drop is proportional to hydraulic diffusivity. If hydraulic diffusivity is 0.02 m2/s, estimated from borehole samples of fault zone material, the threshold propagation distance is 300 m. The stress wave in an earthquake will induce an unknown amount of dilatancy and will increase hydraulic diffusivity, both of which will lessen the fluid pressure effect. Nevertheless, if hydraulic diffusivity is no more than two orders of magnitude larger than the laboratory value, then stress drop is complete in large earthquakes.

Esterification Reaction of Glycerol and Palm Oil Oleic Acid Using Methyl Ester Sulfonate Acid Catalyst as Drilling Fluid Formulation

NASA Astrophysics Data System (ADS)

Sari, V. I.; Hambali, E.; Suryani, A.; Permadi, P.

2017-02-01

Esterification reaction between glycerol with palm oil oleic acid to produce glycerol ester and one of the utilization of glycerol esters is as ingredients of drilling fluids formula for oil drilling needs. The purpose of this research is to get the best conditions of the esterification process. The esterification reaction does with the reactants is glycerol with purity of 97.6%, palm oil oleic acid with the molar ratio is 1:1, Methyl Ester Sulfonate Acid (MESA) catalyst 0.5%, and stirring speed 400 rpm. The temperature range of 180°C to 240°C and the processing time between 120 to 180 minutes. The results showed that the best conditions of the esterification reaction at the temperature 240°C and time process are 180 minute. The increasing temperature resulted that the acid number decreases and causing the conversion increased. The maximum conversion is 99.24%, density 0.93 g/cm3, flash point 241°C, pour point -3°C, the boiling point of 244 °C, the acid value of 1.90 mg KOH/g sample, kinematic viscosity 31.51 cSt (40°C), surface tension 37.0526 dyne/cm and GCMS identification, glycerol ester at 22,256 retention time (minutes) and wide area 73.75 (%). From the research results obtained glycerol ester with characteristics suitable for drilling fluid formulations.

Computational Fluid Dynamics (CFD) simulations of a Heisenberg Vortex Tube

NASA Astrophysics Data System (ADS)

Bunge, Carl; Sitaraman, Hariswaran; Leachman, Jake

2017-11-01

A 3D Computational Fluid Dynamics (CFD) simulation of a Heisenberg Vortex Tube (HVT) is performed to estimate cooling potential with cryogenic hydrogen. The main mechanism driving operation of the vortex tube is the use of fluid power for enthalpy streaming in a highly turbulent swirl in a dual-outlet tube. This enthalpy streaming creates a temperature separation between the outer and inner regions of the flow. Use of a catalyst on the peripheral wall of the centrifuge enables endothermic conversion of para-ortho hydrogen to aid primary cooling. A κ- ɛ turbulence model is used with a cryogenic, non-ideal equation of state, and para-orthohydrogen species evolution. The simulations are validated with experiments and strategies for parametric optimization of this device are presented.

Catalytic hollow spheres

NASA Technical Reports Server (NTRS)

Wang, Taylor G. (Inventor); Elleman, Daniel D. (Inventor); Lee, Mark C. (Inventor); Kendall, Jr., James M. (Inventor)

1989-01-01

The improved, heterogeneous catalysts are in the form of gas-impervious, hollow, thin-walled spheres (10) suitably formed of a shell (12) of metal such as aluminum having a cavity (14) containing a gas at a pressure greater than atmospheric pressure. The wall material may be, itself, catalytic or the catalyst can be coated onto the sphere as a layer (16), suitably platinum or iron, which may be further coated with a layer (18) of activator or promoter. The density of the spheres (30) can be uniformly controlled to a preselected value within .+-.10 percent of the density of the fluid reactant such that the spheres either remain suspended or slowly fall or rise through the liquid reactant.

Catalytic hollow spheres

NASA Technical Reports Server (NTRS)

Wang, Taylor G. (Inventor); Elleman, Daniel D. (Inventor); Lee, Mark C. (Inventor); Kendall, Jr., James M. (Inventor)

1986-01-01

The improved, heterogeneous catalysts are in the form of gas-impervious, hollow, thin-walled spheres (10) suitably formed of a shell (12) of metal such as aluminum having a cavity (14) containing a gas at a pressure greater than atmospheric pressure. The wall material may be, itself, catalytic or the catalyst can be coated onto the sphere as a layer (16), suitably platinum or iron, which may be further coated with a layer (18) of activator or promoter. The density of the spheres (30) can be uniformly controlled to a preselected value within .+-.10 percent of the density of the fluid reactant such that the spheres either remain suspended or slowly fall or rise through the liquid reactant.

Laser-Induced Fluorescence Detection in High-Throughput Screening of Heterogeneous Catalysts and Single Cells Analysis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Su, Hui

2001-01-01

Laser-induced fluorescence detection is one of the most sensitive detection techniques and it has found enormous applications in various areas. The purpose of this research was to develop detection approaches based on laser-induced fluorescence detection in two different areas, heterogeneous catalysts screening and single cell study. First, the author introduced laser-induced imaging (LIFI) as a high-throughput screening technique for heterogeneous catalysts to explore the use of this high-throughput screening technique in discovery and study of various heterogeneous catalyst systems. This scheme is based on the fact that the creation or the destruction of chemical bonds alters the fluorescence properties ofmore » suitably designed molecules. By irradiating the region immediately above the catalytic surface with a laser, the fluorescence intensity of a selected product or reactant can be imaged by a charge-coupled device (CCD) camera to follow the catalytic activity as a function of time and space. By screening the catalytic activity of vanadium pentoxide catalysts in oxidation of naphthalene, they demonstrated LIFI has good detection performance and the spatial and temporal resolution needed for high-throughput screening of heterogeneous catalysts. The sample packing density can reach up to 250 x 250 subunits/cm 2 for 40-μm wells. This experimental set-up also can screen solid catalysts via near infrared thermography detection. In the second part of this dissertation, the author used laser-induced native fluorescence coupled with capillary electrophoresis (LINF-CE) and microscope imaging to study the single cell degranulation. On the basis of good temporal correlation with events observed through an optical microscope, they have identified individual peaks in the fluorescence electropherograms as serotonin released from the granular core on contact with the surrounding fluid.« less

Oxygen Isotope and Microtextural Evidence for Fluctuations in Fluid Pressure During Contact Metamorphism, Alta Aureole, Utah, USA

NASA Astrophysics Data System (ADS)

Bowman, J. R.; Valley, J. W.; Kita, N.

2006-12-01

Thin section-scale textures record a detailed history of prograde and retrograde reactions in the periclase (Per) zone of the Alta Stock aureole. New ion microprobe (SIMS) measurements (10 micron spot, ±0.2 permil, 1sd) of the oxygen isotope compositions of the carbonates preserving these textures provide evidence for at least two cycles of oscillation of fluid pressure (Pfl) between lithostatic (PL) and hydrostatic (Phyd) conditions during evolution of the inner aureole. Infiltration of water-rich fluids during prograde metamorphism converted dolomite (Dol) to Per + calcite (Cal) marble and caused significant 18O/16O depletion in the Dol protolith (Initial δ18O (Cal) > +25 permil), producing Cal with δ18O values of +11 permil. The SIMS values approximate oxygen isotope exchange equilibrium with the Alta stock, indicating that infiltrating fluids were likely magmatic. Exsolution of fluid from the crystallizing magma, coupled with geothermometry from the periclase zone marbles, requires Pfl> PL. Horizontally-oriented expansion cracks filled with brucite (Br) extend from Br pseudomorphs after periclase, and cut retrograde Dol that partially to completely rims the Br pseudomorphs. This earlier retrograde Dol is significantly depleted in 18O/16O relative to matrix Cal, with δ18O of +5 to +7.1 permil. These lower δ18O values indicate that meteoric water infiltrated into the Per marbles during cooling and resulting partial back reaction of Per + Cal to Dol, prior to the hydration of the remaining Per to Br. Influx of meteoric water requires sufficient increase in permeability to permit surface- derived meteoric water to penetrate to the estimated 4.5 km depth of this structural level of the Alta aureole, and suggests a resulting decrease in Pfl to hydrostatic pressure conditions. The horizontally-oriented expansion cracks associated with the Br pseudomorphs indicate that sub-vertical expansion accompanied hydration of Per to Br, requiring that Pfl increase again to values equal to and even slightly in excess of PL. Subsequent formation of a second generation of sub-vertical Dol veins with very low δ18O values (-1.9 to +1.2 permil) indicates another stage of infiltration involving even greater amounts of meteoric water, and a return to hydrostatic Pflconditions. Hence the detailed microtextures in the Per zone marbles, and their δ18O values, measureable with the spatial resolution capability of the ion microprobe, record a history of fluctuating fluid pressure between lithostatic and hydrostatic conditions in the inner Alta aureole. Such fluctuations should not be surprising. Contact metamorphic environments are characterized by strong spatial and temporal gradients in temperature, and a number of thermally-dependent factors (e.g., compaction, crystallization, reaction-generated porosity, thermally-controlled expansion and contraction) would then interact dynamically as sealing and cracking mechanisms to both increase and decrease permeability. Further, transient increases in fluid pressure would be expected from production of volatiles by metamorphic reactions and from multiple pulses of magmatic fluid produced during the assembly of an igneous intrusion.

Enhancement of plasma generation in catalyst pores with different shapes

NASA Astrophysics Data System (ADS)

Zhang, Yu-Ru; Neyts, Erik C.; Bogaerts, Annemie

2018-05-01

Plasma generation inside catalyst pores is of utmost importance for plasma catalysis, as the existence of plasma species inside the pores affects the active surface area of the catalyst available to the plasma species for catalytic reactions. In this paper, the electric field enhancement, and thus the plasma production inside catalyst pores with different pore shapes is studied with a two-dimensional fluid model. The results indicate that the electric field will be significantly enhanced near tip-like structures. In a conical pore with small opening, the strongest electric field appears at the opening and bottom corners of the pore, giving rise to a prominent ionization rate throughout the pore. For a cylindrical pore, the electric field is only enhanced at the bottom corners of the pore, with lower absolute value, and thus the ionization rate inside the pore is only slightly enhanced. Finally, in a conical pore with large opening, the electric field is characterized by a maximum at the bottom of the pore, yielding a similar behavior for the ionization rate. These results demonstrate that the shape of the pore has a significantly influence on the electric field enhancement, and thus modifies the plasma properties.

Efficiency of magnetorheological fluid finishing on the elimination of defects in fused silica optics

NASA Astrophysics Data System (ADS)

Catrin, R.; Taroux, D.; Cormont, P.; Maunier, C.; Corbineau, T.; Razé, G.; Néauport, J.

2013-09-01

The MegaJoule laser being constructed at the CEA near Bordeaux (France) is designed to focus more than 1 MJ of energy of UV light, on a millimeter scale target in the centre of an experiment chamber. After amplification and transport at the wavelength of 1053 nm, frequency conversion at 351 nm is done with KH2PO4 crystals. The final optic assembly of this system is made up of large fused silica optics, working in transmission, that are used to convey, focus or shape the laser beam. When exposed to fluences of some joules per square centimeter at 351 nm within nanosecond pulse duration, fused silica optics can exhibit localized damage. Damage sites grow exponentially after further laser exposition and therefore dramatically limit the optic lifetime. The nature of the surface finishing process has been established to determine the lifetime of these components under high UV fluences (i.e. more than 5 J/cm2 for 3 ns pulses). Being able to reduce or eliminate the damage initiators such as subsurface cracks present in subsurface damage (SSD) layer of conventionally polished optical components aims this study. Magneto-rheological fluid finishing (MRF) is chosen as a final polishing tool to remove layers of material without inducing further damages. MRF enables to process optics with very small normal stresses applied to the surface during material removal and thus permits the elimination of the residual subsurface cracks. This study offers a better understanding of the efficiency of MRF polishing on the elimination of subsurface cracks in SSD layers.

An integrated structural and geochemical study of fracture aperture growth in the Campito Formation of eastern California

NASA Astrophysics Data System (ADS)

Doungkaew, N.; Eichhubl, P.

2015-12-01

Processes of fracture formation control flow of fluid in the subsurface and the mechanical properties of the brittle crust. Understanding of fundamental fracture growth mechanisms is essential for understanding fracture formation and cementation in chemically reactive systems with implications for seismic and aseismic fault and fracture processes, migration of hydrocarbons, long-term CO2 storage, and geothermal energy production. A recent study on crack-seal veins in deeply buried sandstone of east Texas provided evidence for non-linear fracture growth, which is indicated by non-elliptical kinematic fracture aperture profiles. We hypothesize that similar non-linear fracture growth also occurs in other geologic settings, including under higher temperature where solution-precipitation reactions are kinetically favored. To test this hypothesis, we investigate processes of fracture growth in quartzitic sandstone of the Campito Formation, eastern California, by combining field structural observations, thin section petrography, and fluid inclusion microthermometry. Fracture aperture profile measurements of cemented opening-mode fractures show both elliptical and non-elliptical kinematic aperture profiles. In general, fractures that contain fibrous crack-seal cement have elliptical aperture profiles. Fractures filled with blocky cement have linear aperture profiles. Elliptical fracture aperture profiles are consistent with linear-elastic or plastic fracture mechanics. Linear aperture profiles may reflect aperture growth controlled by solution-precipitation creep, with the aperture distribution controlled by solution-precipitation kinetics. We hypothesize that synkinematic crack-seal cement preserves the elliptical aperture profiles of elastic fracture opening increments. Blocky cement, on the other hand, may form postkinematically relative to fracture opening, with fracture opening accommodated by continuous solution-precipitation creep.

Challenging dyke ascent models using novel laboratory experiments: Implications for reinterpreting evidence of magma ascent and volcanism

NASA Astrophysics Data System (ADS)

Kavanagh, Janine L.; Burns, Alec J.; Hilmi Hazim, Suraya; Wood, Elliot P.; Martin, Simon A.; Hignett, Sam; Dennis, David J. C.

2018-04-01

Volcanic eruptions are fed by plumbing systems that transport magma from its source to the surface, mostly fed by dykes. Here we present laboratory experiments that model dyke ascent to eruption using a tank filled with a crust analogue (gelatine, which is transparent and elastic) that is injected from below by a magma analogue (dyed water). This novel experimental setup allows, for the first time, the simultaneous measurement of fluid flow, sub-surface and surface deformation during dyke ascent. During injection, a penny-shaped fluid-filled crack is formed, intrudes, and traverses the gelatine slab vertically to then erupt at the surface. Polarised light shows the internal stress evolution as the dyke ascends, and an overhead laser scanner measures the surface elevation change in the lead-up to dyke eruption. Fluorescent passive-tracer particles that are illuminated by a laser sheet are monitored, and the intruding fluid's flow dynamics and gelatine's sub-surface strain evolution is measured using particle image velocimetry and digital image correlation, respectively. We identify 4 previously undescribed stages of dyke ascent. Stage 1, early dyke growth: the initial dyke grows from the source, and two fluid jets circulate as the penny-shaped crack is formed. Stage 2, pseudo-steady dyke growth: characterised by the development of a rapidly uprising, central, single pseudo-steady fluid jet, as the dyke grows equally in length and width, and the fluid down-wells at the dyke margin. Sub-surface host strain is localised at the head region and the tail of the dyke is largely static. Stage 3, pre-eruption unsteady dyke growth: an instability in the fluid flow appears as the central fluid jet meanders, the dyke tip accelerates towards the surface and the tail thins. Surface deformation is only detected in the immediate lead-up to eruption and is characterised by an overall topographic increase, with axis-symmetric topographic highs developed above the dyke tip. Stage 4 is the onset of eruption, when fluid flow is projected outwards and focused towards the erupting fissure as the dyke closes. A simultaneous and abrupt decrease in sub-surface strain occurs as the fluid pressure is released. Our results provide a comprehensive physical framework upon which to interpret evidence of dyke ascent in nature, and suggest dyke ascent models need to be re-evaluated to account for coupled intrusive and extrusive processes and improve the recognition of monitoring signals that lead to volcanic eruptions in nature.

Sphere based fluid systems

NASA Technical Reports Server (NTRS)

Elleman, Daniel D. (Inventor); Wang, Taylor G. (Inventor)

1989-01-01

Systems are described for using multiple closely-packed spheres. In one system for passing fluid, a multiplicity of spheres lie within a container, with all of the spheres having the same outside diameter and with the spheres being closely nested in one another to create multiple interstitial passages of a known size and configuration and smooth walls. The container has an inlet and outlet for passing fluid through the interstitial passages formed between the nested spheres. The small interstitial passages can be used to filter out material, especially biological material such as cells in a fluid, where the cells can be easily destroyed if passed across sharp edges. The outer surface of the spheres can contain a material that absorbs a constitutent in the flowing fluid, such as a particular contamination gas, or can contain a catalyst to chemically react the fluid passing therethrough, the use of multiple small spheres assuring a large area of contact of these surfaces of the spheres with the fluid. In a system for storing and releasing a fluid such as hydrogen as a fuel, the spheres can include a hollow shell containing the fluid to be stored, and located within a compressable container that can be compressed to break the shells and release the stored fluid.

3D printing in chemical engineering and catalytic technology: structured catalysts, mixers and reactors.

PubMed

Parra-Cabrera, Cesar; Achille, Clement; Kuhn, Simon; Ameloot, Rob

2018-01-02

Computer-aided fabrication technologies combined with simulation and data processing approaches are changing our way of manufacturing and designing functional objects. Also in the field of catalytic technology and chemical engineering the impact of additive manufacturing, also referred to as 3D printing, is steadily increasing thanks to a rapidly decreasing equipment threshold. Although still in an early stage, the rapid and seamless transition between digital data and physical objects enabled by these fabrication tools will benefit both research and manufacture of reactors and structured catalysts. Additive manufacturing closes the gap between theory and experiment, by enabling accurate fabrication of geometries optimized through computational fluid dynamics and the experimental evaluation of their properties. This review highlights the research using 3D printing and computational modeling as digital tools for the design and fabrication of reactors and structured catalysts. The goal of this contribution is to stimulate interactions at the crossroads of chemistry and materials science on the one hand and digital fabrication and computational modeling on the other.

Integrated reformer and shift reactor

DOEpatents

Bentley, Jeffrey M.; Clawson, Lawrence G.; Mitchell, William L.; Dorson, Matthew H.

2006-06-27

A hydrocarbon fuel reformer for producing diatomic hydrogen gas is disclosed. The reformer includes a first reaction vessel, a shift reactor vessel annularly disposed about the first reaction vessel, including a first shift reactor zone, and a first helical tube disposed within the first shift reactor zone having an inlet end communicating with a water supply source. The water supply source is preferably adapted to supply liquid-phase water to the first helical tube at flow conditions sufficient to ensure discharge of liquid-phase and steam-phase water from an outlet end of the first helical tube. The reformer may further include a first catalyst bed disposed in the first shift reactor zone, having a low-temperature shift catalyst in contact with the first helical tube. The catalyst bed includes a plurality of coil sections disposed in coaxial relation to other coil sections and to the central longitudinal axis of the reformer, each coil section extending between the first and second ends, and each coil section being in direct fluid communication with at least one other coil section.

Monitoring corrosion in reinforced concrete structures

NASA Astrophysics Data System (ADS)

Kung, Peter; Comanici, Maria I.

2014-06-01

Many defects can cause deterioration and cracks in concrete; these are results of poor concrete mix, poor workmanship, inadequate design, shrinkage, chemical and environmental attack, physical or mechanical damage, and corrosion of reinforcing steel (RS). We want to develop a suite of sensors and systems that can detect that corrosion is taking place in RS and inform owners how serious the problem is. By understanding the stages of the corrosion process, we can develop special a sensor that detects each transition. First, moisture ingress can be monitored by a fiber optics humidity sensor, then ingress of Chloride, which acts as a catalyst and accelerates the corrosion process by converting iron into ferrous compounds. We need a fiber optics sensor which can quantify Chloride ingress over time. Converting ferric to ferrous causes large volume expansion and cracks. Such pressure build-up can be detected by a fiber optic pressure sensor. Finally, cracks emit acoustic waves, which can be detected by a high frequency sensor made with phase-shifted gratings. This paper will discuss the progress in our development of these special sensors and also our plan for a field test by the end of 2014. We recommend that we deploy these sensors by visually inspecting the affected area and by identifying locations of corrosion; then, work with the designers to identify spots that would compromise the integrity of the structure; finally, drill a small hole in the concrete and insert these sensors. Interrogation can be done at fixed intervals with a portable unit.

Silica precipitation potentially controls earthquake recurrence in seismogenic zones.

PubMed

Saishu, Hanae; Okamoto, Atsushi; Otsubo, Makoto

2017-10-17

Silica precipitation is assumed to play a significant role in post-earthquake recovery of the mechanical and hydrological properties of seismogenic zones. However, the relationship between the widespread quartz veins around seismogenic zones and earthquake recurrence is poorly understood. Here we propose a novel model of quartz vein formation associated with fluid advection from host rocks and silica precipitation in a crack, in order to quantify the timescale of crack sealing. When applied to sets of extensional quartz veins around the Nobeoka Thrust of SW Japan, an ancient seismogenic splay fault, our model indicates that a fluid pressure drop of 10-25 MPa facilitates the formation of typical extensional quartz veins over a period of 6.6 × 10 0 -5.6 × 10 1 years, and that 89%-100% of porosity is recovered within ~3 × 10 2 years. The former and latter sealing timescales correspond to the extensional stress period (~3 × 10 1 years) and the recurrence interval of megaearthquakes in the Nankai Trough (~3 × 10 2 years), respectively. We therefore suggest that silica precipitation in the accretionary wedge controls the recurrence interval of large earthquakes in subduction zones.

Waveform inversion of oscillatory signatures in long-period events beneath volcanoes

USGS Publications Warehouse

Kumagai, H.; Chouet, B.A.; Nakano, M.

2002-01-01

The source mechanism of long-period (LP) events is examined using synthetic waveforms generated by the acoustic resonance of a fluid-filled crack. We perform a series of numerical tests in which the oscillatory signatures of synthetic LP waveforms are used to determine the source time functions of the six moment tensor components from waveform inversions assuming a point source. The results indicate that the moment tensor representation is valid for the odd modes of crack resonance with wavelengths 2L/n, 2W/n, n = 3, 5, 7, ..., where L and W are the crack length and width, respectively. For the even modes with wavelengths 2L/n, 2W/n, n = 2, 4, 6,..., a generalized source representation using higher-order tensors is required, although the efficiency of seismic waves radiated by the even modes is expected to be small. We apply the moment tensor inversion to the oscillatory signatures of an LP event observed at Kusatsu-Shirane Volcano, central Japan. Our results point to the resonance of a subhorizontal crack located a few hundred meters beneath the summit crater lakes. The present approach may be useful to quantify the source location, geometry, and force system of LP events, and opens the way for moment tensor inversions of tremor.

MRF, ELSM and STED: tools to study defects in fused silica optics

NASA Astrophysics Data System (ADS)

Catrin, R.; Taroux, D.; Cormont, P.; Maunier, C.; Neauport, J.

2013-11-01

The MegaJoule laser being constructed at the CEA near Bordeaux (France) is designed to focus more than 1 MJ of energy at 351 nm, on a millimetre scale target in the centre of an experiment chamber. The final optic assembly of this system operating at a wavelength of 351 nm is made up of large fused silica optics, working in transmission, that are used to convey and focus the laser beam. Under high fluences (i.e. more than 5 J/cm2 for 3 ns pulses), the limited lifetime of final optical assembly is a major concern for fusion scale laser facilities. Previous works have shown that surface finishing processes applied to manufacture these optical components can leave subsurface cracks (SSD), pollution or similar defects that act as initiators of the laser damage. In this work, we used epi-fluorescent light scanning microscopy (ELSM) and Stimulated Emission Depletion (STED) in confocal mode with fluorescent dye tagging to get a better knowledge of size and depth of these subsurface cracks. Magnetorheological fluid finishing technique (MRF) was also used as a tool to remove these cracks and thus assess depths measured by confocal microscopy. Subsurface cracks with a width of about 120 nm are observed up to ten micrometers below the surface.

Magnesium alloys as body implants: fracture mechanism under dynamic and static loadings in a physiological environment.

PubMed

Choudhary, Lokesh; Raman, R K Singh

2012-02-01

It is essential that a metallic implant material possesses adequate resistance to cracking/fracture under the synergistic action of a corrosive physiological environment and mechanical loading (i.e. stress corrosion cracking (SCC)), before the implant can be put to actual use. This paper presents a critique of the fundamental issues with an assessment of SCC of a rapidly corroding material such as magnesium alloys, and describes an investigation into the mechanism of SCC of a magnesium alloy in a physiological environment. The SCC susceptibility of the alloy in a simulated human body fluid was established by slow strain rate tensile (SSRT) testing using smooth specimens under different electrochemical conditions for understanding the mechanism of SCC. However, to assess the life of the implant devices that often possess fine micro-cracks, SCC susceptibility of notched specimens was investigated by circumferential notch tensile (CNT) testing. CNT tests also produced important design data, i.e. threshold stress intensity for SCC (KISCC) and SCC crack growth rate. Fractographic features of SCC were examined using scanning electron microscopy. The SSRT and CNT results, together with fractographic evidence, confirmed the SCC susceptibility of both smooth and notched specimens of a magnesium alloy in the physiological environment. Copyright © 2011 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Infrasonic wave accompanying a crack opening during the 2015 Hakone eruption

NASA Astrophysics Data System (ADS)

Yukutake, Yohei; Ichihara, Mie; Honda, Ryou

2018-03-01

To understand the initial process of the phreatic eruption of the Hakone volcano from June 29 to July 01, 2015, we analyzed infrasound data using the cross-correlation between infrasound and vertical ground velocity and compared the results of our analysis to the crustal deformation detected by tiltmeters and broadband seismometers. An infrasound signal and vertical ground motion due to an infrasound wave coupled to the ground were detected simultaneously with the opening of a crack source beneath the Owakudani geothermal region during the 2-min time period after 07:32 JST on June 29, 2015 (JST = UTC + 8 h). Given that the upper end of the open crack was approximately 150 m beneath the surface, the time for the direct emission of highly pressurized fluid from the upper end of the open crack to the surface should have exceeded the duration of the inflation owing to the hydraulic diffusivity in the porous media. Therefore, the infrasound signal coincident with the opening of the crack may reflect a sudden emission of volcanic gas resulting from the rapid vaporization of pre-existing groundwater beneath Owakudani because of the transfer of the volumetric strain change from the deformation source. We also noticed a correlation pattern corresponding to discrete impulsive infrasound signals during vent formation, which occurred several hours to 2 days after the opening of the crack. In particular, we noted that the sudden emission of vapor coincided with the inflation of the shallow pressure source, whereas the eruptive burst events accompanied by the largest vent formation were delayed by approximately 2 days. Furthermore, we demonstrated that the correlation method is a useful tool in detecting small infrasound signals and provides important information regarding the initial processes of the eruption.[Figure not available: see fulltext.

Experimental and theoretical fracture mechanics applied to volcanic conduits and domes

NASA Astrophysics Data System (ADS)

Sammonds, P.; Matthews, C.; Kilburn, C.; Smith, R.; Tuffen, H.; Meredith, P.

2008-12-01

We present an integrated modelling and experimental approach to magma deformation and fracture, which we attempt to validate against field observations of seismicity. The importance of fracture processes in magma ascent dynamics and lava dome growth and collapse are apparent from the associated seismicity. Our laboratory experiments have shown that brittle fracture of magma can occur at high temperature and stress conditions prevalent in the shallow volcanic system. Here, we use a fracture mechanics approach to model seismicity preceding volcanic eruptions. Starting with the fracture mechanics concept of a crack in an elastic body, we model crack growth around the volcanic conduit through the processes of crack interactions, leading either to the propagation and linkage of cracks, or crack avoidance and the inhibition of crack propagation. The nature of that interaction is governed by the temperature and plasticity of the magma. We find that fracture mechanics rules can account for the style of seismicity preceding eruptions. We have derived the changes in seismic b-value predicted by the model and interpret these in terms of the style of fracturing, fluid flow and heat transport. We compare our model with results from our laboratory experiments where we have deformed lava at high temperatures under triaxial stresses. These experiments were conducted in dry and water saturated conditions at effective pressures up to 10 MPa, temperatures up to 1000°C and strain rates from 10-4 s-1 to 10-6 s-1. The behaviour of these magmas was largely brittle under these conditions. We monitored the acoustic emission emitted and calculate the change in micro-seismic b-value with deformation. These we find are in accord with volcano seismicity and our fracture mechanics model.

Bentonite modification with pillarization method using metal stannum

NASA Astrophysics Data System (ADS)

Widjaya, Robert R.; Juwono, Ariadne L.; Rinaldi, Nino

2017-11-01

Clay minerals have received considerable attention in the last years because of their environmental compatibility, low cost, high selectivity, and operational simplicity. Although clays are very useful for many application in the field of catalysis, they have main disadvantage: their lack of pore volume and spesific surface area. Porosity and stability of these materials are improved by pillaring the clay layers with SnCl4, which leads to materials known as pillared clays (PILC). This research aims were to characterize the Bentonite and Sn-Bentonite as catalysts for cracking and oligomerization. The Sn-Bentonite was prepared by pillarization method with a variation in metal ratio of 5 mmol dan 10 mmol.gr-1 of bentonit. The catalyst characterized by X-ray Diffraction, X-ray Fluorescence, Fourier Transform Infra Red, Brunauer Emmett Teller, Thermogravimetric Analysis. The results showed that the Sn-Bentonite catalyst had large basal spacing and good porous structure, and the specific surface areas increased. XRF detected the Sn in the Bentonite and TGA results showed the ability Sn-Bentonite in receiving heat. FTIR test showed two type of acidity, broansted and lewis acid. The characterized results indicated that Sn-Bentonite with metal ratio 5 mmol.gr-1 better than Sn-Bentonite with metal ratio 10 mmol.gr-1, in which there was a significant increase the basal spacings, specific surface area, and pore volume. The TGA results for Sn-Bentonite appeared to be more thermally stable than Bentonite.

Field Investigation of Surface Deformation Induced by the 2016 Meinong Earthquake and its Implications to Regional Geological Structures

NASA Astrophysics Data System (ADS)

Yi, De-Cheng; Chuang, Ray Y.; Lin, Ching-Weei

2017-04-01

We demonstrate mapping results of a newly-identified active folding-associated fault in southwestern Taiwan, which was triggered by the distant ML 6.6 Meinong earthquake in 2016. The 14.6-km-deep main shock occurred in Meinong at 3:57 (GMT +08) on February 6th while a series of 21-27 km deep aftershocks were induced after 160 seconds in Guanmiao, where is 25km NW away from the epicenter of the main shock. The focal mechanism of the Meinong main shock shows a westward oblique thrust with the fault plane of 275°/42°/17° (strike/dip/rake) but Guanmiao aftershocks show the N-S striking eastward normal movement. The study area locates at an on-going fold-and-thrust belt close to the deformation front of Taiwan orogeny with high rates of convergence, uplift and erosion. The geology of SW Taiwan is characterized by the 3-km-thick mudstones with high fluid pressure underlying the loose sedimentary rocks forming mud diapirs or mud-core anticlines. The significance of the Meinong earthquake is (1) aftershocks are far away from the main shock, and (2) the surface cracks partially distributed systematically along lineaments observed from InSAR, which has never been recognized as geological structures before. This study aims to establish possible kinematic processes of shallow deformation induced by the Meinong earthquake. We mapped surface cracks around the lineaments by using hand-held GPS and measured surface cracks by the compass and vernier. Among 249 kinematic data measured from 244 observed surface cracks and ruptures, the type of deformation was mostly identified as dilation or lateral translation and only 4 data were compressional deformation. The overall surface displacement moved to the northwest and west, consistent with the regional coseismic movement. The opening of the surface cracks range from 0.5 to 105 mm and 85% of them are less than 10 mm. Preseismic deformed features such as failure of the retaining wall were also observed along the western and eastern boundary of the coseismic deformation area, indicating accumulated deformation and repeated structural activity in this area. In addition, we found a series of centimeters to meters long, N-S to N-W striking and eastern-side-down surface ruptures with the 4-19 cm heave distributed along the 4-km-long, nearly N-S striking and range-facing scarp with the 4-12 m height at the west of Guanmiao, where locate between the Chungchou anticline and Guanmiao syncline. We interpret these surface ruptures as a sign of the bending-moment fault associated with folding amplified by seismic energy through fluid-rich mud diapirs. Thus, seismic potential in this region needs to be re-evaluated, and the mechanism of seismic-induced amplification through high fluid pressure medium may play a critical role in assessing earthquake hazards in regions with similar geology to SW Taiwan.

Study on influence of three kinds of stress on crack propagation in butt welds of spiral coil waterwall for ultra supercritical boiler

NASA Astrophysics Data System (ADS)

Yan, Zhenrong; Si, Jun

2017-09-01

The spiral coil waterwall is the main pressure parts and the core functional components of Ultra Supercritical Boiler. In the process of operation, the spiral coil waterwall is under the combined action of welding residual stress, installation defects stress and working fluid stress, Cracks and crack propagation are easy to occur in butt welds with defects. In view of the early cracks in the butt welds of more T23 water cooled walls, in this paper, the influence of various stresses on the crack propagation in the butt welds of spiral coil waterwall was studied by numerical simulation. Firstly, the welding process of T23 water cooled wall tube was simulated, and the welding residual stress field was obtained. Then,on the basis, put the working medium load on the spiral coil waterwall, the supercoated stress distribution of the welding residual stress and the stress of the working medium is obtained. Considering the bending moment formed by stagger joint which is the most common installation defects, the stress field distribution of butt welds in T23 water-cooled wall tubes was obtained by applying bending moment on the basis of the stress field of the welding residual stress and the working medium stress. The results show that, the welding residual stress is small, the effect of T23 heat treatment after welding to improve the weld quality is not obvious; The working medium load plays a great role in the hoop stress of the water cooled wall tube, and promotes the cracks in the butt welds; The axial stress on the water cooled wall tube produced by the installation defect stress is obvious, the stagger joint, and other installation defects are the main reason of crack propagation of spiral coil waterwall. It is recommended that the control the bending moment resulting from the stagger joint not exceed 756.5 NM.

Self-powered automatic secondary air controllers for woodstoves and small furnaces

DOEpatents

Siemer, Darryl D.

1991-01-01

A controller for automatically regulating the supply of secondary combustion air to woodstoves and small furnaces. The controller includes a movable air valve for controlling the amount of secondary air admitted into the chamber. A self powered means monitors the concentration of combustible gases and vapors and actuates the movable air valve to increase the supply of secondary air in response to increasing concentrations of the combustible gases and vapors. The self-powered means can be two fluid filled sensor bulbs, one of which has a coating of a combustion catalyst. Alternatively, the self powered means can be two metallic stripes laminated together, one of which is coated with a combustion catalyst, and when heated, causes the air valve to actuate.

Effect of Hydrofracking Fluid on Colloid Transport in the Unsaturated Zone

PubMed Central

2014-01-01

Hydraulic fracturing is expanding rapidly in the US to meet increasing energy demand and requires high volumes of hydrofracking fluid to displace natural gas from shale. Accidental spills and deliberate land application of hydrofracking fluids, which return to the surface during hydrofracking, are common causes of environmental contamination. Since the chemistry of hydrofracking fluids favors transport of colloids and mineral particles through rock cracks, it may also facilitate transport of in situ colloids and associated pollutants in unsaturated soils. We investigated this by subsequently injecting deionized water and flowback fluid at increasing flow rates into unsaturated sand columns containing colloids. Colloid retention and mobilization was measured in the column effluent and visualized in situ with bright field microscopy. While <5% of initial colloids were released by flushing with deionized water, 32–36% were released by flushing with flowback fluid in two distinct breakthrough peaks. These peaks resulted from 1) surface tension reduction and steric repulsion and 2) slow kinetic disaggregation of colloid flocs. Increasing the flow rate of the flowback fluid mobilized an additional 36% of colloids, due to the expansion of water filled pore space. This study suggests that hydrofracking fluid may also indirectly contaminate groundwater by remobilizing existing colloidal pollutants. PMID:24905470

Walking the Razor's Edge: Risks and Rewards for Students and Faculty Adopting Case in Point Teaching and Learning Approaches

ERIC Educational Resources Information Center

Wildermuth, Cristina de-Mello-e-Souza; Smith-Bright, Elaine; Noll-Wilson, Sarah; Fink, Alex

2015-01-01

Case in Point (CIP) is an interactive leadership development method pioneered by Ronald Heifetz. CIP instructors follow a fluid class structure, in which group dynamics and student concerns become catalysts for learning. CIP proponents defend the method's potential to help students experience real life leadership challenges. To date, however, very…

Enhancement mechanisms of graphene in nano-58S bioactive glass scaffold: mechanical and biological performance

PubMed Central

Gao, Chengde; Liu, Tingting; Shuai, Cijun; Peng, Shuping

2014-01-01

Graphene is a novel material and currently popular as an enabler for the next-generation nanocomposites. Here, we report the use of graphene to improve the mechanical properties of nano-58S bioactive glass for bone repair and regeneration. And the composite scaffolds were fabricated by a homemade selective laser sintering system. Qualitative and quantitative analysis demonstrated the successful incorporation of graphene into the scaffold without obvious structural damage and weight loss. The optimum compressive strength and fracture toughness reached 48.65 ± 3.19 MPa and 1.94 ± 0.10 MPa·m1/2 with graphene content of 0.5 wt%, indicating significant improvements by 105% and 38% respectively. The mechanisms of pull-out, crack bridging, crack deflection and crack tip shielding were found to be responsible for the mechanical enhancement. Simulated body fluid and cell culture tests indicated favorable bioactivity and biocompatibility of the composite scaffold. The results suggest a great potential of graphene/nano-58S composite scaffold for bone tissue engineering applications. PMID:24736662

Injection initiated fracture in soft solids

NASA Astrophysics Data System (ADS)

Hutchens, Shelby; Yang, Steven

Damage accumulation in soft materials under hydrostatic loading conditions is a primary injury mechanism in blast and blunt force trauma. A recently explored technique known as cavitation rheology (CR) provides a promising avenue for quickly and inexpensively approximating hydrostatic conditions via the reverse loading scenario, void pressurization. Past CR measurements of synthetic, polymeric materials at length scales from mm's to μm's have been found to correlate with both elastic modulus and fracture energy. The technique is performed via pressurization of fluid within a needle that is embedded within a material. This experimental setup allows crack evolution to be monitored, similar to traditional pre-notched failure samples. We observe a systematic evolution of crack morphology as a function of cross-link density in a soft elastomer. Crack shape is quantified using micro-computed tomography and shown to transition from being roughly penny-shaped to multi-lobed (predominately three) to spherical with decreasing crosslinking. Moduli are on the order of kPa. We describe this morphology evolution using a balance between the energetic costs of the strain energy in deforming the surrounding material and the intrinsic fracture energy necessary to form a new surface.

Isotropic events observed with a borehole array in the Chelungpu fault zone, Taiwan.

PubMed

Ma, Kuo-Fong; Lin, Yen-Yu; Lee, Shiann-Jong; Mori, Jim; Brodsky, Emily E

2012-07-27

Shear failure is the dominant mode of earthquake-causing rock failure along faults. High fluid pressure can also potentially induce rock failure by opening cavities and cracks, but an active example of this process has not been directly observed in a fault zone. Using borehole array data collected along the low-stress Chelungpu fault zone, Taiwan, we observed several small seismic events (I-type events) in a fluid-rich permeable zone directly below the impermeable slip zone of the 1999 moment magnitude 7.6 Chi-Chi earthquake. Modeling of the events suggests an isotropic, nonshear source mechanism likely associated with natural hydraulic fractures. These seismic events may be associated with the formation of veins and other fluid features often observed in rocks surrounding fault zones and may be similar to artificially induced hydraulic fracturing.

Neutron Radiography of Fluid Flow for Geothermal Energy Research

NASA Astrophysics Data System (ADS)

Bingham, P.; Polsky, Y.; Anovitz, L.; Carmichael, J.; Bilheux, H.; Jacobsen, D.; Hussey, D.

Enhanced geothermal systems seek to expand the potential for geothermal energy by engineering heat exchange systems within the earth. A neutron radiography imaging method has been developed for the study of fluid flow through rock under environmental conditions found in enhanced geothermal energy systems. For this method, a pressure vessel suitable for neutron radiography was designed and fabricated, modifications to imaging instrument setups were tested, multiple contrast agents were tested, and algorithms developed for tracking of flow. The method has shown success for tracking of single phase flow through a manufactured crack in a 3.81 cm (1.5 inch) diameter core within a pressure vessel capable of confinement up to 69 MPa (10,000 psi) using a particle tracking approach with bubbles of fluorocarbon-based fluid as the ;particles; and imaging with 10 ms exposures.

Powder-Metallurgical Bearings For Turbopumps

NASA Technical Reports Server (NTRS)

Bhat, B. N.; Humphries, T. S.; Thom, R. L.; Moxson, V.; Friedman, G. I.; Dolan, F. J.; Shipley, R. J.

1993-01-01

Bearings fabricated by powder metallurgy developed for use in machines subjected to extremes of temperature, rolling-contact cyclic stresses, and oxidizing or otherwise corrosive fluids. Bearings also extend operating lives of other machines in which bearings required to resist extreme thermal, mechanical, and chemical stresses. One alloy exhibiting outstanding properties was MRC-2001. Resistance to fatigue, stress corrosion cracking, and wear found superior to that of 440C stainless steel.

Instability in Rotating Machinery

NASA Technical Reports Server (NTRS)

1985-01-01

The proceedings contain 45 papers on a wide range of subjects including flow generated instabilities in fluid flow machines, cracked shaft detection, case histories of instability phenomena in compressors, turbines, and pumps, vibration control in turbomachinery (including antiswirl techniques), and the simulation and estimation of destabilizing forces in rotating machines. The symposium was held to serve as an update on the understanding and control of rotating machinery instability problems.

A new method for synthesizing fluid inclusions in fused silica capillaries containing organic and inorganic material

USGS Publications Warehouse

Chou, I.-Ming; Song, Y.; Burruss, R.C.

2008-01-01

Considerable advances in our understanding of physicochemical properties of geological fluids and their roles in many geological processes have been achieved by the use of synthetic fluid inclusions. We have developed a new method to synthesize fluid inclusions containing organic and inorganic material in fused silica capillary tubing. We have used both round (0.3 mm OD and 0.05 or 0.1 mm ID) and square cross-section tubing (0.3 ?? 0.3 mm with 0.05 ?? 0.05 mm or 0.1 ?? 0.1 mm cavities). For microthermometric measurements in a USGS-type heating-cooling stage, sample capsules must be less than 25 mm in length. The square-sectioned capsules have the advantage of providing images without optical distortion. However, the maximum internal pressure (P; about 100 MPa at 22 ??C) and temperature (T; about 500 ??C) maintained by the square-sectioned capsules are less than those held by the round-sectioned capsules (about 300 MPa at room T, and T up to 650 ??C). The fused silica capsules can be applied to a wide range of problems of interest in fluid inclusion and hydrothermal research, such as creating standards for the calibration of thermocouples in heating-cooling stages and frequency shifts in Raman spectrometers. The fused silica capsules can also be used as containers for hydrothermal reactions, especially for organic samples, including individual hydrocarbons, crude oils, and gases, such as cracking of C18H38 between 350 and 400 ??C, isotopic exchanges between C18H38 and D2O and between C19D40 and H2O at similar temperatures. Results of these types of studies provide information on the kinetics of oil cracking and the changes of oil composition under thermal stress. When compared with synthesis of fluid inclusions formed by healing fractures in quartz or other minerals or by overgrowth of quartz at elevated P-T conditions, the new fused-silica method has the following advantages: (1) it is simple; (2) fluid inclusions without the presence of water can be formed; (3) synthesized inclusions are large and uniform, and they are able to tolerate high internal P; (4) it is suitable for the study of organic material; and (5) redox control is possible due to high permeability of the fused silica to hydrogen.

Supercritical Water Process for the Chemical Recycling of Waste Plastics

NASA Astrophysics Data System (ADS)

Goto, Motonobu

2010-11-01

The development of chemical recycling of waste plastics by decomposition reactions in sub- and supercritical water is reviewed. Decomposition reactions proceed rapidly and selectively using supercritical fluids compared to conventional processes. Condensation polymerization plastics such as PET, nylon, and polyurethane, are relatively easily depolymerized to their monomers in supercritical water. The monomer components are recovered in high yield. Addition polymerization plastics such as phenol resin, epoxy resin, and polyethylene, are also decomposed to monomer components with or without catalysts. Recycling process of fiber reinforced plastics has been studied. Pilot scale or commercial scale plants have been developed and are operating with sub- and supercritical fluids.

Pressure loss modulus correlation for Delta p across uniformly distributed-loss devices

NASA Technical Reports Server (NTRS)

Nunz, Gregory J.

1994-01-01

A dimensionless group, called a pressure loss modulus (N(sub PL)), is introduced that, in conjunction with an appropriately defined Reynolds number, is of considerable engineering utility in correlating steady-state Delta p vs flow calibration data and subsequently as a predictor, using the same or a different fluid, in uniformly distributed pressure loss devices. It is particularly useful under operation in the transition regime. Applications of this simple bivariate correlation to three diverse devices of particular interest for small liquid rocket engine fluid systems are discussed: large L/D capillary tube restrictors, packed granular catalyst beds, and stacked vortex-loss disk restrictors.

Thermal Shock Resistance of Si3N4/h -BN Composites Prepared via Catalytic Reaction-Bonding Route

NASA Astrophysics Data System (ADS)

Yang, Wanli; Peng, Zhigang; Dai, Lina; Shi, Zhongqi; Jin, Zhihao

2017-09-01

Si3N4/h-BN ceramic matrix composites were prepared via a catalytic reaction-bonding route by using ZrO2 as nitridation catalyst, and the water quenching (fast cooling) and molten aluminum quenching tests (fast heating) were carried out to evaluate the thermal shock resistance of the composites. The results showed that the thermal shock resistance was improved obviously with the increase in h-BN content, and the critical thermal shock temperature difference (Δ T c) reaches as high as 780 °C when the h-BN content was 30 wt.%. The improvement of thermal shock resistance of the composites was mainly due to the crack tending to quasi static propagating at weak bonding interface between Si3N4 and h-BN with the increase in h-BN content. For the molten aluminum quenching test, the residual strength showed no obvious decrease compared with water quenching test, which could be caused by the mild stress condition on the surface. In addition, a calculated parameter, volumetric crack density ( N f), was presented to quantitative evaluating the thermal shock resistance of the composites in contrast to the conventional R parameter.

Multifaceted effects of HZSM-5 (Proton-exchanged Zeolite Socony Mobil-5) on catalytic cracking of pinewood pyrolysis vapor in a two-stage fixed bed reactor.

PubMed

Wang, Yimeng; Wang, Jie

2016-08-01

The pinewood was pyrolyzed in the first reactor at a heating rate of 10°Cmin(-1) from room temperature to 700°C, and the vapor was allowed to be cracked through the second reactor in a temperature range of 450-750°C without and with HZSM-5. Attempts were made to determine a wide spectrum of gaseous and liquid products, as well as the mass and element partitions to gas, water, bio-oil, coke and char. HZSM-5 showed a preferential deoxygenation effect via the facilitated decarbonylation and decarboxylation with the inhibited dehydration at 550-600°C. This catalyst also displayed a high selectivity for the formations of aromatic hydrocarbons and olefins by the promoted hydrogen transfer to these products at 550-600°C. The bio-oil produced with HZSM-5 at 500-600°C had the yields of 14.5-16.8%, the high heat values of 39.1-42.4MJkg(-1), and the energy recoveries of 33-35% (all dry biomass basis). Copyright © 2016 Elsevier Ltd. All rights reserved.

Self-healing woven glass fabric/epoxy composites with the healant consisting of micro-encapsulated epoxy and latent curing agent

NASA Astrophysics Data System (ADS)

Yin, Tao; Zhou, Lin; Zhi Rong, Min; Qiu Zhang, Ming

2008-02-01

This paper reports a study of self-healing woven glass fabric reinforced epoxy composites. The healing agent was a two-component one synthesized in the authors' laboratory, which consisted of epoxy-loaded urea-formaldehyde microcapsules as the polymerizable binder and CuBr2(2-methylimidazole)4 (CuBr2(2-MeIm)4) as the latent hardener. Both the microcapsules and the matching catalyst were pre-embedded and pre-dissolved in the composites' matrix, respectively. When the microcapsules are split by propagating cracks, the uncured epoxy can be released into the damaged areas and then consolidated under the catalysis of CuBr2(2-MeIm)4 that was homogeneously distributed in the composites' matrix on a molecular scale. As a result, the cracked faces can be bonded together. The influence of the content of the self-healing agent on the composites' tensile properties, interlaminar fracture toughness and healing efficiency was evaluated. It was found that a healing efficiency over 70% relative to the fracture toughness of virgin composites was obtained in the case of 30 wt% epoxy-loaded microcapsules and 2 wt% latent hardener.

The effect of fault-bend folding on seismic velocity in the marginal ridge of accretionary prisms

USGS Publications Warehouse

Cai, Y.; Wang, Chun-Yong; Hwang, W.-t.; Cochrane, G.R.

1995-01-01

Fluid venting in accretionary prisms, which feeds chemosynthetic biological communities, occurs mostly on the marginal thrust ridge. New seismic data for the marginal ridge of the Cascadia prism show significantly lower velocity than that in the adjacent oceanic basin and place important constraints on the interpretations of why fluid venting occurs mostly on the marginal ridge. We employed a finite-element method to analyze a typical fault-bend folding model to explain the phenomenon. The fault in the model is simulated by contact elements. The elements are characterized not only by finite sliding along a slide line, but also by elastoplastic deformation. We present the results of a stress analysis which show that the marginal ridge is under subhorizontal extension and the frontal thrust is under compression. This state of stress favors the growth of tensile cracks in the marginal ridge, facilitates fluid flow and reduces seismic velocities therein; on the other hand, it may close fluid pathways along the frontal thrust and divert fluid flow to the marginal ridge. ?? 1995 Birkha??user Verlag.

A case study of the fluid structure interaction of a Francis turbine

NASA Astrophysics Data System (ADS)

Müller, C.; Staubli, T.; Baumann, R.; Casartelli, E.

2014-03-01

The Francis turbine runners of the Grimsel 2 pump storage power plant showed repeatedly cracks during the last decade. It is assumed that these cracks were caused by flow induced forces acting on blades and eventual resonant runner vibrations lead to high stresses in the blade root areas. The eigenfrequencies of the runner were simulated in water using acoustic elements and compared to experimental data. Unsteady blades pressure distribution determined by a transient CFD simulation of the turbine were coupled to a FEM simulation. The FEM simulation enabled analyzing the stresses in the runner and the eigenmodes of the runner vibrations. For a part-load operating point, transient CFD simulations of the entire turbine, including the spiral case, the runner and the draft tube were carried out. The most significant loads on the turbine runner resulted from the centrifugal forces and the fluid forces. Such forces effect temporally invariant runner blades loads, in contrast rotor stator interaction or draft tube instabilities induce pressure fluctuations which cause the temporally variable forces. The blades pressure distribution resulting from the flow simulation was coupled by unidirectional-harmonic FEM simulation. The dominant transient blade pressure distribution of the CFD simulation were Fourier transformed, and the static and harmonic portion assigned to the blade surfaces in the FEM model. The evaluation of the FEM simulation showed that the simulated part load operating point do not cause critical stress peaks in the crack zones. The pressure amplitudes and frequencies are very small and interact only locally with the runner blades. As the frequencies are far below the modal frequencies of the turbine runner, resonant vibrations obviously are not excited.

A Novel CO2-Responsive Viscoelastic Amphiphilic Surfactant Fluid for Fracking in Enhanced Oil/Gas Recovery

NASA Astrophysics Data System (ADS)

Zhong, L.; Wu, X.; Dai, C.

2017-12-01

Over the past decade, the rapid rise of unconventional shale gas and tight sandstone oil development through horizontal drilling and high volume hydraulic fracturing has expanded the extraction of hydrocarbon resources. Hydraulic fracturing fluids play very important roles in enhanced oil/gas recovery. However, damage to the reservoir rock and environmental contamination caused by hydraulic fracturing flowback fluids has raised serious concerns. The development of reservoir rock friendly and environmental benign fracturing fluids is in immediate demand. Studies to improve properties of hydraulic fracturing fluids have found that viscoelastic surfactant (VES) fracturing fluid can increase the productivity of gas/oil and be efficiently extracted after fracturing. Compared to conventional polymer fracturing fluid, VES fracturing fluid has many advantages, such as few components, easy preparation, good proppant transport capacity, low damage to cracks and formations, and environment friendly. In this work, we are developing a novel CO2-responsive VES fracking fluid that can readily be reused. This fluid has a gelling-breaking process that can be easily controlled by the presence of CO2 and its pressure. We synthesized erucamidopropyl dimethylamine (EA) as a thickening agent for hydraulic fracturing fluid. The influence of temperature, presence of CO2 and pressure on the viscoelastic behavior of this fluid was then investigated through rheological measurements. The fracturing fluid performance and recycle property were lastly studied using core flooding tests. We expect this fluid finds applications not only in enhanced oil/gas recovery, but also in areas such as controlling groundwater pollution and microfluidics.

Alkali Metal CO2 Sorbents and the Resulting Metal Carbonates: Potential for Process Intensification of Sorption-Enhanced Steam Reforming.

PubMed

Memon, Muhammad Zaki; Zhao, Xiao; Sikarwar, Vineet Singh; Vuppaladadiyam, Arun K; Milne, Steven J; Brown, Andy P; Li, Jinhui; Zhao, Ming

2017-01-03

Sorption-enhanced steam reforming (SESR) is an energy and cost efficient approach to produce hydrogen with high purity. SESR makes it economically feasible to use a wide range of feedstocks for hydrogen production such as methane, ethanol, and biomass. Selection of catalysts and sorbents plays a vital role in SESR. This article reviews the recent research aimed at process intensification by the integration of catalysis and chemisorption functions into a single material. Alkali metal ceramic powders, including Li 2 ZrO 3 , Li 4 SiO 4 and Na 2 ZrO 3 display characteristics suitable for capturing CO 2 at low concentrations (<15% CO 2 ) and high temperatures (>500 °C), and thus are applicable to precombustion technologies such as SESR, as well as postcombustion capture of CO 2 from flue gases. This paper reviews the progress made in improving the operational performance of alkali metal ceramics under conditions that simulate power plant and SESR operation, by adopting new methods of sorbent synthesis and doping with additional elements. The paper also discusses the role of carbonates formed after in situ CO 2 chemisorption during a steam reforming process in respect of catalysts for tar cracking.

A superhard, quenchable carbon polymorph formed by the room-temperature compression of graphite (Invited)

NASA Astrophysics Data System (ADS)

Wang, Y.; Kiefer, B.; Lee, K. K.

2010-12-01

As one of the revolutionary inventions of the 20th century, synthetic diamond has had a large impact on industry and on scientific research. However, the necessities of high pressures, high temperatures and a metal catalyst during the manufacturing of synthetic diamond make it energy consuming thus limits its availability and use. Here, we report on the synthesis of a superhard non-diamond material resulting from the compression of graphite above ~20 GPa at room temperature without the utilization of metal catalysts. The final product includes a nano-sized phase of carbon that is recoverable at ambient conditions. Furthermore, the ring cracks left on the diamond anvils suggest that the hardness of this post-graphite phase is at least comparable to that of diamond. We use high-resolution synchrotron x-ray diffraction and micro-Raman spectroscopy to monitor the structural transformation in graphite under high pressure and room temperature and find the transition to be sluggish. The possible crystal structure of the new, quenchable phase will be discussed and the time-dependent formation of this superhard post-graphite carbon will be addressed and compared to first-principle predictions.

In situ {sup 13}C MAS NMR study of n-hexane conversion on Pt and Pd supported on basic materials

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ivanova, I.I.; Pasau-Claerbout, A.; Seivert, M.

n-Hexane conversion was studied in situ on Pt and Pd supported on aluminum-stabilized magnesium oxide and Pt on Zeolite KL catalysts (Pt/Mg(Al)O, Pd/Mg(Al)O and Pt/KL) by means of {sup 13}C MAS NMR spectroscopy. n-Hexane 1-{sup 13}C was used as a labelled reactant. Forty NMR lines corresponding to 14 different products were resolved and identified. The NMR line assignments were confirmed by adsorption of model compounds. The NMR results were further quantified and compared with continuous flow microreactor tests. Four parallel reaction pathways were identified under flow conditions: isomerization, cracking, dehydrocyclization, and dehydrogenation. Aromatization occurs via two reaction routes: (1) n-hexanemore » dehydrogenation towards hexadienes and hexatrienes, followed by dehydrogenation of a cyclic intermediate. The former reaction pathway is prevented under NMR batch conditions. High pressures induced in the NMR cells at high reaction temperatures (573, 653 K) shift the reaction equilibrium towards hydrogenation. NMR experiments showed that on Pt catalysts aromatization occurs via a cyclohexane intermediate, whereas on Pd it takes place via methylcyclopentane ring enlargement. 54 refs., 15 figs., 3 tabs.« less

Influence of strain on the corrosion of magnesium alloys and zinc in physiological environments.

PubMed

Törne, Karin; Örnberg, Andreas; Weissenrieder, Jonas

2017-01-15

During implantation load-bearing devices experience stress that may influence its mechanical and corrosion profile and potentially lead to premature rupture. The susceptibility to stress corrosion cracking (SCC) of the Mg-Al alloy AZ61 and Zn was studied in simulated body fluid (m-SBF) and whole blood by slow strain rate (SSR) testing in combination with electrochemical impedance spectroscopy (EIS) and further ex situ analysis including scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy. AZ61 was found to be highly susceptible to SCC. EIS analysis show that although the majority of cracking occurred during the apparent plastic straining, cracking initiation occurs already in the elastic region at ∼50% of the ultimate tensile strength (UTS). Shifts in EIS phase angle and open circuit potential can be used to detect the onset of SCC. Zinc demonstrated a highly ductile behavior with limited susceptibility to SCC. No significant decrease in UTS was observed in m-SBF but a decrease in time to failure by ∼25% compared to reference samples indicates some effect on the mechanical properties during the ductile straining. The formation of micro cracks, ∼10μm deep, was indicated by the EIS analysis and later confirmed by ex situ SEM. The results of SSR analysis of zinc in whole blood showed a reduced effect compared to m-SBF and no cracks were detected. It appears that formation of an organic surface layer protects the corroding surface from cracking. These results highlight the importance of considering the effect of biological species on the degradation of implants in the clinical situation. Strain may deteriorate the corrosion properties of metallic implants drastically. We study the influence of load on the corrosion properties of a magnesium alloy and zinc by a combination of electrochemical impedance spectroscopy (EIS) and slow strain rate analysis. This combination of techniques has previously not been used for studying degradation in physiological relevant electrolytes. EIS provide valuable information on the initial formation of cracks, detecting crack nucleation before feasible in slow strain rate analysis. This sensitivity of EIS shows the potential for electrochemical methods to be used for in situ monitoring crack formation of implants in more applied studies. Copyright © 2016 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Bio-Oil Separation and Stabilization by Near-Critical Propane Fractionation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ginosar, Daniel M.; Petkovic, Lucia M.; Agblevor, Foster A.

Bio-oils produced by thermal process are promising sources of sustainable, low greenhouse gas alternative fuels. These thermal processes are also well suited to decentralized energy production due to low capital and operating costs. Algae feedstocks for bio-oil production are of particular interest, due in part to their high-energy growth yields. Further, algae can be grown in non-arable areas in fresh, brackish, salt water, or even waste water. Unfortunately, bio-oils produced by thermal processes present significant stability challenges. These oils have complex chemical compositions, are viscous, reactive, and thermally unstable. Further, the components within the oils are difficult to separate bymore » fractional distillation. By far, the most effective separation and stabilization method has been solvent extraction. However, liquid phase extraction processes pose two main obstacles to commercialization; they require a significant amount of energy to remove and recover the solvent from the product, and they have a propensity for the solvent to become contaminated with minerals from the char and ash present in the original bio-oil. Separation and fractionation of thermally produced bio-oils using supercritical fluids (SCF) offers the advantages of liquid solvent extraction while drastically reducing energy demands and the predisposition to carry over solids into the extracted phase. SCFs are dense fluids with liquid-like solvent properties and gas-like transport properties. Further, SCF density and solvent strength can be tuned with minor adjustments in pressure, co-solvent addition, or gas anti-solvent addition. Catalytic pyrolysis oils were produced from Scenedesmus dimorphus algae using a fluid catalytic cracking catalyst. Bio-oil produced from catalytic fast pyrolysis (CFP) was separated using critical fluids. Propane extraction was performed at 65 °C at a fluid reduced pressure of 2.0 (85 bar) using an eight to one solvent to feed ratio by weight. Extraction of catalytic fast pyrolysis oil with near critical propane produced an oil extract that was physically and chemically different from and more stable than the original oil. The propane extract displayed lower viscosity and lower average molecular weight. The species present in the propane extract were likely the less polar that would be expected from using a non-polar solvent (propane). Carbonyl containing species in the extract were likely ketones and esters. The raffinate contained a higher amnount of OH bonded species along with the more polar more polar acids, amides, and alcohols. The higher concentration of nitrogen in the raffinate may confirm the presence of amides. Viscosity of the propane extract increased only half as much as that of the CFP bio-oil. Further, In situ NMR aging studies showed that the propane extract was more stable than the raw oil. In conclusion, propane extraction is a promising method to decrease the nitrogen content of bio-oils and to improve the stability of bio-oils obtained by the catalytic pyrolysis of algae based biomass.« less

Heat transfer and fluid flow analysis of self-healing in metallic materials

NASA Astrophysics Data System (ADS)

Martínez Lucci, J.; Amano, R. S.; Rohatgi, P. K.

2017-03-01

This paper explores imparting self-healing characteristics to metal matrices similar to what are observed in biological systems and are being developed for polymeric materials. To impart self-healing properties to metal matrices, a liquid healing method was investigated; the met hod consists of a container filled with low melting alloy acting as a healing agent, embedded into a high melting metal matrix. When the matrix is cracked; self-healing is achieved by melting the healing agent allowing the liquid metal to flow into the crack. Upon cooling, solidification of the healing agent occurs and seals the crack. The objective of this research is to investigate the fluid flow and heat transfer to impart self-healing property to metal matrices. In this study, a dimensionless healing factor, which may help predict the possibility of healing is proposed. The healing factor is defined as the ratio of the viscous forces and the contact area of liquid metal and solid which prevent flow, and volume expansion, density, and velocity of the liquid metal, gravity, crack size and orientation which promote flow. The factor incorporates the parameters that control self-healing mechanism. It was observed that for lower values of the healing factor, the liquid flows, and for higher values of healing factor, the liquid remains in the container and healing does not occur. To validate and identify the critical range of the healing factor, experiments and simulations were performed for selected combinations of healing agents and metal matrices. The simulations were performed for three-dimensional models and a commercial software 3D Ansys-Fluent was used. Three experimental methods of synthesis of self-healing composites were used. The first method consisted of creating a hole in the matrices, and liquid healing agent was poured into the hole. The second method consisted of micro tubes containing the healing agent, and the third method consisted of incorporating micro balloons containing the healing agent in the matrix. The observed critical range of the healing factor is between 407 and 495; only for healing factor values below 407 healing was observed in the matrices.

Solar heated fluidized bed gasification system

NASA Technical Reports Server (NTRS)

Qader, S. A. (Inventor)

1981-01-01

A solar-powered fluidized bed gasification system for gasifying carbonaceous material is presented. The system includes a solar gasifier which is heated by fluidizing gas and steam. Energy to heat the gas and steam is supplied by a high heat capacity refractory honeycomb which surrounds the fluid bed reactor zone. The high heat capacity refractory honeycomb is heated by solar energy focused on the honeycomb by solar concentrator through solar window. The fluid bed reaction zone is also heated directly and uniformly by thermal contact of the high heat capacity ceramic honeycomb with the walls of the fluidized bed reactor. Provisions are also made for recovering and recycling catalysts used in the gasification process. Back-up furnace is provided for start-up procedures and for supplying heat to the fluid bed reaction zone when adequate supplies of solar energy are not available.

Mathematical Models of Seafloor Hydrothermal Systems Driven by Serpentinization of Peridotite

NASA Astrophysics Data System (ADS)

Lowell, R. P.; Rona, P. A.; Germanovich, L. N.

2001-12-01

Most seafloor hydrothermal systems are driven by heat transfer from subsurface magma bodies. At slow spreading ridges of the Atlantic and Indian oceans, however, magma supply is low; and tectonic activity brings mantle rocks to shallow depths in the crust. Then, the heat of formation released upon serpentinization of peridotite provides the energy source for hydrothermal circulation. This latter class of system has been relatively unstudied, but recent discoveries of peridotite-hosted hydrothermal systems along the Mid-Atlantic Ridge suggest that such systems may play an important role in geochemical cycling and biogeochemical processes. The likelihood that peridotite-hosted hydrothermal systems was more prevalent during the Archean further suggests that such systems may have played a role in the origin of life. We present the first mathematical models of seafloor hydrothermal systems driven by heat released upon serpentinization of peridotite. We assume seawater circulates through a major crack network in the host-peridotite and that cooling of the host-rock leads to the formation of microcracks through which the fluid infiltrates. Reaction of the fluid in microcracks with the host rock results in serpentinization and the heat released upon serpentinization is transported to the seafloor by the fluid circulating in the main crack network. The temperature and heat output of the resulting hydrothermal system is a function of the main network permeability and the rate at which the serpentinization reaction proceeds via diffusion and propagation of the microcracks. Although the temperature of such a system can be quite variable, vent temperatures between 10° C and 100° C are likely for typical crustal parameters.

Study on fracturing flowback fluid treatment technology for shale gas in Yangzhou

NASA Astrophysics Data System (ADS)

Shi, Shengwei; Du, Jiajia; Kang, Dingyu; Chen, Xinjian; Qu, Chengtun; Yu, Tao

2018-02-01

Shale gas fracturing flowback fluid has the characteristics of high viscosity, large displacement, complex components and difficult to deal with. Therefore, it is of great significance for environmental protection to treat and reuse it. In this paper, Yangzhou shale gas is taken as an object to study the treatment of shale gas fracturing flowback fluid. The results shown that the viscosity of the fracturing flowback fluid before treatment was 16.75mPa·s, and when the pH was adjusted to 3.5, with Cerium(III) sulfate and ferrous sulfate as catalyst and the dosage were 60mg/L and 120 mg/L respectively, and hydrogen peroxide dosage was 0.5%, the viscosity of fracturing folwback fluid was reduced from 16.75mPa·s to 1.97mPa·s After the oxidation treatment, adjusting pH to 7.5, and treating it with inorganic flocculant and organic flocculant, the water quality met the reinjection requirement of the average air permeability of less than or equal to 0.01 μm2.

Evaluation of Mobil OCTGAIN{trademark} technology for the manufacture of reformulated gasoline via LP modeling

DOE Office of Scientific and Technical Information (OSTI.GOV)

Poddar, S.K.; Chum, K.; Ragsdale, R.

1995-09-01

Sulfur and olefins content of gasoline come primarily from the cat-cracked blendstock. Therefore hydrotreating cat cracked naphtha is a straight forward approach to reduce sulfur and olefin contents of gasoline and thereby reduce auto exhaust emission. However, this approach reduces the Octane number of gasoline which requires addition of Octane enhancer like MTBE to meet the stringent requirement of 1990 Clean Air Act Amendments and to produce Reformulated Gasoline (RFG). The paper examines the economic incentives of an innovative process technology which was developed and commercialized by Mobil known as OCTGAIN. The process utilizes fixed bed low pressure hardware andmore » uses a Mobil proprietary catalyst system to produce catalytically cracked (CC) gasoline component with thorough desulfurization and olefin reduction and practically no loss in Octane number. The economic evaluation of the OCTGAIN technology was conducted with Bechtel`s proprietary linear programming software, Process Industry Modeling System by introducing an OCTGAIN process block to a typical PADD-3 refinery configuration for gasoline production and satisfying RFG specifications. The results of the evaluation which involved twenty case studies, show that within the limitations of the study scope, the introduction of OCTGAIN technology creates a definite economic incentive over conventional hydrofinishing of CC naphtha. The profitability of OCTGAIN technology is dependent on the aromatics component of the gasoline pool. The economic advantage of OCTGAIN technology is realized primarily by higher production of premium gasoline and the ability to process lower cost high sulfur crude. The process also allows a better utilization of the FCCU and hydrocracker, if the refinery operation permits.« less

75 FR 39251 - Control of Air Pollution From New Motor Vehicles: Announcement of Public Workshop for Heavy-Duty...

Federal Register 2010, 2011, 2012, 2013, 2014

2010-07-08

...A public workshop is being held to discuss the operation of heavy-duty engines equipped with selective catalyst reduction (SCR). EPA will be reviewing its policies regarding the operation of SCR- equipped heavy-duty diesel engines without diesel exhaust fluid (DEF), with improper DEF, or when tampering (or some other defect in the SCR system) is detected.

Single crystal growth of Ga3Ni2 by the Czochralski method

NASA Astrophysics Data System (ADS)

Wencka, Magdalena; Pillaca, Mirtha; Gille, Peter

2016-09-01

Intermetallic compounds have proved to be interesting alternatives to heterogeneous catalysts prepared from pure noble metals or their alloys. As to study their intrinsic properties, to determine the crystalline structures of specific surfaces and finally to understand elementary processes of heterogeneous catalysis, single crystals of these intermetallics are needed. Inspired by the recent discovery of Ga-Ni catalysts for carbon dioxide reduction to methanol, we have grown for the first time cm3-size single crystals of trigonal Ga3Ni2. We report in detail on the synthesis and Czochralski growth from high-temperature solution using Ga as native solvent. Inclusion formation of Ga-rich fluid proved to be the most severe problem that was minimized by using an extremely low pulling rate down to 25 μm/h.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lucia M. Petkovic; Daniel M. Ginosar

Since the year 2000, the United States Patent and Trademark Office (USPTO) has granted a dozen patents for inventions related to methane dehydroaromatization processes. One of them was granted to UOP LLC (Des Plaines). It relates to a catalyst composition and preparation method. Two patents were granted to Conoco Phillips Company (Houston, TX). One was aimed at securing a process and operating conditions for methane aromatization. The other was aimed at securing a process that may be integrated with separation of wellhead fluids and blending of the aromatics produced from the gas with the crude. Nine patents were granted tomore » ExxonMobil Chemical Patents Inc. (Houston, TX). Most of these were aimed at securing a dehydroaromatization process where methane-containing feedstock moves counter currently to a particulate catalyst. The coked catalyst is heated or regenerated either in the reactor, by cyclic operation, or in annex equipment, and returned to the reactor. The reactor effluent stream may be separated in its main components and used or recycled as needed. A brief summary of those inventions is presented in this review.« less

Fluid Structure Interaction Effects on Composites Under Low Velocity Impact

DTIC Science & Technology

2012-06-01

Nanotubes ( MWCNTs ) and the second had no reinforcements at the interface layer in front of the pre-cracks. Output from both tests was recorded using...these samples were tested. The first was reinforced with Multi-Walled Carbon Nanotubes ( MWCNTs ) and the second had no reinforcements at the interface...Ethyl Ketone Peroxide MWCNT Multi-Walled Carbon Nanotube VARTM Vacuum-Assisted Resin Transfer Molding xiv THIS PAGE INTENTIONALLY LEFT BLANK

Introduction: energy and the subsurface.

PubMed

Christov, Ivan C; Viswanathan, Hari S

2016-10-13

This theme issue covers topics at the forefront of scientific research on energy and the subsurface, ranging from carbon dioxide (CO2) sequestration to the recovery of unconventional shale oil and gas resources through hydraulic fracturing. As such, the goal of this theme issue is to have an impact on the scientific community, broadly, by providing a self-contained collection of articles contributing to and reviewing the state-of-the-art of the field. This collection of articles could be used, for example, to set the next generation of research directions, while also being useful as a self-study guide for those interested in entering the field. Review articles are included on the topics of hydraulic fracturing as a multiscale problem, numerical modelling of hydraulic fracture propagation, the role of computational sciences in the upstream oil and gas industry and chemohydrodynamic patterns in porous media. Complementing the reviews is a set of original research papers covering growth models for branched hydraulic crack systems, fluid-driven crack propagation in elastic matrices, elastic and inelastic deformation of fluid-saturated rock, reaction front propagation in fracture matrices, the effects of rock mineralogy and pore structure on stress-dependent permeability of shales, topographic viscous fingering and plume dynamics in porous media convection.This article is part of the themed issue 'Energy and the subsurface'. © 2016 The Author(s).

Effect of Carbon in the Dielectric Fluid and Workpieces on the Characteristics of Recast Layers Machined by Electrical Discharge Machining

NASA Astrophysics Data System (ADS)

Muttamara, Apiwat; Kanchanomai, Chaosuan

2016-06-01

Electrical discharge machining (EDM) is a popular non-traditional machining technique that is usually performed in kerosene. Carbon from the kerosene is mixed into the recast layer during EDM, increasing its hardness. EDM can be performed in deionized water, which causes decarburization. We studied the effects of carbon in the dielectric fluid and workpiece on the characteristics of recast layers. Experiments were conducted using gray cast iron and mild steel workpieces in deionized water or kerosene under identical operating conditions. Scanning electron microscopy revealed that the recast layer formed on gray iron was rougher than that produced on mild steel. Moreover, the dispersion of graphite flakes in the gray iron seemed to cause subsurface cracks, even when EDM was performed in deionized water. Dendritic structures and iron carbides were found in the recast layer of gray iron treated in deionized water. Kerosene caused more microcracks to form and increased surface roughness compared with deionized water. The microcrack length per unit area of mild steel treated in deionized water was greater than that treated in kerosene, but the cracks formed in kerosene were wider. The effect of the diffusion of carbon during cooling on the characteristics of the recast layer was discussed.

Introduction: energy and the subsurface

PubMed Central

Viswanathan, Hari S.

2016-01-01

This theme issue covers topics at the forefront of scientific research on energy and the subsurface, ranging from carbon dioxide (CO2) sequestration to the recovery of unconventional shale oil and gas resources through hydraulic fracturing. As such, the goal of this theme issue is to have an impact on the scientific community, broadly, by providing a self-contained collection of articles contributing to and reviewing the state-of-the-art of the field. This collection of articles could be used, for example, to set the next generation of research directions, while also being useful as a self-study guide for those interested in entering the field. Review articles are included on the topics of hydraulic fracturing as a multiscale problem, numerical modelling of hydraulic fracture propagation, the role of computational sciences in the upstream oil and gas industry and chemohydrodynamic patterns in porous media. Complementing the reviews is a set of original research papers covering growth models for branched hydraulic crack systems, fluid-driven crack propagation in elastic matrices, elastic and inelastic deformation of fluid-saturated rock, reaction front propagation in fracture matrices, the effects of rock mineralogy and pore structure on stress-dependent permeability of shales, topographic viscous fingering and plume dynamics in porous media convection. This article is part of the themed issue ‘Energy and the subsurface’. PMID:27597784