40 CFR 60.107 - Reporting and recordkeeping requirements.

Code of Federal Regulations, 2011 CFR

2011-07-01

... in the gases discharged to the atmosphere from any fluid catalytic cracking unit catalyst regenerator... concurrent with a startup, shutdown, or malfunction of the fluid catalytic cracking unit or control system... cracking unit catalyst regenerator for which the owner or operator seeks to comply with § 60.104(b)(1) is...

40 CFR 60.107 - Reporting and recordkeeping requirements.

Code of Federal Regulations, 2010 CFR

2010-07-01

... in the gases discharged to the atmosphere from any fluid catalytic cracking unit catalyst regenerator... concurrent with a startup, shutdown, or malfunction of the fluid catalytic cracking unit or control system... cracking unit catalyst regenerator for which the owner or operator seeks to comply with § 60.104(b)(1) is...

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.

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-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

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

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.

Catalytic cracking of model compounds of bio-oil over HZSM-5 and the catalyst deactivation.

PubMed

Chen, Guanyi; Zhang, Ruixue; Ma, Wenchao; Liu, Bin; Li, Xiangping; Yan, Beibei; Cheng, Zhanjun; Wang, Tiejun

2018-08-01

The catalytic cracking upgrading reactions over HZSM-5 of different model compounds of bio-oil have been studied with a self-designed fluid catalytic cracking (FCC) equipment. Typical bio-oil model compounds, such as acetic acid, guaiacol, n-heptane, acetol and ethyl acetate, were chosen to study the products distribution, reaction pathway and deactivation of catalysts. The results showed: C 6 -C 8 aromatic hydrocarbons, C 2 -C 4 olefins, C 1 -C 5 alkanes, CO and CO 2 were the main products, and the selectivity of olefins was: ethylene>propylene>butylene. Catalyst characterization methods, such as FI-IR, TG-TPO and Raman, were used to study the deactivation mechanism of catalysts. According to the catalyst characterization results, a catalyst deactivation mechanism was proposed as follows: Firstly, the precursor which consisted of a large number of long chain saturated aliphatic hydrocarbons and a small amount CC of aromatics formed on the catalyst surface. Then the active sites of catalysts had been covered, the coke type changed from thermal coke to catalytic coke and gradually blocked the channels of the molecular sieve, which accelerated the deactivation of catalyst. Copyright © 2018 Elsevier B.V. All rights reserved.

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.

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

40 CFR 60.100 - Applicability, designation of affected facility, and reconstruction.

Code of Federal Regulations, 2013 CFR

2013-07-01

... petroleum refineries: fluid catalytic cracking unit catalyst regenerators, fuel gas combustion devices, and... petroleum refinery. (b) Any fluid catalytic cracking unit catalyst regenerator or fuel gas combustion device... regenerator under paragraph (b) of this section which commences construction, reconstruction, or modification...

40 CFR 60.100 - Applicability, designation of affected facility, and reconstruction.

Code of Federal Regulations, 2014 CFR

2014-07-01

... petroleum refineries: fluid catalytic cracking unit catalyst regenerators, fuel gas combustion devices, and... petroleum refinery. (b) Any fluid catalytic cracking unit catalyst regenerator or fuel gas combustion device... regenerator under paragraph (b) of this section which commences construction, reconstruction, or modification...

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.

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.

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

Fluid catalytic cracking: recent developments on the grand old lady of zeolite catalysis.

PubMed

Vogt, E T C; Weckhuysen, B M

2015-10-21

Fluid catalytic cracking (FCC) is one of the major conversion technologies in the oil refinery industry. FCC currently produces the majority of the world's gasoline, as well as an important fraction of propylene for the polymer industry. In this critical review, we give an overview of the latest trends in this field of research. These trends include ways to make it possible to process either very heavy or very light crude oil fractions as well as to co-process biomass-based oxygenates with regular crude oil fractions, and convert these more complex feedstocks in an increasing amount of propylene and diesel-range fuels. After providing some general background of the FCC process, including a short history as well as details on the process, reactor design, chemical reactions involved and catalyst material, we will discuss several trends in FCC catalysis research by focusing on ways to improve the zeolite structure stability, propylene selectivity and the overall catalyst accessibility by (a) the addition of rare earth elements and phosphorus, (b) constructing hierarchical pores systems and (c) the introduction of new zeolite structures. In addition, we present an overview of the state-of-the-art micro-spectroscopy methods for characterizing FCC catalysts at the single particle level. These new characterization tools are able to explain the influence of the harsh FCC processing conditions (e.g. steam) and the presence of various metal poisons (e.g. V, Fe and Ni) in the crude oil feedstocks on the 3-D structure and accessibility of FCC catalyst materials.

Fluid catalytic cracking: recent developments on the grand old lady of zeolite catalysis

PubMed Central

2015-01-01

Fluid catalytic cracking (FCC) is one of the major conversion technologies in the oil refinery industry. FCC currently produces the majority of the world's gasoline, as well as an important fraction of propylene for the polymer industry. In this critical review, we give an overview of the latest trends in this field of research. These trends include ways to make it possible to process either very heavy or very light crude oil fractions as well as to co-process biomass-based oxygenates with regular crude oil fractions, and convert these more complex feedstocks in an increasing amount of propylene and diesel-range fuels. After providing some general background of the FCC process, including a short history as well as details on the process, reactor design, chemical reactions involved and catalyst material, we will discuss several trends in FCC catalysis research by focusing on ways to improve the zeolite structure stability, propylene selectivity and the overall catalyst accessibility by (a) the addition of rare earth elements and phosphorus, (b) constructing hierarchical pores systems and (c) the introduction of new zeolite structures. In addition, we present an overview of the state-of-the-art micro-spectroscopy methods for characterizing FCC catalysts at the single particle level. These new characterization tools are able to explain the influence of the harsh FCC processing conditions (e.g. steam) and the presence of various metal poisons (e.g. V, Fe and Ni) in the crude oil feedstocks on the 3-D structure and accessibility of FCC catalyst materials. PMID:26382875

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

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.

Particles of spilled oil-absorbing carbon in contact with water

DOEpatents

Muradov, Nazim [Melbourne, FL

2011-03-29

Hydrogen generator coupled to or integrated with a fuel cell for portable power applications. Hydrogen is produced via thermocatalytic decomposition (cracking, pyrolysis) of hydrocarbon fuels in oxidant-free environment. The apparatus can utilize a variety of hydrocarbon fuels, including natural gas, propane, gasoline, kerosene, diesel fuel, crude oil (including sulfurous fuels). The hydrogen-rich gas produced is free of carbon oxides or other reactive impurities, so it could be directly fed to any type of a fuel cell. The catalysts for hydrogen production in the apparatus are carbon-based or metal-based materials and doped, if necessary, with a sulfur-capturing agent. Additionally disclosed are two novel processes for the production of two types of carbon filaments, and a novel filamentous carbon product. Carbon particles with surface filaments having a hydrophobic property of oil film absorption, compositions of matter containing those particles, and a system for using the carbon particles for cleaning oil spills.

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

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.

Carbonate fuel cell matrix

DOEpatents

Farooque, Mohammad; Yuh, Chao-Yi

1996-01-01

A carbonate fuel cell matrix comprising support particles and crack attenuator particles which are made platelet in shape to increase the resistance of the matrix to through cracking. Also disclosed is a matrix having porous crack attenuator particles and a matrix whose crack attenuator particles have a thermal coefficient of expansion which is significantly different from that of the support particles, and a method of making platelet-shaped crack attenuator particles.

Carbonate fuel cell matrix

DOEpatents

Farooque, M.; Yuh, C.Y.

1996-12-03

A carbonate fuel cell matrix is described comprising support particles and crack attenuator particles which are made platelet in shape to increase the resistance of the matrix to through cracking. Also disclosed is a matrix having porous crack attenuator particles and a matrix whose crack attenuator particles have a thermal coefficient of expansion which is significantly different from that of the support particles, and a method of making platelet-shaped crack attenuator particles. 8 figs.

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

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.

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

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.

Fracture mechanisms of glass particles under dynamic compression

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

Parab, Niranjan D.; Guo, Zherui; Hudspeth, Matthew C.

2017-08-01

In this study, dynamic fracture mechanisms of single and contacting spherical glass particles were observed using high speed synchrotron X-ray phase contrast imaging. A modified Kolsky bar setup was used to apply controlled dynamic compressive loading on the soda-lime glass particles. Four different configurations of particle arrangements with one, two, three, and five particles were studied. In single particle experiments, cracking initiated near the contact area between the particle and the platen, subsequently fragmenting the particle in many small sub-particles. In multi-particle experiments, a crack was observed to initiate from the point just outside the contact area between two particles.more » The initiated crack propagated at an angle to the horizontal loading direction, resulting in separation of a fragment. However, this fragment separation did not affect the ability of the particle to withstand further contact loading. On further compression, large number of cracks initiated in the particle with the highest number of particle-particle contacts near one of the particle-particle contacts. The initiated cracks roughly followed the lines joining the contact points. Subsequently, the initiated cracks along with the newly developed sub-cracks bifurcated rapidly as they propagated through the particle and fractured the particle explosively into many small fragments, leaving the other particles nearly intact.« less

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.

Heterogeneous kinetic modeling of the catalytic conversion of cycloparaffins

NASA Astrophysics Data System (ADS)

Al-Sabawi, Mustafa N.

The limited availability of high value light hydrocarbon feedstocks along with the rise in crude prices has resulted in the international recognition of the vast potential of Canada's oil sands. With the recent expansion of Canadian bitumen production come, however, many technical challenges, one of which is the significant presence of aromatics and cycloparaffins in bitumen-derived feedstocks. In addition to their negative environmental impact, aromatics limit fluid catalytic cracking (FCC) feedstock conversion, decrease the yield and quality of valuable products such as gasoline and middle distillates, increase levels of polyaromatic hydrocarbons prone to form coke on the catalyst, and ultimately compromise the FCC unit performance. Although cycloparaffins do not have such negative impacts, they are precursors of aromatics as they frequently undergo hydrogen transfer reactions. However, cycloparaffin cracking chemistry involves other competing reactions that are complex and need much investigation. This dissertation provides insights and understanding of the fundamentals of the catalytic cracking of cycloparaffins using carefully selected model compounds such as methylcyclohexane (MCH) and decalin. Thermal and catalytic cracking of these cycloparaffins on FCC-type catalysts are carried out using the CREC Riser Simulator under operating conditions similar to those of the industrial FCC units in terms of temperature, reaction time, reactant partial pressure and catalyst-to-hydrocarbon ratio. The crystallite size of the supported zeolites is varied between 0.4 and 0.9 microns, with both activity and selectivity being monitored. Catalytic conversions ranged between 4 to 16 wt% for MCH and between 8 to 27 wt% for decalin. Reaction pathways of cycloparaffins are determined, and these include ring-opening, protolytic cracking, isomerization, hydrogen transfer and transalkylation. The yields and selectivities of over 60 and 140 products, formed during MCH and decalin catalytic conversions respectively, are reported. Using these data, heterogeneous kinetic models accounting for intracrystallite molecular transport, adsorption and thermal and catalytic cracking of both cycloparaffin reactants are established. Results show that undesirable hydrogen transfer reactions are more pronounced and selectively favoured against other reactions at lower reaction temperatures, while the desirable ring-opening and cracking reactions predominate at the higher reaction temperatures. Moreover, results of the present work show that while crystallite size may have an effect on the overall conversion in some situations, there is a definite effect on the selectivity of products obtained during the cracking of MCH and decalin and the cracking of MCH in a mixture with co-reactants such as 1,3,5-triisopropylbenzene. Keywords. cycloparaffins, naphthenes, fluid catalytic cracking, kinetic modeling, Y-zeolites, diffusion, adsorption, ring-opening, hydrogen transfer, catalyst selectivity.

Development and Characterization of Embedded Sensory Particles Using Multi-Scale 3D Digital Image Correlation

NASA Technical Reports Server (NTRS)

Cornell, Stephen R.; Leser, William P.; Hochhalter, Jacob D.; Newman, John A.; Hartl, Darren J.

2014-01-01

A method for detecting fatigue cracks has been explored at NASA Langley Research Center. Microscopic NiTi shape memory alloy (sensory) particles were embedded in a 7050 aluminum alloy matrix to detect the presence of fatigue cracks. Cracks exhibit an elevated stress field near their tip inducing a martensitic phase transformation in nearby sensory particles. Detectable levels of acoustic energy are emitted upon particle phase transformation such that the existence and location of fatigue cracks can be detected. To test this concept, a fatigue crack was grown in a mode-I single-edge notch fatigue crack growth specimen containing sensory particles. As the crack approached the sensory particles, measurements of particle strain, matrix-particle debonding, and phase transformation behavior of the sensory particles were performed. Full-field deformation measurements were performed using a novel multi-scale optical 3D digital image correlation (DIC) system. This information will be used in a finite element-based study to determine optimal sensory material behavior and density.

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.

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

Numerical computation of central crack growth in an active particle of electrodes influenced by multiple factors

NASA Astrophysics Data System (ADS)

Zhang, Yuwei; Guo, Zhansheng

2018-03-01

Mechanical degradation, especially fractures in active particles in an electrode, is a major reason why the capacity of lithium-ion batteries fades. This paper proposes a model that couples Li-ion diffusion, stress evolution, and damage mechanics to simulate the growth of central cracks in cathode particles (LiMn2O4) by an extended finite element method by considering the influence of multiple factors. The simulation shows that particles are likely to crack at a high discharge rate, when the particle radius is large, or when the initial central crack is longer. It also shows that the maximum principal tensile stress decreases and cracking becomes more difficult when the influence of crack surface diffusion is considered. The fracturing process occurs according to the following stages: no crack growth, stable crack growth, and unstable crack growth. Changing the charge/discharge strategy before unstable crack growth sets in is beneficial to prevent further capacity fading during electrochemical cycling.

Oxidation catalysts on alkaline earth supports

DOEpatents

Mohajeri, Nahid

2017-03-21

An oxidation catalyst includes a support including particles of an alkaline earth salt, and first particles including a palladium compound on the support. The oxidation catalyst can also include precious metal group (PMG) metal particles in addition to the first particles intermixed together on the support. A gas permeable polymer that provides a continuous phase can completely encapsulate the particles and the support. The oxidation catalyst may be used as a gas sensor, where the first particles are chemochromic particles.

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

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.

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.

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

Laboratory Production of Biofuels and Biochemicals from a Rapeseed Oil through Catalytic Cracking Conversion.

PubMed

Ng, Siauw H; Shi, Yu; Heshka, Nicole E; Zhang, Yi; Little, Edward

2016-09-02

The work is based on a reported study which investigates the processability of canola oil (bio-feed) in the presence of bitumen-derived heavy gas oil (HGO) for production of transportation fuels through a fluid catalytic cracking (FCC) route. Cracking experiments are performed with a fully automated reaction unit at a fixed weight hourly space velocity (WHSV) of 8 hr(-1), 490-530 °C, and catalyst/oil ratios of 4-12 g/g. When a feed is in contact with catalyst in the fluid-bed reactor, cracking takes place generating gaseous, liquid, and solid products. The vapor produced is condensed and collected in a liquid receiver at -15 °C. The non-condensable effluent is first directed to a vessel and is sent, after homogenization, to an on-line gas chromatograph (GC) for refinery gas analysis. The coke deposited on the catalyst is determined in situ by burning the spent catalyst in air at high temperatures. Levels of CO2 are measured quantitatively via an infrared (IR) cell, and are converted to coke yield. Liquid samples in the receivers are analyzed by GC for simulated distillation to determine the amounts in different boiling ranges, i.e., IBP-221 °C (gasoline), 221-343 °C (light cycle oil), and 343 °C+ (heavy cycle oil). Cracking of a feed containing canola oil generates water, which appears at the bottom of a liquid receiver and on its inner wall. Recovery of water on the wall is achieved through washing with methanol followed by Karl Fischer titration for water content. Basic results reported include conversion (the portion of the feed converted to gas and liquid product with a boiling point below 221 °C, coke, and water, if present) and yields of dry gas (H2-C2's, CO, and CO2), liquefied petroleum gas (C3-C4), gasoline, light cycle oil, heavy cycle oil, coke, and water, if present.

Self-Sealing Cementitious Materials by Using Water-Swelling Rubber Particles

PubMed Central

Lv, Leyang; Schlangen, Erik; Xing, Feng

2017-01-01

Water ingress into cracked concrete structures is a serious problem, as it can cause leakage and reinforcement corrosion and thus reduce functionality and safety of the structures. In this study, the application of water-swelling rubber particles for providing the cracked concrete a self-sealing function was developed. The feasibility of applying water-swelling rubber particles and the influence of incorporating water-swelling rubber particles on the mechanical properties of concrete was investigated. The self-sealing efficiency of water-swelling rubber particles with different content and particle size was quantified through a permeability test. The sealing effect of the water swelling rubber particles was monitored by X-ray computed tomography. The experimental results show that, by using 6% of these water swelling rubber particles as a replacement of aggregates in concrete, up to 64% and 61% decrease of water permeability was realized for 0.7 mm and 1.0 mm cracks. Furthermore, when the concrete cracks, the water swelling rubber particles can act as a crack bridging filler, preventing the crack from fully separating the specimens in two pieces. PMID:28829384

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

Colloidal polymer particles as catalyst carriers and phase transfer agents in multiphasic hydroformylation reactions.

PubMed

Peral, D; Stehl, D; Bibouche, B; Yu, H; Mardoukh, J; Schomäcker, R; Klitzing, R von; Vogt, D

2018-03-01

Colloidal particles have been used to covalently bind ligands for the heterogenization of homogeneous catalysts. The replacement of the covalent bonds by electrostatic interactions between particles and the catalyst could preserve the selectivity of a truly homogeneous catalytic process. Functionalized polymer particles with trimethylammonium moieties, dispersed in water, with a hydrophobic core and a hydrophilic shell have been synthesized by emulsion polymerization and have been thoroughly characterized. The ability of the particles with different monomer compositions to act as catalyst carriers has been studied. Finally, the colloidal dispersions have been applied as phase transfer agents in the multiphasic rhodium-catalyzed hydroformylation of 1-octene. The hydrodynamic radius of the particles has been shown to be around 100 nm, and a core-shell structure could be observed by atomic force microscopy. The polymer particles were proven to act as carriers for the water-soluble hydroformylation catalyst, due to electrostatic interaction between the functionalized particles bearing ammonium groups and the sulfonated ligands of the catalyst. The particles were stable under the hydroformylation conditions and the aqueous catalyst phase could be recycled three times. Copyright © 2017 Elsevier Inc. All rights reserved.

Modeling crack growth during Li insertion in storage particles using a fracture phase field approach

NASA Astrophysics Data System (ADS)

Klinsmann, Markus; Rosato, Daniele; Kamlah, Marc; McMeeking, Robert M.

2016-07-01

Fracture of storage particles is considered to be one of the major reasons for capacity fade and increasing power loss in many commercial lithium ion batteries. The appearance of fracture and cracks in the particles is commonly ascribed to mechanical stress, which evolves from inhomogeneous swelling and shrinkage of the material when lithium is inserted or extracted. Here, a coupled model of lithium diffusion, mechanical stress and crack growth using a phase field method is applied to investigate how the formation of cracks depends on the size of the particle and the presence or absence of an initial crack, as well as the applied flux at the boundary. The model shows great versatility in that it is free of constraints with respect to particle geometry, dimension or crack path and allows simultaneous observation of the evolution of lithium diffusion and crack growth. In this work, we focus on the insertion process. In particular, we demonstrate the presence of intricate fracture phenomena, such as, crack branching or complete breakage of storage particles within just a single half cycle of lithium insertion, a phenomenon that was only speculated about before.

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

Overcoming the Instability of Nanoparticle-Based Catalyst Films in Alkaline Electrolyzers by using Self-Assembling and Self-Healing Films.

PubMed

Barwe, Stefan; Masa, Justus; Andronescu, Corina; Mei, Bastian; Schuhmann, Wolfgang; Ventosa, Edgar

2017-07-10

Engineering stable electrodes using highly active catalyst nanopowders for electrochemical water splitting remains a challenge. We report an innovative and general approach for attaining highly stable catalyst films with self-healing capability based on the in situ self-assembly of catalyst particles during electrolysis. The catalyst particles are added to the electrolyte forming a suspension that is pumped through the electrolyzer. Particles with negatively charged surfaces stick onto the anode, while particles with positively charged surfaces stick to the cathode. The self-assembled catalyst films have self-healing properties as long as sufficient catalyst particles are present in the electrolyte. The proof-of-concept was demonstrated in a non-zero gap alkaline electrolyzer using NiFe-LDH and Ni x B catalyst nanopowders for anode and cathode, respectively. Steady cell voltages were maintained for at least three weeks during continuous electrolysis at 50-100 mA cm -2 . © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

Fracture of a Brittle-Particle Ductile Matrix Composite with Applications to a Coating System

NASA Astrophysics Data System (ADS)

Bianculli, Steven J.

In material systems consisting of hard second phase particles in a ductile matrix, failure initiating from cracking of the second phase particles is an important failure mechanism. This dissertation applies the principles of fracture mechanics to consider this problem, first from the standpoint of fracture of the particles, and then the onset of crack propagation from fractured particles. This research was inspired by the observation of the failure mechanism of a commercial zinc-based anti-corrosion coating and the analysis was initially approached as coatings problem. As the work progressed it became evident that failure mechanism was relevant to a broad range of composite material systems and research approach was generalized to consider failure of a system consisting of ellipsoidal second phase particles in a ductile matrix. The starting point for the analysis is the classical Eshelby Problem, which considered stress transfer from the matrix to an ellipsoidal inclusion. The particle fracture problem is approached by considering cracks within particles and how they are affected by the particle/matrix interface, the difference in properties between the particle and matrix, and by particle shape. These effects are mapped out for a wide range of material combinations. The trends developed show that, although the particle fracture problem is very complex, the potential for fracture among a range of particle shapes can, for certain ranges in particle shape, be considered easily on the basis of the Eshelby Stress alone. Additionally, the evaluation of cracks near the curved particle/matrix interface adds to the existing body of work of cracks approaching bi-material interfaces in layered material systems. The onset of crack propagation from fractured particles is then considered as a function of particle shape and mismatch in material properties between the particle and matrix. This behavior is mapped out for a wide range of material combinations. The final section of this dissertation qualitatively considers an approach to determine critical particle sizes, below which crack propagation will not occur for a coating system that exhibited stable cracks in an interfacial layer between the coating and substrate.

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.

Self-healing of cracks formed in Silicon-Aluminum anodes electrochemically cycled at high lithiation rates

NASA Astrophysics Data System (ADS)

Bhattacharya, Sandeep; Alpas, Ahmet T.

2016-10-01

Lithiation-induced volume changes in Si result in fracture and fragmentation of Si anodes in Li-ion batteries. This paper reports the self-healing behaviour of cracks observed in micron-sized Si particles dispersed in a ductile Al matrix of a Si-Al electrode electrochemically cycled vs. Li/Li+ using a high lithiation rate of 15.6 C. Cross-sectional high-resolution transmission electron microscopy and Raman spectroscopy revealed that an amorphous layer with a depth up to ∼100 nm was formed at the surface of Si particles. In-situ optical microscopy performed during electrochemical experiments revealed development of cracks in Si particles as the voltage decreased to 0.02 V during lithiation. Self-healing of cracks in Si particles occurred in two steps: i) arresting of the crack growth at the Si/Al interface as the surrounding Al matrix had a higher fracture toughness and thus acted as a barrier to crack propagation, and ii) closure of cracks due to compressive stresses applied to the crack faces by the amorphous zones formed on each side of the crack paths.

Method for regeneration and activity improvement of syngas conversion catalyst

DOEpatents

Lucki, Stanley J.; Brennan, James A.

1980-01-01

A method is disclosed for the treatment of single particle iron-containing syngas (synthes.s gas) conversion catalysts comprising iron, a crystalline acidic aluminosilicate zeolite having a silica to alumina ratio of at least 12, a pore size greater than about 5 Angstrom units and a constraint index of about 1-12 and a matrix. The catalyst does not contain promoters and the treatment is applicable to either the regeneration of said spent single particle iron-containing catalyst or for the initial activation of fresh catalyst. The treatment involves air oxidation, hydrogen reduction, followed by a second air oxidation and contact of the iron-containing single particle catalyst with syngas prior to its use for the catalytic conversion of said syngas. The single particle iron-containing catalysts are prepared from a water insoluble organic iron compound.

Doped palladium containing oxidation catalysts

DOEpatents

Mohajeri, Nahid

2014-02-18

A supported oxidation catalyst includes a support having a metal oxide or metal salt, and mixed metal particles thereon. The mixed metal particles include first particles including a palladium compound, and second particles including a precious metal group (PMG) metal or PMG metal compound, wherein the PMG metal is not palladium. The oxidation catalyst may also be used as a gas sensor.

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

Effect of Silica Particle Size on Texture, Structure, and Catalytic Performance of Cu/SiO2 Catalysts for Glycerol Hydrogenolysis

NASA Astrophysics Data System (ADS)

Qi, Ye Tong; Zhe, Chen Hong; Ning, Xiang

2018-03-01

The influences of carrier particle sizes of Cu/SiO2 catalysts for hydrogenolysis of glycerol were studied use mono-dispersed silica as models. Catalysts were prepared by precipitation method with the average size of the mono-dispersed silica supports varying of 10, 20, and 90 nm. Characterization of the catalysts show that the physical properties such as pore volume and BET surface area of the catalysts were largely affected by the carrier particle size of silica. However, the copper dispersion of the three samples were similar. XPS patterns show a difference in the chemical states of copper species, small carrier particle size induced formation of copper phyllosilicate, which benefits on the stability of copper species in reaction. The overall activity in the reaction of glycerol hydrogenolysis shows a correlation with the carrier particle size. The small carrier particles prevent the copper species from aggregation thus such catalysts exhibit good catalytic activity and stability.

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

Photoreactor with self-contained photocatalyst recapture

DOEpatents

Gering, Kevin L.

2004-12-07

A system for the continuous use and recapture of a catalyst in liquid, comprising: a generally vertical reactor having a reaction zone with generally downwardly flowing liquid, and a catalyst recovery chamber adjacent the reaction zone containing a catalyst consisting of buoyant particles. The liquid in the reaction zone flows downward at a rate which exceeds the speed of upward buoyant migration of catalyst particles in the liquid, whereby catalyst particles introduced into the liquid in the reaction zone are drawn downward with the liquid. A slow flow velocity flotation chamber disposed below the reaction zone is configured to recapture the catalyst particles and allow them to float back into the catalyst recovery chamber for recycling into the reaction zone, rather than being swept downstream. A novel 3-dimensionally adjustable solar reflector directs light into the reaction zone to induce desired photocatalytic reactions within the liquid in the reaction zone.

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.

Residual stress and crack initiation in laser clad composite layer with Co-based alloy and WC + NiCr

NASA Astrophysics Data System (ADS)

Lee, Changmin; Park, Hyungkwon; Yoo, Jaehong; Lee, Changhee; Woo, WanChuck; Park, Sunhong

2015-08-01

Although laser cladding process has been widely used to improve the wear and corrosion resistance, there are unwanted cracking issues during and/or after laser cladding. This study investigates the tendency of Co-based WC + NiCr composite layers to cracking during the laser cladding process. Residual stress distributions of the specimen are measured using neutron diffraction and elucidate the correlation between the residual stress and the cracking in three types of cylindrical specimens; (i) no cladding substrate only, (ii) cladding with 100% stellite#6, and (iii) cladding with 55% stellite#6 and 45% technolase40s. The microstructure of the clad layer was composed of Co-based dendrite and brittle eutectic phases at the dendritic boundaries. And WC particles were distributed on the matrix forming intermediate composition region by partial melting of the surface of particles. The overlaid specimen exhibited tensile residual stress, which was accumulated through the beads due to contraction of the coating layer generated by rapid solidification, while the non-clad specimen showed compressive. Also, the specimen overlaid with 55 wt% stellite#6 and 45 wt% technolase40s showed a tensile stress higher than the specimen overlaid with 100% stellite#6 possibly, due to the difference between thermal expansion coefficients of the matrix and WC particles. Such tensile stresses can be potential driving force to provide an easy crack path ways for large brittle fractures combined with the crack initiation sites such as the fractured WC particles, pores and solidification cracks. WC particles directly caused clad cracks by particle fracture under the tensile stress. The pores and solidification cracks also affected as initiation sites and provided an easy crack path ways for large brittle fractures.

Research on a Lamb Wave and Particle Filter-Based On-Line Crack Propagation Prognosis Method.

PubMed

Chen, Jian; Yuan, Shenfang; Qiu, Lei; Cai, Jian; Yang, Weibo

2016-03-03

Prognostics and health management techniques have drawn widespread attention due to their ability to facilitate maintenance activities based on need. On-line prognosis of fatigue crack propagation can offer information for optimizing operation and maintenance strategies in real-time. This paper proposes a Lamb wave-particle filter (LW-PF)-based method for on-line prognosis of fatigue crack propagation which takes advantages of the possibility of on-line monitoring to evaluate the actual crack length and uses a particle filter to deal with the crack evolution and monitoring uncertainties. The piezoelectric transducers (PZTs)-based active Lamb wave method is adopted for on-line crack monitoring. The state space model relating to crack propagation is established by the data-driven and finite element methods. Fatigue experiments performed on hole-edge crack specimens have validated the advantages of the proposed method.

Design of slurry bubble column reactors: novel technique for optimum catalyst size selection contractual origin of the invention

DOEpatents

Gamwo, Isaac K [Murrysville, PA; Gidaspow, Dimitri [Northbrook, IL; Jung, Jonghwun [Naperville, IL

2009-11-17

A method for determining optimum catalyst particle size for a gas-solid, liquid-solid, or gas-liquid-solid fluidized bed reactor such as a slurry bubble column reactor (SBCR) for converting synthesis gas into liquid fuels considers the complete granular temperature balance based on the kinetic theory of granular flow, the effect of a volumetric mass transfer coefficient between the liquid and the gas, and the water gas shift reaction. The granular temperature of the catalyst particles representing the kinetic energy of the catalyst particles is measured and the volumetric mass transfer coefficient between the gas and liquid phases is calculated using the granular temperature. Catalyst particle size is varied from 20 .mu.m to 120 .mu.m and a maximum mass transfer coefficient corresponding to optimum liquid hydrocarbon fuel production is determined. Optimum catalyst particle size for maximum methanol production in a SBCR was determined to be in the range of 60-70 .mu.m.

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

Mechanical alloying of a hydrogenation catalyst used for the remediation of contaminated compounds

NASA Technical Reports Server (NTRS)

Quinn, Jacqueline W. (Inventor); Geiger, Cherie L. (Inventor); Aitken, Brian S. (Inventor); Clausen, Christian A. (Inventor)

2012-01-01

A hydrogenation catalyst including a base material coated with a catalytic metal is made using mechanical milling techniques. The hydrogenation catalysts are used as an excellent catalyst for the dehalogenation of contaminated compounds and the remediation of other industrial compounds. Preferably, the hydrogenation catalyst is a bimetallic particle including zero-valent metal particles coated with a catalytic material. The mechanical milling technique is simpler and cheaper than previously used methods for producing hydrogenation catalysts.

Mechanical alloying of a hydrogenation catalyst used for the remediation of contaminated compounds

NASA Technical Reports Server (NTRS)

Quinn, Jacqueline W. (Inventor); Aitken, Brian S. (Inventor); Clausen, Christian A. (Inventor); Geiger, Cherie L. (Inventor)

2010-01-01

A hydrogenation catalyst including a base material coated with a catalytic metal is made using mechanical milling techniques. The hydrogenation catalysts are used as an excellent catalyst for the dehalogenation of contaminated compounds and the remediation of other industrial compounds. Preferably, the hydrogenation catalyst is a bimetallic particle including zero-valent metal particles coated with a catalytic material. The mechanical milling technique is simpler and cheaper than previously used methods for producing hydrogenation catalysts.

Bioleaching of metals from spent refinery petroleum catalyst using moderately thermophilic bacteria: effect of particle size.

PubMed

Srichandan, Haragobinda; Singh, Sradhanjali; Pathak, Ashish; Kim, Dong-Jin; Lee, Seoung-Won; Heyes, Graeme

2014-01-01

The present work investigated the leaching potential of moderately thermophilic bacteria in the recovery of metals from spent petroleum catalyst of varying particle sizes. The batch bioleaching experiments were conducted by employing a mixed consortium of moderate thermophilic bacteria at 45°C and by using five different particle sizes (from 45 to >2000 μm) of acetone-washed spent catalyst. The elemental mapping by FESEM confirmed the presence of Al, Ni, V and Mo along with sulfur in the spent catalyst. During bioleaching, Ni (92-97%) and V (81-91%) were leached in higher concentrations, whereas leaching yields of Al (23-38%) were found to be lowest in all particle sizes investigated. Decreasing the particle size from >2000 μm to 45-106 μm caused an increase in leaching yields of metals during initial hours. However, the final metals leaching yields were almost independent of particle sizes of catalyst. Leaching kinetics was observed to follow the diffusion-controlled model showing the linearity more close than the chemical control. The results of the present study suggested that bioleaching using moderate thermophilic bacteria was highly effective in removing the metals from spent catalyst. Moreover, bioleaching can be conducted using spent catalyst of higher particle size (>2000 μm), thus saving the grinding cost and making process attractive for larger scale application.

77 FR 60285 - Airworthiness Directives; The Boeing Company Airplanes

Federal Register 2010, 2011, 2012, 2013, 2014

2012-10-03

... the MLG for chicken- wire cracks, corrosion, and chrome plate distress; repetitive magnetic particle... center axles of the MLG for chicken-wire cracks, corrosion, and chrome plate distress; repetitive... the MLG for chicken- wire cracks, corrosion, and chrome plate distress; do a magnetic particle...

Suppressing Crack Formation in Particulate Systems by Utilizing Capillary Forces

PubMed Central

Schneider, Monica; Maurath, Johannes; Fischer, Steffen B.; Weiß, Moritz; Willenbacher, Norbert; Koos, Erin

2017-01-01

Cracks, formed during the drying of particulate films, can reduce the effectiveness or even render products useless. We present a novel, generic approach to suppress crack formation in thin films made from hard particle suspensions, which are otherwise highly susceptible to cracking, using the capillary force between particles present when a trace amount of an immiscible liquid is added to a suspension. This secondary liquid preserves the particle cohesion, modifying the structure and increasing the drying rate. Crack-free films can be produced at thicknesses much greater than the critical cracking thickness for a suspension without capillary interactions, and even persists after sintering. This capillary suspension strategy is applicable to a broad range of materials including suspensions of metals, semiconductive and ceramic oxides or glassy polymeric particles and can be easily implemented in many industrial processes since it is based on well-established unit operations. Promising fields of application include ceramic foils and printed electronic devices. PMID:28263554

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.

The self-healing composite anticorrosion coating

NASA Astrophysics Data System (ADS)

Yang, Zhao; Wei, Zhang; Le-ping, Liao; Hong-mei, Wang; Wu-jun, Li

Self-healing coatings, which autonomically repair and prevent corrosion of the underlying substrate, are of particular interest for the researchers. In the article, effectiveness of epoxy resin filled microcapsules was investigated for healing of cracks generated in coatings. Microcapsules were prepared by in situ polymerization of urea-formaldehyde resin to form shell over epoxy resindroplets. Characteristics of these capsules were studied by scanning electron microscope (SEM), thermo gravimetric analyzer (TGA) and particle size analyzer. The model system of self-healing antisepsis coating consists of an epoxy resin matrix, 10 wt% microencapsulated healing agent, 2wt% catalyst solution. The self-healing function of this coating system is evaluated through corrosion testing of damaged and healed coated steel samples compared to control samples. Electrochemical testing provides further evidence of passivation of the substrate by self-healing coatings.

Tetraethyl orthosilicate-based glass composition and method

DOEpatents

Wicks, George G.; Livingston, Ronald R.; Baylor, Lewis C.; Whitaker, Michael J.; O'Rourke, Patrick E.

1997-01-01

A tetraethyl orthosilicate-based, sol-gel glass composition with additives selected for various applications. The composition is made by mixing ethanol, water, and tetraethyl orthosilicate, adjusting the pH into the acid range, and aging the mixture at room temperature. The additives, such as an optical indicator, filler, or catalyst, are then added to the mixture to form the composition which can be applied to a substrate before curing. If the additive is an indicator, the light-absorbing characteristics of which vary upon contact with a particular analyte, the indicator can be applied to a lens, optical fiber, reagant strip, or flow cell for use in chemical analysis. Alternatively, an additive such as alumina particles is blended into the mixture to form a filler composition for patching cracks in metal, glass, or ceramic piping.

Effect of Particle Size and Operating Conditions on Pt 3Co PEMFC Cathode Catalyst Durability

DOE PAGES

Gummalla, Mallika; Ball, Sarah; Condit, David; ...

2015-05-29

The initial performance and decay trends of polymer electrolyte membrane fuel cells (PEMFC) cathodes with Pt 3Co catalysts of three mean particle sizes (4.9 nm, 8.1 nm, and 14.8 nm) with identical Pt loadings are compared. Even though the cathode based on 4.9 nm catalyst exhibited the highest initial electrochemical surface area (ECA) and mass activity, the cathode based on 8.1 nm catalyst showed better initial performance at high currents. Owing to the low mass activity of the large particles, the initial performance of the 14.8 nm Pt3Co-based electrode was the lowest. The performance decay rate of the electrodes withmore » the smallest Pt 3Co particle size was the highest and that of the largest Pt 3Co particle size was lowest. Interestingly, with increasing number of decay cycles (0.6 to 1.0 V, 50 mV/s), the relative improvement in performance of the cathode based on 8.1 nm Pt 3Co over the 4.9 nm Pt 3Co increased, owing to better stability of the 8.1 nm catalyst. The electron microprobe analysis (EMPA) of the decayed membrane-electrode assembly (MEA) showed that the amount of Co in the membrane was lower for the larger particles, and the platinum loss into the membrane also decreased with increasing particle size. This suggests that the higher initial performance at high currents with 8.1 nm Pt 3Co could be due to lower contamination of the ionomer in the electrode. Furthermore, lower loss of Co from the catalyst with increased particle size could be one of the factors contributing to the stability of ECA and mass activity of electrodes with larger cathode catalyst particles. To delineate the impact of particle size and alloy effects, these results are compared with prior work from our research group on size effects of pure platinum catalysts. The impact of PEMFC operating conditions, including upper potential, relative humidity, and temperature on the alloy catalyst decay trends, along with the EMPA analysis of the decayed MEAs, are reported.« less

Embedded Shape Memory Alloy Particles for the Self-Sensing of Fatigue Crack Growth in an Aluminum Alloy

NASA Astrophysics Data System (ADS)

Leser, William Paul

Future aerospace vehicles will be built using novel materials for mission conditions that are difficult to replicate in a laboratory. Structural health monitoring and condition-based maintenance will be critical to ensure the reliability of such vehicles. A multi-functional aluminum alloy containing embedded shape memory alloy (SMA) particles to detect fatigue crack growth is proposed. The regions of intensified strain near the tip of a growing fatigue crack cause the SMA particles to undergo a solid-to-solid phase transformation from austenite to martensite, releasing a detectable and identifiable acoustic emission (AE) signal that can be used to locate the crack in the affected component. This study investigates the AE response of two SMA systems, Ni-Ti, and Co-Ni-Al. Tensile (Ni-Ti) and compressive (Co-Ni-Al) tests were conducted to study the strain-induced transformation response in both of the alloy systems. It was found that the critical stress for transformation in both SMA systems was easily identified by a burst of AE activity during both transformation and reverse transformation. AE signals from these experiments were collected for use as training data for a Bayesian classifier to be used to identify transformation signals in a Al7050 matrix with embedded SMA particles. The Al/SMA composite was made by vacuum hot pressing SMA powder between aluminum plates. The effect of hot pressing temperature and subsequent heat treatments (solutionizing and peak aging) on the SMA particles was studied. It was found that, at the temperatures required, Co-Ni-Al developed a second phase that restricted the transformation from austenite to martensite, thus rendering it ineffective as a candidate for the embedded particles. Conversely, Ni-Ti did survive the embedding process and it was found that the solutionizing heat treatment applied after hot pressing was the main driver in determining the final transformation temperatures for the Ni-Ti particles. The effect of hot pressing on the transformation temperatures was negated upon solutionizing and peak aging occurred at a sufficiently low temperature to as not affect the properties of the Ni-Ti. Strain-induced transformation was confirmed in the Ni-Ti particles by digital image correlation (DIC) using an environmental scanning electron microscope (ESEM). Specimens were fatigue pre-cracked until a crack was produced and observed to be approaching a particle that could be monitored on the surface, at which point it was put into the ESEM for DIC under tensile loading. Acoustic emission activity was observed during this experiment. In order to distinguish AE signals arising due to phase transformation in the particles from those due to crack extension in the matrix, a Bayesian classifier was constructed based on frequency parameters calculated using the Hilbert-Huang transform (HHT). Using this classifier, AE signals consistent with those arising from phase transformation in bulk Ni-Ti were identified during phase transformation in the particles as observed with DIC. In addition to tensile crack growth in the ESEM, a fatigue crack was grown through a specimen with particles interspersed along the specimen center line. Several low amplitude AE events were observed as the crack grew through the aluminum. As the fatigue crack passed through the line of particles AE events increased dramatically in rate of occurance and amplitude. Amplitudes were 6-10 times higher as the crack passed near the particles. These AE events were also shown to be consistent with Ni-Ti phase transformation. A successful proof-of-concept was demonstrated for an aluminum alloy with embedded particles that emit an identifiable and repeatable AE signal in the presence of a fatigue crack, allowing for quick diagnosis of fatigue crack damage in this material.

The Particle Shape of WC Governing the Fracture Mechanism of Particle Reinforced Iron Matrix Composites.

PubMed

Li, Zulai; Wang, Pengfei; Shan, Quan; Jiang, Yehua; Wei, He; Tan, Jun

2018-06-11

In this work, tungsten carbide particles (WC p , spherical and irregular particles)-reinforced iron matrix composites were manufactured utilizing a liquid sintering technique. The mechanical properties and the fracture mechanism of WC p /iron matrix composites were investigated theoretically and experimentally. The crack schematic diagram and fracture simulation diagram of WC p /iron matrix composites were summarized, indicating that the micro-crack was initiated both from the interface for spherical and irregular WC p /iron matrix composites. However, irregular WC p had a tendency to form spherical WC p . The micro-cracks then expanded to a wide macro-crack at the interface, leading to a final failure of the composites. In comparison with the spherical WC p , the irregular WC p were prone to break due to the stress concentration resulting in being prone to generating brittle cracking. The study on the fracture mechanisms of WC p /iron matrix composites might provide a theoretical guidance for the design and engineering application of particle reinforced composites.

Effects of powder characteristics on injection molding and burnout cracking

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

Bandyopadhyay, G.; French, K.W.

Silicon nitride particle size and size distributions were varied widely to determine their effects on burnout cracking of injection-molded test parts containing thick and thin sections. Elimination of internal cracking required significant burnout shrinkage, which did not occur by changes of particle size and size distribution. However, isopressing of test parts after burnout provided the dimensional shrinkage necessary for producing crack-free components.

The nature of catalyst particles and growth mechanisms of GaN nanowires grown by Ni-assisted metal-organic chemical vapor deposition.

PubMed

Weng, Xiaojun; Burke, Robert A; Redwing, Joan M

2009-02-25

The structure and chemistry of the catalyst particles that terminate GaN nanowires grown by Ni-assisted metal-organic chemical vapor deposition were investigated using a combination of electron diffraction, high-resolution transmission electron microscopy, and x-ray energy dispersive spectrometry. The crystal symmetry, lattice parameter, and chemical composition obtained reveal that the catalyst particles are Ni(3)Ga with an ordered L 1(2) structure. The results suggest that the catalyst is a solid particle during growth and therefore favor a vapor-solid-solid mechanism for the growth of GaN nanowires under these conditions.

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.

Damage in gamma titanium aluminides due to small particle impacts

NASA Astrophysics Data System (ADS)

Stief, P. S.; Rubal, M. P.; Gray, G. T., III; Pereiras, J. M.

1998-10-01

Initiation of cracking due to small particle impacts on low ductility intermetallics is investigated experimentally and theoretically. The gamma titanium aluminide alloys of interest which are being considered for elevated temperature structural applications in aircraft engines exhibit tensile ductilities on the order of 1-2%. Cracking due to any source, including small particle impacts, is of concern given the rapid growth of cracks in fatigue. This investigation focuses on a model geometry which reproduces the rear face cracking that is induced by a small particle impinging on an air foil leading edge. Small steel spheres are projected onto thin plates at velocities ranging from 76 to 305 ms ; cracking is thereby induced on the rear surface of the plates. Through finite element analyses of the dynamic impact event and some analytical estimates, we examine the hypothesis that crack initiation due to small particle impacts can be correlated with material ductility and with the severity and spatial extent of the straining during the impact event. In addition, with the use of static indentation tests in which similar strain distributions are present, some insight is gained into the difference in ductility between high and low strain rates. 1998 Elsevier Science Ltd.

Method of forming supported doped palladium containing oxidation catalysts

DOEpatents

Mohajeri, Nahid

2014-04-22

A method of forming a supported oxidation catalyst includes providing a support comprising a metal oxide or a metal salt, and depositing first palladium compound particles and second precious metal group (PMG) metal particles on the support while in a liquid phase including at least one solvent to form mixed metal comprising particles on the support. The PMG metal is not palladium. The mixed metal particles on the support are separated from the liquid phase to provide the supported oxidation catalyst.

Effect of the relationship between particle size, inter-particle distance, and metal loading of carbon supported fuel cell catalysts on their catalytic activity

NASA Astrophysics Data System (ADS)

Corradini, Patricia Gon; Pires, Felipe I.; Paganin, Valdecir A.; Perez, Joelma; Antolini, Ermete

2012-09-01

The effect of the relationship between particle size ( d), inter-particle distance ( x i ), and metal loading ( y) of carbon supported fuel cell Pt or PtRu catalysts on their catalytic activity, based on the optimum d (2.5-3 nm) and x i / d (>5) values, was evaluated. It was found that for y < 30 wt%, the optimum values of both d and x i / d can be always obtained. For y ≥ 30 wt%, instead, the positive effect of a thinner catalyst layer of the fuel cell electrode than that using catalysts with y < 30 wt% is concomitant to a decrease of the effective catalyst surface area due to an increase of d and/or a decrease of x i / d compared to their optimum values, with in turns gives rise to a decrease in the catalytic activity. The effect of the x i / d ratio has been successfully verified by experimental results on ethanol oxidation on PtRu/C catalysts with same particle size and same degree of alloying but different metal loading. Tests in direct ethanol fuel cells showed that, compared to 20 wt% PtRu/C, the negative effect of the lower x i / d on the catalytic activity of 30 and 40 wt% PtRu/C catalysts was superior to the positive effect of the thinner catalyst layer.

Separation of catalyst from Fischer-Tropsch slurry

DOEpatents

White, Curt M.; Quiring, Michael S.; Jensen, Karen L.; Hickey, Richard F.; Gillham, Larry D.

1998-10-27

In a catalytic process for converting synthesis gas including hydrogen and carbon monoxide to hydrocarbons and oxygenates by a slurry Fischer-Tropsch synthesis, the wax product along with dispersed catalyst is removed from the slurry and purified by removing substantially all of the catalyst prior to upgrading the wax and returning a portion to the Fischer-Tropsch reaction. Separation of the catalyst particles from the wax product is accomplished by dense gas and/or liquid extraction in which the organic compounds in the wax are dissolved and carried away from the insoluble inorganic catalyst particles that are primarily inorganic in nature. The purified catalyst free wax product can be subsequently upgraded by various methods such as hydrogenation, isomerization, hydrocracking, conversion to gasoline and other products over ZSM-5 aluminosilicate zeolite, etc. The catalyst particles are returned to the Fischer-Tropsch Reactor by slurring them with a wax fraction of appropriate molecular weight, boiling point and viscosity to avoid reactor gelation.

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

Amitava Sarkar; James K. Neathery; Burtron H. Davis

A fundamental filtration study was started to investigate the separation of Fischer-Tropsch Synthesis (FTS) liquids from iron-based catalyst particles. Slurry-phase FTS in slurry bubble column reactor systems is the preferred mode of operation since the reaction is highly exothermic. Consequently, heavy wax products in one approach may be separated from catalyst particles before being removed from the reactor system. Achieving an efficient wax product separation from iron-based catalysts is one of the most challenging technical problems associated with slurry-phase iron-based FTS and is a key factor for optimizing operating costs. The separation problem is further compounded by attrition of ironmore » catalyst particles and the formation of ultra-fine particles.« less

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

James K. Neathery; Gary Jacobs; Burtron H. Davis

In this reporting period, a fundamental filtration study was started to investigate the separation of Fischer-Tropsch Synthesis (FTS) liquids from iron-based catalyst particles. Slurry-phase FTS in slurry bubble column reactor systems is the preferred mode of production since the reaction is highly exothermic. Consequently, heavy wax products must be separated from catalyst particles before being removed from the reactor system. Achieving an efficient wax product separation from iron-based catalysts is one of the most challenging technical problems associated with slurry-phase FTS. The separation problem is further compounded by catalyst particle attrition and the formation of ultra-fine iron carbide and/or carbonmore » particles. Existing pilot-scale equipment was modified to include a filtration test apparatus. After undergoing an extensive plant shakedown period, filtration tests with cross-flow filter modules using simulant FTS wax slurry were conducted. The focus of these early tests was to find adequate mixtures of polyethylene wax to simulate FTS wax. Catalyst particle size analysis techniques were also developed. Initial analyses of the slurry and filter permeate particles will be used by the research team to design improved filter media and cleaning strategies.« less

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

A modified Brownian force for ultrafine particle penetration through building crack modeling

NASA Astrophysics Data System (ADS)

Chen, Chen; Zhao, Bin

2017-12-01

Combustion processes related to industry, traffic, agriculture, and waste treatment and disposal increase the amount of outdoor ultrafine particles (UFPs), which have adverse effects on human health. Given that people spend the majority of their time indoors, it is critical to understand the penetration of outdoor UFPs through building cracks in order to estimate human exposure to outdoor-originated UFPs. Lagrangian tracking is an efficient approach for modeling particle penetration. However, the Brownian motion for Lagrangian tracking in ANSYS Fluent®, a widely used software for particle dispersion modeling, is not able to model UFP dispersion accurately. In this study, we modified the Brownian force by rewriting the Brownian diffusion coefficient and particle integration time step with a user-defined function in ANSYS Fluent® to model particle penetration through building cracks. The results obtained using the modified model agree much better with the experimental results, with the averaged relative error less than 14% for the smooth crack cases and 21% for the rough crack case. We expect the modified Brownian force model proposed herein to be applied for UFP dispersion modeling in more indoor air quality studies.

An efficient and reusable “hairy” particle acid catalyst for the synthesis of 5-hydroxymethylfurfural from dehydration of fructose in water

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

Tian, Chengcheng; Bao, Chunhui; Binder, Andrew

We employed poly(4-styrenesulfonic acid) brush-grafted silica particles, synthesized by surface-initiated atom transfer radical polymerization, as a reusable acid catalyst for dehydration of fructose to 5-hydroxymethylfurfural (HMF) in water. Furthermore, the particles exhibited a high activity with the HMF yield of up to 31%, in contrast to 26% from the corresponding free homopolymer catalyst.

Tailoring Silica-alumina Supported Pt-Pd As Poison Tolerant Catalyst For Aromatics Hydrogenation

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

Yu, Yanzhe; Gutierrez, Oliver Y.; Haller, Gary L.

2013-08-01

The tailoring of the physicochemical and catalytic properties of mono- and bimetallic Pt-Pd catalysts supported on amorphous silica-alumina is studied. Electron energy loss spectroscopy and extended X-ray absorption fine structure analyses indicated that bimetallic Pt-Pd and relatively large monometallic Pd particles were formed, whereas the X-ray absorption near edge structure provided direct evidence for the electronic deficiency of the Pt atoms. The heterogeneous distribution of metal particles was also shown by high resolution transmission electron microscopy. The average structure of the bimetallic particles (Pt-rich core and Pd-rich shell) and the presence of Pd particles led to surface Pd enrichment, whichmore » was independently shown by IR spectra of adsorbed CO. The specific metal distribution, average size, and surface composition of the Pt-Pd particles depend to a large extent on the metal precursors. In the presence of NH3 ligands, Pt-Pd particles with a fairly homogeneous bulk and surface metal distribution were formed. Also high Lewis acid site concentration of the carrier leads to more homogeneous bimetallic particles. All catalysts were active for the hydrogenation of tetralin in the absence and presence of quinoline and dibenzothiophene (DBT). Monometallic Pt catalysts had the highest hydrogenation activity in poison-free and quinoline-containing feed. When DBT was present, bimetallic Pt-Pd catalysts with the most homogenous metal distribution showed the highest activity. The higher resistance of bimetallic catalysts towards sulfur poisoning compared to their monometallic Pt counterparts results from the weakened metal-sulfur bond on the electron deficient Pt atoms. Thus, increasing the fraction of electron deficient Pt on the surface of the bimetallic particles increases the efficiency of the catalyst in the presence of sulfur.« 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.

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

Hydrogenation of p-chloronitrobenzene on Ni-B Nanometal Catalysts

NASA Astrophysics Data System (ADS)

Liu, Yu-Chang; Huang, Chung-Yin; Chen, Yu-Wen

2006-04-01

A series of Ni-B catalysts were prepared by mixing nickel acetate in 50% ethanol/water or methanol/water solution. The solution of sodium borohydride (1 M) in excess amount to nickel was then added dropwise into the mixture to ensure full reduction of nickel cations. The mol ratio of boron to nickel in mother solution was 3 to 1. The effects of preparation conditions such as temperature, stirring speed, and sheltering gas on the particle size, surface compositions, electronic states of surface atoms and catalytic activities of the Ni-B catalysts were studied. Ranel nickel catalyst was included for comparison. These catalysts were characterized by N2 sorption, X-ray diffraction, transmission electron microscopy, and X-ray photoelectron spectroscopy. The catalysts were tested for liquid phase hydrogenation of p-chloronitrobenzene. All of the catalysts prepared in this study had nanosized particles. The preparation condition has significant influence on the particle size and surface compositions of the catalyst. The Ni-B catalyst was passivated by boron; therefore it was more stable than Raney nickel and did not catch fire after exposure to air. The catalysts prepared under N2 flow could suppress the oxidation of Ni by the dissolved oxygen in water and had metallic state of nickel. The catalyst prepared with vigorous stirring at 25°C under N2 stream yielded the smallest particles and resulted in the highest activity. It was much more active than the Raney nickel catalyst. The reaction condition also has pronounced effect on the hydrogenation activity. Using methanol as the reaction solvent increased p-chloronitrobenzene conversion to a large extent, compared to that using ethanol as the reaction medium. The selectivity of main product ( p-chloroaniline) was greater than 99% on all of the Ni-B catalysts.

Effects of External Hydrogen on Hydrogen Transportation and Distribution Around the Fatigue Crack Tip in Type 304 Stainless Steel

NASA Astrophysics Data System (ADS)

Chen, Xingyang; Zhou, Chengshuang; Cai, Xiao; Zheng, Jinyang; Zhang, Lin

2017-10-01

The effects of external hydrogen on hydrogen transportation and distribution around the fatigue crack tip in type 304 stainless steel were investigated by using hydrogen microprint technique (HMT) and thermal desorption spectrometry. HMT results show that some silver particles induced by hydrogen release are located near the fatigue crack and more silver particles are concentrated around the crack tip, which indicates that hydrogen accumulates in the vicinity of the crack tip during the crack growth in hydrogen gas environment. Along with the crack propagation, strain-induced α' martensite forms around the crack tip and promotes hydrogen invasion into the matrix, which will cause the crack initiation and propagation at the austenite/ α' martensite interface. In addition, the hydrogen content in the vicinity of the crack tip is higher than that at the crack edge far away from the crack tip, which is related to the stress state and strain-induced α' martensite.

Fracture behavior of 20% Nb particulate reinforced alumina composite

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

Lane, S.; Biner, S.B.; Buck, O.

1993-11-01

The composites consist of alumina matrix with 0.05 wt % MgO and 20 Vol % Nb with an average particle size of 30 to 100 microns produced by dry mixing and sintering to near their theoretical densities. Fracture toughness tests were carried out in three point bending on chevron notched samples. Results indicate that R-curve of the composites exhibited more than 300% increase in crack growth resistance compared to crack growth resistance of alumina produced with the identical procedures. Crack growth resistance curve of the composites increased with increasing Nb particle size. Metallorgraph indicated that failure of Nb particles inmore » crack path ranges from full interface separation without any significant deformation of Nb particles to cleavage failure without any evidence of interface separation.« less

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.

On the role of particle cracking in flow and fracture of metal matrix composites

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

Brockenbrough, J.R.; Zok, F.W.

1995-01-01

The flow response of particle-reinforced metal matrix composites is studied using finite element methods. Unit cells containing either intact or cracked particles in a power law hardening matrix are used to determine the corresponding asymptotic flow strengths. The effects of the hardening exponent and the elastic mismatch between the particles and the matrix on the flow response are examined. For comparison, the flow response of power law hardening solids containing penny-shaped cracks is also evaluated. The latter results are found to be in reasonable agreement with those corresponding to composites that contain low volume fractions of cracked particles. The asymptoticmore » results are used to develop a one-dimensional constitutive law for composites which undergo progressive damage during tensile straining. This law is used to evaluate the strain at the onset of plastic instability. It is proposed that the instability strain be used as a measure of tensile ductility when the particle content is low and the particles are uniformly distributed through the matrix.« less

Tetraethyl orthosilicate-based glass composition and method

DOEpatents

Wicks, G.G.; Livingston, R.R.; Baylor, L.C.; Whitaker, M.J.; O`Rourke, P.E.

1997-06-10

A tetraethyl orthosilicate-based, sol-gel glass composition with additives selected for various applications is described. The composition is made by mixing ethanol, water, and tetraethyl orthosilicate, adjusting the pH into the acid range, and aging the mixture at room temperature. The additives, such as an optical indicator, filler, or catalyst, are then added to the mixture to form the composition which can be applied to a substrate before curing. If the additive is an indicator, the light-absorbing characteristics of which vary upon contact with a particular analyte, the indicator can be applied to a lens, optical fiber, reagent strip, or flow cell for use in chemical analysis. Alternatively, an additive such as alumina particles is blended into the mixture to form a filler composition for patching cracks in metal, glass, or ceramic piping. 12 figs.

Dynamic fracture behavior of single and contacting Poly(methyl methacrylate) particles

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

Parab, Niranjan D.; Guo, Zherui; Hudspeth, Matthew C.

Fracture behaviors of single, two, and multiple contacting spherical Poly (methyl methacrylate) (PMMA) particles were recorded using high speed synchrotron X-ray phase contrast imaging. A miniaturized Kolsky bar setup was used to apply dynamic compressive loading on the PMMA particles. In both single and two particle experiments, cracking initiated near the center of the particles and propagated towards the contacts. The crack bifurcated near the contact points for single particle experiments, thus forming conical fragments. The crack bifurcation and subsequent conical fragment formation was observed only at the particle-particle contact for two particle experiments. The particles were observed to fracturemore » in hemispherical fragments normal to the contact plane in the multiparticle experiments. The observed failure mechanisms strongly suggest that the maximum tensile stress near the center of the particle is the critical parameter governing fracture of the particles. Moreover, the compressive stress under the contact areas led to the bifurcation and subsequent conical fragment formation.« less

Dynamic fracture behavior of single and contacting Poly(methyl methacrylate) particles

DOE PAGES

Parab, Niranjan D.; Guo, Zherui; Hudspeth, Matthew C.; ...

2017-09-19

Fracture behaviors of single, two, and multiple contacting spherical Poly (methyl methacrylate) (PMMA) particles were recorded using high speed synchrotron X-ray phase contrast imaging. A miniaturized Kolsky bar setup was used to apply dynamic compressive loading on the PMMA particles. In both single and two particle experiments, cracking initiated near the center of the particles and propagated towards the contacts. The crack bifurcated near the contact points for single particle experiments, thus forming conical fragments. The crack bifurcation and subsequent conical fragment formation was observed only at the particle-particle contact for two particle experiments. The particles were observed to fracturemore » in hemispherical fragments normal to the contact plane in the multiparticle experiments. The observed failure mechanisms strongly suggest that the maximum tensile stress near the center of the particle is the critical parameter governing fracture of the particles. Moreover, the compressive stress under the contact areas led to the bifurcation and subsequent conical fragment formation.« less

Recent Advances in Catalyst Accelerated Stress Tests for Polymer Electrolyte Membrane Fuel Cells

DOE PAGES

Stariha, Sarah; Macauley, Natalia; Sneed, Brian T.; ...

2018-03-15

The U.S. Department of Energy (DOE) set the 2020 durability target for polymer electrolyte membrane fuel cell transportation applications at 5000 hours. Since it is impractical to test every fuel cell for this length of time, there is ever increasing interest in developing accelerated stress tests (ASTs) that can accurately simulate the material component degradation in the membrane electrode assembly (MEA) observed under automotive operating conditions, but over a much shorter time frame. In this study, a square-wave catalyst AST was examined that shows a 5X time acceleration factor over the triangle-wave catalyst AST and a 25X time acceleration factormore » over the modified wet drive-cycle catalyst durability protocol, significantly decreasing the testing time. These acceleration factors were correlated to the platinum (Pt) particle size increase and associated decrease in electrochemical surface area (ECSA). This square-wave AST has been adopted by the DOE as a standard protocol to evaluate catalyst durability. We also compare three catalyst-durability protocols using state-of-the-art platinum-cobalt catalysts supported on high surface area carbon (SOA Pt-Co/HSAC) in the cathode catalyst layer. The results for each of the three tests showed both catalyst particle size increase and transition metal leaching. Moreover the acceleration factors for the alloy catalysts were smaller due to Co leaching being the predominant mechanism of voltage decay in ~5 nm PtCo/C catalysts. Finally, an extremely harsh carbon corrosion AST was run using the same SOA Pt-Co/HSAC catalyst. This showed minimal change in particle size and a low percentage Co loss from the cathode catalyst particles, despite a significant loss in catalyst layer thickness and cell performance. The carbon corrosion rates during these various ASTs were directly measured by monitoring the CO 2 emission from the cathode, further confirming the ability of the square-wave AST to evaluate the electro-catalyst independently of the support.« less

Recent Advances in Catalyst Accelerated Stress Tests for Polymer Electrolyte Membrane Fuel Cells

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

Stariha, Sarah; Macauley, Natalia; Sneed, Brian T.

The U.S. Department of Energy (DOE) set the 2020 durability target for polymer electrolyte membrane fuel cell transportation applications at 5000 hours. Since it is impractical to test every fuel cell for this length of time, there is ever increasing interest in developing accelerated stress tests (ASTs) that can accurately simulate the material component degradation in the membrane electrode assembly (MEA) observed under automotive operating conditions, but over a much shorter time frame. In this study, a square-wave catalyst AST was examined that shows a 5X time acceleration factor over the triangle-wave catalyst AST and a 25X time acceleration factormore » over the modified wet drive-cycle catalyst durability protocol, significantly decreasing the testing time. These acceleration factors were correlated to the platinum (Pt) particle size increase and associated decrease in electrochemical surface area (ECSA). This square-wave AST has been adopted by the DOE as a standard protocol to evaluate catalyst durability. We also compare three catalyst-durability protocols using state-of-the-art platinum-cobalt catalysts supported on high surface area carbon (SOA Pt-Co/HSAC) in the cathode catalyst layer. The results for each of the three tests showed both catalyst particle size increase and transition metal leaching. Moreover the acceleration factors for the alloy catalysts were smaller due to Co leaching being the predominant mechanism of voltage decay in ~5 nm PtCo/C catalysts. Finally, an extremely harsh carbon corrosion AST was run using the same SOA Pt-Co/HSAC catalyst. This showed minimal change in particle size and a low percentage Co loss from the cathode catalyst particles, despite a significant loss in catalyst layer thickness and cell performance. The carbon corrosion rates during these various ASTs were directly measured by monitoring the CO 2 emission from the cathode, further confirming the ability of the square-wave AST to evaluate the electro-catalyst independently of the support.« less

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

A Meta-Analysis Of Corrosion Studies for Maritime Patrol and Reconnaissance Aircraft (MPRA)

DTIC Science & Technology

2016-09-01

performed onsite. Aircraft rating was based upon the presence and/or extent of paint adhesion, paint cracking , clean ability, fluid damage, oxidation...because of corrosion control maintenance. No significant issues were observed related to paint cracking , fluid damage, corrosion, and clean ability of...HEXAMETHYLENEDIISOCYANATE 822-06-0 83194 X-310A; POLYURETHANE CATALYST XYLENE 1330-20-7 82649 X-530; HS EPOXY ENAMEL CURING SOLUTION BUTANOL 71-36-3

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

Separation of catalyst from Fischer-Tropsch slurry

DOEpatents

White, C.M.; Quiring, M.S.; Jensen, K.L.; Hickey, R.F.; Gillham, L.D.

1998-10-27

In a catalytic process for converting synthesis gas including hydrogen and carbon monoxide to hydrocarbons and oxygenates by a slurry Fischer-Tropsch synthesis, the wax product along with dispersed catalyst is removed from the slurry and purified by removing substantially all of the catalyst prior to upgrading the wax and returning a portion to the Fischer-Tropsch reaction. Separation of the catalyst particles from the wax product is accomplished by dense gas and/or liquid extraction in which the organic compounds in the wax are dissolved and carried away from the insoluble inorganic catalyst particles that are primarily inorganic in nature. The purified catalyst-free wax product can be subsequently upgraded by various methods such as hydrogenation, isomerization, hydrocracking, conversion to gasoline and other products over ZSM-5 aluminosilicate zeolite, etc. The catalyst particles are returned to the Fischer-Tropsch Reactor by mixing them with a wax fraction of appropriate molecular weight, boiling point and viscosity to avoid reactor gelation. 2 figs.

Process for coal liquefaction using electrodeposited catalyst

DOEpatents

Moore, Raymond H.

1978-01-01

A process for the liquefaction of solid hydrocarbonaceous materials is disclosed. Particles of such materials are electroplated with a metal catalyst and are then suspended in a hydrocarbon oil and subjected to hydrogenolysis to liquefy the solid hydrocarbonaceous material. A liquid product oil is separated from residue solid material containing char and the catalyst metal. The catalyst is recovered from the solid material by electrolysis for reuse. A portion of the product oil can be employed as the hydrocarbon oil for suspending additional particles of catalyst coated solid carbonaceous material for hydrogenolysis.

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.

Radiolytic Synthesis of Pt-Particle/ABS Catalysts for H₂O₂ Decomposition in Contact Lens Cleaning.

PubMed

Ohkubo, Yuji; Aoki, Tomonori; Seino, Satoshi; Mori, Osamu; Ito, Issaku; Endo, Katsuyoshi; Yamamura, Kazuya

2017-08-23

A container used in contact lens cleaning requires a Pt plating weight of 1.5 mg for H₂O₂ decomposition although Pt is an expensive material. Techniques that decrease the amount of Pt are therefore needed. In this study, Pt nanoparticles instead of Pt plating film were supported on a substrate of acrylonitrile-butadiene-styrene copolymer (ABS). This was achieved by the reduction of Pt ions in an aqueous solution containing the ABS substrate using high-energy electron-beam irradiation. Pt nanoparticles supported on the ABS substrate (Pt-particle/ABS) had a size of 4-10 nm. The amount of Pt required for Pt-particle/ABS was 250 times less than that required for an ABS substrate covered with Pt plating film (Pt-film/ABS). The catalytic activity for H₂O₂ decomposition was estimated by measuring the residual H₂O₂ concentration after immersing the catalyst for 360 min. The Pt-particle/ABS catalyst had a considerably higher specific catalytic activity for H₂O₂ decomposition than the Pt-film/ABS catalyst. In addition, sterilization performance was estimated from the initial rate of H₂O₂ decomposition over 60 min. The Pt-particle/ABS catalyst demonstrated a better sterilization performance than the Pt-film/ABS catalyst. The difference between Pt-particle/ABS and Pt-film/ABS was shown to reflect the size of the O₂ bubbles formed during H₂O₂ decomposition.

Re-examination of the Pt Particle Size Effect on the Oxygen Reduction Reaction for Ultrathin Uniform Pt/C Catalyst Layers without Influence from Nafion

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

Shinozaki, Kazuma; Morimoto, Yu; Pivovar, Bryan S.

The platinum 'particle size effect' on the oxygen reduction reaction (ORR) has been re-evaluated using commercial Pt/C catalysts (2-10 nm Pt particle) and polycrystalline Pt (poly-Pt) in 0.1 M HClO4 with a rotating disk electrode method. Nafion-free catalyst layers were employed to obtain specific activities (SA) that were not perturbed (suppressed) by sulfonate anion adsorption/blocking. By using ultrathin uniform catalyst layers, O2 diffusion limitation was minimized as confirmed from the high SAs of our supported catalysts that were comparable to unsupported sputtered Pt having controlled sizes. The specific activity (SA) steeply increased for the particle sizes in the range -2-10more » nm (0.8-1.8 mA/cm2Pt at 0.9 V vs. RHE) and plateaued over -10 nm to 2.7 mA/cm2Pt for bulk poly-Pt. On the basis of the activity trend for the range of particle sizes studied, it appears that the effect of carbon support on activity is negligible. The experimental results and the concomitant profile of SA vs. particle size was found to be in an agreement to a truncated octahedral particle model that assumes active terrace sites.« less

Intragranular cracking as a critical barrier for high-voltage usage of layer-structured cathode for lithium-ion batteries

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

Yan, Pengfei; Zheng, Jianming; Gu, Meng

LiNi 1/3Mn 1/3Co 1/3O 2 (NMC333) layered cathode is often fabricated as secondary particles of consisting of densely packed primary particles, which offers advantage of high energy density and alleviation of cathode side reactions/corrosions, but introduces other drawbacks, such as intergranular cracking. Here, we report unexpected observations on the nucleation and growth of intragranular cracks in the commercial NMC333 layered cathode by using advanced S/TEM. We found that the formation of the intragranular cracks is directly associated with high voltage cycling, which is an electrochemically driven and diffusion controlled process. The intragranular cracks were noticed to be characteristically initiated frommore » grain interior, a consequence of dislocation based crack incubation mechanism. This observation is in sharp contrast with the general theoretical models, predicting the initiation of intragranular cracks from grain boundaries or particle surface. As a result, our study indicates that maintain a structural stability is the key step toward high voltage operation of layered cathode materials.« less

Intragranular cracking as a critical barrier for high-voltage usage of layer-structured cathode for lithium-ion batteries

DOE PAGES

Yan, Pengfei; Zheng, Jianming; Gu, Meng; ...

2017-01-16

LiNi 1/3Mn 1/3Co 1/3O 2 (NMC333) layered cathode is often fabricated as secondary particles of consisting of densely packed primary particles, which offers advantage of high energy density and alleviation of cathode side reactions/corrosions, but introduces other drawbacks, such as intergranular cracking. Here, we report unexpected observations on the nucleation and growth of intragranular cracks in the commercial NMC333 layered cathode by using advanced S/TEM. We found that the formation of the intragranular cracks is directly associated with high voltage cycling, which is an electrochemically driven and diffusion controlled process. The intragranular cracks were noticed to be characteristically initiated frommore » grain interior, a consequence of dislocation based crack incubation mechanism. This observation is in sharp contrast with the general theoretical models, predicting the initiation of intragranular cracks from grain boundaries or particle surface. As a result, our study indicates that maintain a structural stability is the key step toward high voltage operation of layered cathode materials.« less

Synchrotron x-ray microtomography of the interior microstructure of chocolate

NASA Astrophysics Data System (ADS)

Lügger, Svenja K.; Wilde, Fabian; Dülger, Nihan; Reinke, Lennart M.; Kozhar, Sergii; Beckmann, Felix; Greving, Imke; Vieira, Josélio; Heinrich, Stefan; Palzer, Stefan

2016-10-01

The structure of chocolate, a multicomponent food product, was analyzed using microtomography. Chocolate consists of a semi-solid cocoa butter matrix and a dense network of suspended particles. A detailed analysis of the microstructure is needed to understand mass transport phenomena. Transport of lipids from e.g. a filling or liquid cocoa butter is responsible for major problems in the confectionery industry such as formation of chocolate bloom, which is the formation of visible white spots or a grayish haze on the chocolate surface and leads to consumer rejections and thus large sales losses for the confectionery industry. In this study it was possible to visualize the inner structure of chocolate and clearly distinguish the particles from the continuous phase by taking advantage of the high density contrast of synchrotron radiation. Consequently, particle arrangement and cracks within the sample were made visible. The cracks are several micrometers thick and propagate throughout the entire sample. Images of pure cocoa butter, chocolate without any particles, did not show any cracks and thus confirmed that cracks are a result of embedded particles. They arise during the manufacturing process. Thus, the solidification process, a critical manufacturing step, was simulated with finite element methods in order to understand crack formation during this step. The simulation showed that cracks arise because of significant contraction of cocoa butter, the matrix phase, without any major change of volume of the suspended particles. Tempering of the chocolate mass prior to solidification is another critical step for a good product quality. We found that samples which solidified in an uncontrolled manner are less homogeneous than tempered samples. In summary, our study visualized for the first time the inner microstructure of tempered and untempered cocoa butter as well as chocolate without sample destruction and revealed cracks, which might act as transport pathways.

Dynamic fracture and hot-spot modeling in energetic composites

NASA Astrophysics Data System (ADS)

Grilli, Nicolò; Duarte, Camilo A.; Koslowski, Marisol

2018-02-01

Defects such as cracks, pores, and particle-matrix interface debonding affect the sensitivity of energetic materials by reducing the time-to-ignition and the threshold pressure to initiate an explosion. Frictional sliding of preexisting cracks is considered to be one of the most important causes of localized heating. Therefore, understanding the dynamic fracture of crystalline energetic materials is of extreme importance to assess the reliability and safety of polymer-bonded explosives. Phase field damage model simulations, based on the regularization of the crack surface as a diffuse delta function, are used to describe crack propagation in cyclotetramethylene-tetranitramine crystals embedded in a Sylgard matrix. A thermal transport model that includes heat generation by friction at crack interfaces is coupled to the solution of crack propagation. 2D and 3D dynamic compression simulations are performed with different boundary velocities and initial distributions of cracks and interface defects to understand their effect on crack propagation and heat generation. It is found that, at an impact velocity of 400 m/s, localized damage at the particle-binder interface is of key importance and that the sample reaches temperatures high enough to create a hot-spot that will lead to ignition. At an impact velocity of 10 m/s, preexisting cracks advanced inside the particle, but the increase of temperature will not cause ignition.

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

Stariha, Sarah; Macauley, Natalia; Sneed, Brian T.

The U.S. Department of Energy (DOE) set the 2020 durability target for polymer electrolyte membrane fuel cell transportation applications at 5000 hours. Since it is impractical to test every fuel cell for this length of time, there is ever increasing interest in developing accelerated stress tests (ASTs) that can accurately simulate the material component degradation in the membrane electrode assembly (MEA) observed under automotive operating conditions, but over a much shorter time frame. In this study, a square-wave catalyst AST was examined that shows a 5X time acceleration factor over the triangle-wave catalyst AST and a 25X time acceleration factormore » over the modified wet drive-cycle catalyst durability protocol, significantly decreasing the testing time. These acceleration factors were correlated to the platinum (Pt) particle size increase and associated decrease in electrochemical surface area (ECSA). This square-wave AST has been adopted by the DOE as a standard protocol to evaluate catalyst durability. We also compare three catalyst-durability protocols using state-of-the-art platinum-cobalt catalysts supported on high surface area carbon (SOA Pt-Co/HSAC) in the cathode catalyst layer. The results for each of the three tests showed both catalyst particle size increase and transition metal leaching. Moreover the acceleration factors for the alloy catalysts were smaller due to Co leaching being the predominant mechanism of voltage decay in ~5 nm PtCo/C catalysts. Finally, an extremely harsh carbon corrosion AST was run using the same SOA Pt-Co/HSAC catalyst. This showed minimal change in particle size and a low percentage Co loss from the cathode catalyst particles, despite a significant loss in catalyst layer thickness and cell performance. The carbon corrosion rates during these various ASTs were directly measured by monitoring the CO 2 emission from the cathode, further confirming the ability of the square-wave AST to evaluate the electro-catalyst independently of the support.« less

Investigation of the Interaction between Nafion Ionomer and Surface Functionalized Carbon Black Using Both Ultrasmall Angle X-ray Scattering and Cryo-TEM

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

Yang, Fan; Xin, Le; Uzunoglu, Aytekin

In making a catalyst ink, the interaction between Nafion ionomer and catalyst support are the key factors that directly affect both ionic conductivity and electronic conductivity of the catalyst layer in a membrane electrode assembly (MEA). One of the major aims of this investigation is to understand the behavior of the catalyst support, Vulcan XC-72 (XC-72) aggregates, in the existence of the Nafion ionomer in a catalyst ink to fill the knowledge gap of the interaction of these components. The dispersion of catalyst ink not only depends on the solvent, but also depends on the interaction of Nafion and carbonmore » particles in the ink. The interaction of Nafion ionomer particles and XC-72 catalyst aggregates in liquid media was studied using ultra small angle x-ray scattering (USAXS) and cryogenic TEM techniques. Carbon black XC-72) and functionalized carbon black systems were introduced to study the interaction behaviors. A multiple curve fitting was used to extract the particle size and size distribution from scattering data. The results suggest that the particle size and size distribution of each system changed significantly in Nafion + XC-72 system, Nafion + NH2-XC72 system, and Nafion + SO3H-XC-72 system, which indicates that an interaction among these components (i.e. ionomer particles and XC-72 aggregates) exists. The cryogenic TEM, which allows for the observation the size of particles in a liquid, was used to validate the scattering results and shows excellent agreement.« less

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.

Particle size and support effects in electrocatalysis.

PubMed

Hayden, Brian E

2013-08-20

Researchers increasingly recognize that, as with standard supported heterogeneous catalysts, the activity and selectivity of supported metal electrocatalysts are influenced by particle size, particle structure, and catalyst support. Studies using model supported heterogeneous catalysts have provided information about these effects. Similarly, model electrochemical studies on supported metal electrocatalysts can provide insight into the factors determining catalytic activity. High-throughput methods for catalyst synthesis and screening can determine systematic trends in activity as a function of support and particle size with excellent statistical certainty. In this Account, we describe several such studies investigating methods for dispersing precious metals on both carbon and oxide supports, with particular emphasis on the prospects for the development of low-temperature fuel-cell electrocatalysts. One key finding is a decrease in catalytic activity with decreasing particle size independent of the support for both oxygen reduction and CO oxidation on supported gold and platinum. For these reactions, there appears to be an intrinsic particle size effect that results in a loss of activity at particle sizes below 2-3 nm. A titania support, however, also increases activity of gold particles in the electrooxidation of CO and in the reduction of oxygen, with an optimum at 3 nm particle size. This optimum may represent the superposition of competing effects: a titania-induced enhanced activity versus deactivation at small particle sizes. The titania support shows catalytic activity at potentials where carbon-supported and bulk-gold surfaces are normally oxidized and CO electrooxidation is poisoned. On the other hand, platinum on amorphous titania shows a different effect: the oxidation reduction reaction is strongly poisoned in the same particle size range. We correlated the influence of the titania support with titania-induced changes in the surface redox behavior of the platinum particles. For both supported gold and platinum particles in electrocatalysis, we observe parallels to the effects of particle size and support in the equivalent heterogeneous catalysts. Studies of model supported-metal electrocatalysts, performs efficiently using high throughput synthetic and screening methodologies, will lead to a better understanding of the mechanisms responsible for support and particle size effects in electrocatalysis, and will drive the development of more effective and robust catalysts in the future.

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

Mechanistic Analysis of Mechano-Electrochemical Interaction in Silicon Electrodes with Surface Film

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

Verma, Ankit; Mukherjee, Partha P.

2017-11-17

High-capacity anode materials for lithium-ion batteries, such as silicon, are prone to large volume change during lithiation/delithiation which may cause particle cracking and disintegration, thereby resulting in severe capacity fade and reduction in cycle life. In this work, a stochastic analysis is presented in order to understand the mechano-electrochemical interaction in silicon active particles along with a surface film during cycling. Amorphous silicon particles exhibiting single-phase lithiation incur lower amount of cracking as compared to crystalline silicon particles exhibiting two-phase lithiation for the same degree of volumetric expansion. Rupture of the brittle surface film is observed for both amorphous andmore » crystalline silicon particles and is attributed to the large volumetric expansion of the silicon active particle with lithiation. The mechanical property of the surface film plays an important role in determining the amount of degradation in the particle/film assembly. A strategy to ameliorate particle cracking in silicon active particles is proposed.« 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.

Water-assisted growth of graphene-carbon nanotube hybrids in plasma

NASA Astrophysics Data System (ADS)

Tewari, Aarti; Ghosh, Santanu; Srivastava, Pankaj

2018-04-01

The enhanced growth of graphene-carbon nanotube (CNT) hybrids in a hydrocarbon and hydrogen plasma assisted by water is numerically formulated. The catalyst activity and agglomeration of catalyst particles are the rate determining factors in the growth of hybrids and their constituents, i.e., the CNT and graphene. The water vapor concentration is varied to investigate its effect on the growth process. The enhanced catalyst activity on account of oxidation by hydroxyl ions of water to impede the agglomeration of catalyst particles and the removal of amorphous carbon through etching by hydrogen ions of water are seen to be the main driving forces behind the many fold increase in the dimensions of constituent nanostructures and the hybrids with water vapor concentration. Importantly, beyond a certain specific water vapor concentration, the growth rates dropped due to active oxidation of the catalyst particle.

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

Development of a specimen heating holder with an evaporator and gas injector and its application for catalyst.

PubMed

Takeo, Kamino; Toshie, Yaguchi; Mitsuru, Konno; Akira, Watabe; Yasuhira, Nagakubo

2006-10-01

A specimen heating holder equipped with a gas injector and an evaporator has been developed for use with conventional transmission electron microscopes (TEMs). The developed specimen holder allows both synthesis of metal oxide support and deposition of catalyst nano-particles in situ. Since the holder is designed to be used in small gapped high-resolution objective lens pole-piece, all the procedure from the synthesis of support material to the deposition of catalyst as well as the behavior of the catalyst nano-particles on the support can be observed at near atomic resolution. The developed specimen holder was applied to the study of AuPd catalyst. First, air was injected onto heated aluminum particles via a gas injector to synthesize Al(2)O(3) support. Then, nano-particles of AuPd were deposited on the Al(2)O(3) support. After the deposition, the synthesized Al(2)O(3) support was heated and air was injected again to observe behaviors of the deposited AuPd nano-particles at elevated temperatures in the aerial environment. Behaviors of the AuPd nano-particles such as coalescence, segmentation and diffusion to the Al(2)O(3) support were dynamically observed at atomic level high resolution.

Microstructural observation of fuel cell catalyst inks by Cryo-SEM and Cryo-TEM.

PubMed

Shimanuki, Junichi; Takahashi, Shinichi; Tohma, Hajime; Ohma, Atsushi; Ishihara, Ayumi; Ito, Yoshiko; Nishino, Yuri; Miyazawa, Atsuo

2017-06-01

In order to improve the electricity generation performance of fuel cell electric vehicles, it is necessary to optimize the microstructure of the catalyst layer of a polymer electrolyte fuel cell. The catalyst layer is formed by a wet coating process using catalyst inks. Therefore, it is very important to observe the microstructure of the catalyst ink. In this study, the morphology of carbon-supported platinum (Pt/C) particles in catalyst inks with a different solvent composition was investigated by cryogenic scanning electron microscopy (cryo-SEM). In addition, the morphology of the ionomer, which presumably influences the formation of agglomerated Pt/C particles in a catalyst ink, was investigated by cryogenic transmission electron microscopy (cryo-TEM). The results of a cryo-SEM observation revealed that the agglomerated Pt/C particles tended to become coarser with a higher 1-propanol (NPA) weight fraction. The results of a cryo-TEM observation indicated that the actual ionomer dispersion in a catalyst ink formed a network structure different from that of the ionomer in the solvent. © The Author 2017. Published by Oxford University Press on behalf of The Japanese Society of Microscopy. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

Polygonal crack patterns by drying thin films under quasi-two-dimensional confinement

NASA Astrophysics Data System (ADS)

Ma, Xiaolei; Lowensohn, Janna; Burton, Justin

Cracks patterns such as T/Y junction cracks in dried mud are ubiquitous in nature. Although the conditions for cracking in solids is well-known, cracks in colloidal and granular systems are more complex. Here we report the formations of polygonal cracks by drying thin films of corn starch ( 10 μm in diameter) under quasi-2D confinement. We find there are two drying stages before the films are completely dried. Initially, a compaction front invades throughout the film. Then, a second drying stage ''percolates'' throughout the film with a characteristic branching pattern, leading to a dense packing of particles connected by liquid capillary bridges. Finally, polygonal cracks appear as the remaining liquid dries. The same drying kinetics occur for films with different thickness, h, except that fractal-like fracture patterns form in thin films, where the thickness is comparable to the particle size, while polygons form in thick films with many layers of particles. We also find that the average area of the polygons, A, in fully dried films scales with the thickness, A hβ , where β 1 . 5 , and the prefactor depends on the initial packing fraction of the suspension. This form is consistent with a simple energy balance criterion for crack formation.

Nanoscale Catalysts for NMR Signal Enhancement by Reversible Exchange

PubMed Central

2015-01-01

Two types of nanoscale catalysts were created to explore NMR signal enhancement via reversible exchange (SABRE) at the interface between heterogeneous and homogeneous conditions. Nanoparticle and polymer comb variants were synthesized by covalently tethering Ir-based organometallic catalysts to support materials composed of TiO2/PMAA (poly(methacrylic acid)) and PVP (polyvinylpyridine), respectively, and characterized by AAS, NMR, and DLS. Following parahydrogen (pH2) gas delivery to mixtures containing one type of “nano-SABRE” catalyst particle, a target substrate, and ethanol, up to ∼(−)40-fold and ∼(−)7-fold 1H NMR signal enhancements were observed for pyridine substrates using the nanoparticle and polymer comb catalysts, respectively, following transfer to high field (9.4 T). These enhancements appear to result from intact particles and not from any catalyst molecules leaching from their supports; unlike the case with homogeneous SABRE catalysts, high-field (in situ) SABRE effects were generally not observed with the nanoscale catalysts. The potential for separation and reuse of such catalyst particles is also demonstrated. Taken together, these results support the potential utility of rational design at molecular, mesoscopic, and macroscopic/engineering levels for improving SABRE and HET-SABRE (heterogeneous-SABRE) for applications varying from fundamental studies of catalysis to biomedical imaging. PMID:26185545

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.

Process for the production of liquid hydrocarbons

DOEpatents

Bhatt, Bharat Lajjaram; Engel, Dirk Coenraad; Heydorn, Edward Clyde; Senden, Matthijis Maria Gerardus

2006-06-27

The present invention concerns a process for the preparation of liquid hydrocarbons which process comprises contacting synthesis gas with a slurry of solid catalyst particles and a liquid in a reactor vessel by introducing the synthesis gas at a low level into the slurry at conditions suitable for conversion of the synthesis gas into liquid hydrocarbons, the solid catalyst particles comprising a catalytic active metal selected from cobalt or iron on a porous refractory oxide carrier, preferably selected from silica, alumina, titania, zirconia or mixtures thereof, the catalyst being present in an amount between 10 and 40 vol. percent based on total slurry volume liquids and solids, and separating liquid material from the solid catalyst particles by using a filtration system comprising an asymmetric filtration medium (the selective side at the slurry side), in which filtration system the average pressure differential over the filtration medium is at least 0.1 bar, in which process the particle size distribution is such that at least a certain amount of the catalyst particles is smaller than the average pore size of the selective layer of the filtration medium. The invention also comprises an apparatus to carry out the process described above.

Stable carbonous catalyst particles and method for making and utilizing same

DOEpatents

Ganguli, Partha S.; Comolli, Alfred G.

2005-06-14

Stable carbonous catalyst particles composed of an inorganic catalytic metal/metal oxide powder and a carbonaceous binder material are formed having a basic inner substantially uniform-porous carbon coating of the catalytic powder, and may include an outer porous carbon coating layer. Suitable inorganic catalytic powders include zinc-chromite (ZnO/Cr.sub.2 03) and suitable carbonaceous liquid binders having molecular weight of 200-700 include partially polymerized furfuryl alcohol, which are mixed together, shaped and carbonized and partially oxidized at elevated temperature. Such stable carbonous catalyst particles such as 0.020-0.100 inch (0.51-2.54 mm) diameter extrudates, have total carbon content of 2-25 wt. % and improved crush strength of 1.0-5 1b/mn, 50-300 m.sup.2 /g surface area, and can be advantageously utilized in fixed bed or ebullated/fluidized bed reactor operations. This invention also includes method steps for making the stable carbonous catalyst particles having improved particle strength and catalytic activity, and processes for utilizing the active stable carbonous carbon-coated catalysts such as for syn-gas reactions in ebullated/fluidized bed reactors for producing alcohol products and Fischer-Tropsch synthesis liquid products.

Nanocrystalline Iron-Ore-Based Catalysts for Fischer-Tropsch Synthesis.

PubMed

Yong, Seok; Park, Ji Chan; Lee, Ho-Tae; Yang, Jung-Il; Hong, SungJun; Jung, Heon; Chun, Dong Hyun

2016-02-01

Nanocrystalline iron ore particles were fabricated by a wet-milling process using an Ultra Apex Mill, after which they were used as raw materials of iron-based catalysts for low-temperature Fischer-Tropsch synthesis (FTS) below 280 degrees C, which usually requires catalysts with a high surface area, a large pore volume, and a small crystallite size. The wet-milling process using the Ultra Apex Mill effectively destroyed the initial crystallite structure of the natural iron ores of several tens to hundreds of nanometers in size, resulting in the generation of nanocrystalline iron ore particles with a high surface area and a large pore volume. The iron-ore-based catalysts prepared from the nanocrystalline iron ore particles effectively catalyzed the low-temperature FTS, displaying a high CO conversion (about 90%) and good C5+ hydrocarbon productivity (about 0.22 g/g(cat)(-h)). This demonstrates the feasibility of using the iron-ore-based catalysts as inexpensive and disposable catalysts for the low-temperature FTS.

Improved Oxygen Reduction Activity and Durability of Dealloyed PtCo x Catalysts for Proton Exchange Membrane Fuel Cells: Strain, Ligand, and Particle Size Effects.

PubMed

Jia, Qingying; Caldwell, Keegan; Strickland, Kara; Ziegelbauer, Joseph M; Liu, Zhongyi; Yu, Zhiqiang; Ramaker, David E; Mukerjee, Sanjeev

2015-01-02

The development of active and durable catalysts with reduced platinum content is essential for fuel cell commercialization. Herein we report that the dealloyed PtCo/HSC and PtCo 3 /HSC nanoparticle (NP) catalysts exhibit the same levels of enhancement in oxygen reduction activity (~4-fold) and durability over pure Pt/C NPs. Surprisingly, ex situ high-angle annular dark field scanning transmission electron microscopy (HAADF STEM) shows that the bulk morphologies of the two catalysts are distinctly different: D-PtCo/HSC catalyst is dominated by NPs with solid Pt shells surrounding a single ordered PtCo core; however, the D-PtCo 3 /HSC catalyst is dominated by NPs with porous Pt shells surrounding multiple disordered PtCo cores with local concentration of Co. In situ X-ray absorption spectroscopy (XAS) reveals that these two catalysts possess similar Pt-Pt and Pt-Co bond distances and Pt coordination numbers (CNs), despite their dissimilar morphologies. The similar activity of the two catalysts is thus ascribed to their comparable strain, ligand, and particle size effects. Ex situ XAS performed on D-PtCo 3 /HSC under different voltage cycling stage shows that the continuous dissolution of Co leaves behind the NPs with a Pt-like structure after 30k cycles. The attenuated strain and/or ligand effects caused by Co dissolution are presumably counterbalanced by the particle size effects with particle growth, which likely accounts for the constant specific activity of the catalysts along with voltage cycling.

Improved Oxygen Reduction Activity and Durability of Dealloyed PtCo x Catalysts for Proton Exchange Membrane Fuel Cells: Strain, Ligand, and Particle Size Effects

DOE PAGES

Jia, Qingying; Caldwell, Keegan; Strickland, Kara; ...

2014-11-19

The development of active and durable catalysts with reduced platinum content is essential for fuel cell commercialization. Here in this paper, we report that the dealloyed PtCo/HSC and PtCo 3/HSC nanoparticle (NP) catalysts exhibit the same levels of enhancement in oxygen reduction activity (~4-fold) and durability over pure Pt/C NPs. Surprisingly, ex situ high-angle annular dark field scanning transmission electron microscopy (HAADF STEM) shows that the bulk morphologies of the two catalysts are distinctly different: D-PtCo/HSC catalyst is dominated by NPs with solid Pt shells surrounding a single ordered PtCo core; however, the D-PtCo 3/HSC catalyst is dominated by NPsmore » with porous Pt shells surrounding multiple disordered PtCo cores with local concentration of Co. In situ X-ray absorption spectroscopy (XAS) reveals that these two catalysts possess similar Pt–Pt and Pt–Co bond distances and Pt coordination numbers (CNs), despite their dissimilar morphologies. The similar activity of the two catalysts is thus ascribed to their comparable strain, ligand, and particle size effects. Ex situ XAS performed on D-PtCo 3/HSC under different voltage cycling stage shows that the continuous dissolution of Co leaves behind the NPs with a Pt-like structure after 30k cycles. The attenuated strain and/or ligand effects caused by Co dissolution are presumably counterbalanced by the particle size effects with particle growth, which likely accounts for the constant specific activity of the catalysts along with voltage cycling.« less

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.

Multiscale Modeling of Damage Processes in Aluminum Alloys: Grain-Scale Mechanisms

NASA Technical Reports Server (NTRS)

Hochhalter, J. D.; Veilleux, M. G.; Bozek, J. E.; Glaessgen, E. H.; Ingraffea, A. R.

2008-01-01

This paper has two goals related to the development of a physically-grounded methodology for modeling the initial stages of fatigue crack growth in an aluminum alloy. The aluminum alloy, AA 7075-T651, is susceptible to fatigue cracking that nucleates from cracked second phase iron-bearing particles. Thus, the first goal of the paper is to validate an existing framework for the prediction of the conditions under which the particles crack. The observed statistics of particle cracking (defined as incubation for this alloy) must be accurately predicted to simulate the stochastic nature of microstructurally small fatigue crack (MSFC) formation. Also, only by simulating incubation of damage in a statistically accurate manner can subsequent stages of crack growth be accurately predicted. To maintain fidelity and computational efficiency, a filtering procedure was developed to eliminate particles that were unlikely to crack. The particle filter considers the distributions of particle sizes and shapes, grain texture, and the configuration of the surrounding grains. This filter helps substantially reduce the number of particles that need to be included in the microstructural models and forms the basis of the future work on the subsequent stages of MSFC, crack nucleation and microstructurally small crack propagation. A physics-based approach to simulating fracture should ultimately begin at nanometer length scale, in which atomistic simulation is used to predict the fundamental damage mechanisms of MSFC. These mechanisms include dislocation formation and interaction, interstitial void formation, and atomic diffusion. However, atomistic simulations quickly become computationally intractable as the system size increases, especially when directly linking to the already large microstructural models. Therefore, the second goal of this paper is to propose a method that will incorporate atomistic simulation and small-scale experimental characterization into the existing multiscale framework. At the microscale, the nanoscale mechanics are represented within cohesive zones where appropriate, i.e. where the mechanics observed at the nanoscale can be represented as occurring on a plane such as at grain boundaries or slip planes at a crack front. Important advancements that are yet to be made include: 1. an increased fidelity in cohesive zone modeling; 2. a means to understand how atomistic simulation scales with time; 3. a new experimental methodology for generating empirical models for CZMs and emerging materials; and 4. a validation of simulations of the damage processes at the nano-micro scale. With ever-increasing computer power, the long-term ability to employ atomistic simulation for the prognosis of structural components will not be limited by computation power, but by our lack of knowledge in incorporating atomistic models into simulations of MSFC into a multiscale framework.

MicroChannel Reactors for ISRU Applications Using Nanofabricated Catalysts

NASA Astrophysics Data System (ADS)

Carranza, Susana; Makel, Darby B.; Vander Wal, Randall L.; Berger, Gordon M.; Pushkarev, Vladimir V.

2006-01-01

With the new direction of NASA to emphasize the exploration of the Moon, Mars and beyond, quick development and demonstration of efficient systems for In-Situ Resources Utilization (ISRU) is more critical and timely than ever before. Affordable planning and execution of prolonged manned space missions depend upon the utilization of local resources and the waste products which are formed in manned spacecraft and surface bases. This paper presents current development of miniaturized chemical processing systems that combine microchannel reactor design with nanofabricated catalysts. Carbon nanotubes (CNT) are used to produce a nanostructure within microchannel reactors, as support for catalysts. By virtue of their nanoscale dimensions, nanotubes geometrically restrict the catalyst particle size that can be supported upon the tube walls. By confining catalyst particles to sizes smaller than the CNT diameter, a more uniform catalyst particle size distribution may be maintained. The high dispersion permitted by the vast surface area of the nanoscale material serves to retain the integrity of the catalyst by reducing sintering or coalescence. Additionally, catalytic efficiency increases with decreasing catalyst particle size (reflecting higher surface area per unit mass) while chemical reactivity frequently is enhanced at the nanoscale. Particularly significant is the catalyst exposure. Rather than being confined within a porous material or deposited upon a 2-d surface, the catalyst is fully exposed to the reactant gases by virtue of the nanofabricated support structure. The combination of microchannel technology with nanofabricated catalysts provides a synergistic effect, enhancing both technologies with the potential to produce much more efficient systems than either technology alone. The development of highly efficient microchannel reactors will be applicable to multiple ISRU programs. By selection of proper nanofabricated catalysts, the microchannel reactors can be designed for the processes that generate the most benefit for each mission, from early demonstration missions to long term settlements.

High-performance bimetallic alloy catalyst using Ni and N co-doped composite carbon for the oxygen electro-reduction.

PubMed

Jung, Won Suk

2018-03-15

In this study, a novel synthesis method for the bimetallic alloy catalyst is reported, which is subsequently used as an oxygen reduction catalyst in polymer electrolyte membrane fuel cells (PEMFCs). The support prepared from the Ni-chelate complex shows a mesoporous structure with a specific surface area of ca. 400 m 2  g -1 indicating the suitable support for PEMFC applications. Ethylenediamine is converted to the nitrogen and carbon layers to protect the Ni particles which will diffuse into the Pt lattice at 800 °C. The PtNi/NCC catalyst with PtNi cores and Pt-rich shells is successfully formed when acid-treated as evidenced by line scan profiles. The catalyst particles thus synthesized are well-dispersed on the N-doped carbon support, while the average particle size is ca. 3 nm. In the PEMFC test, the maximum power density of the PtNi/NCC catalyst shows approximately 25% higher than that of the commercial Pt/C catalyst. The mass activity of the PtNi/NCC catalyst showed approximately 3-fold higher than that of the commercial Pt/C catalyst. The mass activity strongly depends on the ratio of Pt to Ni since the strain effect can be strong for catalysts due to the mismatch of lattice parameters of the Ni and Pt. Copyright © 2017 Elsevier Inc. All rights reserved.

Bio-oil hydrodeoxygenation catalysts produced using strong electrostatic adsorption

USDA-ARS?s Scientific Manuscript database

We synthesized hydrothermally stable metal catalysts with controlled particle size and distribution, with the goal of determining which catalyst(s) can selectively catalyze the production of aromatics from bio-oil (from pyrolysis of biomass). Both precious and base transition metal catalysts (Ru, Pt...

On-line prognosis of fatigue crack propagation based on Gaussian weight-mixture proposal particle filter.

PubMed

Chen, Jian; Yuan, Shenfang; Qiu, Lei; Wang, Hui; Yang, Weibo

2018-01-01

Accurate on-line prognosis of fatigue crack propagation is of great meaning for prognostics and health management (PHM) technologies to ensure structural integrity, which is a challenging task because of uncertainties which arise from sources such as intrinsic material properties, loading, and environmental factors. The particle filter algorithm has been proved to be a powerful tool to deal with prognostic problems those are affected by uncertainties. However, most studies adopted the basic particle filter algorithm, which uses the transition probability density function as the importance density and may suffer from serious particle degeneracy problem. This paper proposes an on-line fatigue crack propagation prognosis method based on a novel Gaussian weight-mixture proposal particle filter and the active guided wave based on-line crack monitoring. Based on the on-line crack measurement, the mixture of the measurement probability density function and the transition probability density function is proposed to be the importance density. In addition, an on-line dynamic update procedure is proposed to adjust the parameter of the state equation. The proposed method is verified on the fatigue test of attachment lugs which are a kind of important joint components in aircraft structures. Copyright © 2017 Elsevier B.V. All rights reserved.

Nanotransfer and nanoreplication using deterministically grown sacrificial nanotemplates

DOEpatents

Melechko, Anatoli V [Oak Ridge, TN; McKnight, Timothy E. , Guillorn, Michael A.; Ilic, Bojan [Ithaca, NY; Merkulov, Vladimir I [Knoxville, TN; Doktycz, Mitchel J [Knoxville, TN; Lowndes, Douglas H [Knoxville, TN; Simpson, Michael L [Knoxville, TN

2011-05-17

Methods, manufactures, machines and compositions are described for nanotransfer and nanoreplication using deterministically grown sacrificial nanotemplates. A method includes depositing a catalyst particle on a surface of a substrate to define a deterministically located position; growing an aligned elongated nanostructure on the substrate, an end of the aligned elongated nanostructure coupled to the substrate at the deterministically located position; coating the aligned elongated nanostructure with a conduit material; removing a portion of the conduit material to expose the catalyst particle; removing the catalyst particle; and removing the elongated nanostructure to define a nanoconduit.

Filamentous carbon particles for cleaning oil spills and method of production

DOEpatents

Muradov, Nazim

2010-04-06

A compact hydrogen generator is coupled to or integrated with a fuel cell for portable power applications. Hydrogen is produced via thermocatalytic decomposition (cracking, pyrolysis) of hydrocarbon fuels in oxidant-free environment. The apparatus can utilize a variety of hydrocarbon fuels, including natural gas, propane, gasoline, kerosene, diesel fuel, crude oil (including sulfurous fuels). The hydrogen-rich gas produced is free of carbon oxides or other reactive impurities, so it could be directly fed to any type of a fuel cell. The catalysts for hydrogen production in the apparatus are carbon-based or metal-based materials and doped, if necessary, with a sulfur-capturing agent. Additionally disclosed are two novel processes for the production of two types of carbon filaments, and a novel filamentous carbon product. The hydrogen generator can be conveniently integrated with high temperature fuel cells to produce an efficient and self-contained source of electrical power.

Sintering of catalytic nanoparticles: particle migration or Ostwald ripening?

PubMed

Hansen, Thomas W; Delariva, Andrew T; Challa, Sivakumar R; Datye, Abhaya K

2013-08-20

Metal nanoparticles contain the active sites in heterogeneous catalysts, which are important for many industrial applications including the production of clean fuels, chemicals and pharmaceuticals, and the cleanup of exhaust from automobiles and stationary power plants. Sintering, or thermal deactivation, is an important mechanism for the loss of catalyst activity. This is especially true for high temperature catalytic processes, such as steam reforming, automotive exhaust treatment, or catalytic combustion. With dwindling supplies of precious metals and increasing demand, fundamental understanding of catalyst sintering is very important for achieving clean energy and a clean environment, and for efficient chemical conversion processes with atom selectivity. Scientists have proposed two mechanisms for sintering of nanoparticles: particle migration and coalescence (PMC) and Ostwald ripening (OR). PMC involves the mobility of particles in a Brownian-like motion on the support surface, with subsequent coalescence leading to nanoparticle growth. In contrast, OR involves the migration of adatoms or mobile molecular species, driven by differences in free energy and local adatom concentrations on the support surface. In this Account, we divide the process of sintering into three phases. Phase I involves rapid loss in catalyst activity (or surface area), phase II is where sintering slows down, and phase III is where the catalyst may reach a stable performance. Much of the previous work is based on inferences from catalysts that were observed before and after long term treatments. While the general phenomena can be captured correctly, the mechanisms cannot be determined. Advancements in the techniques of in situ TEM allow us to observe catalysts at elevated temperatures under working conditions. We review recent evidence obtained via in situ methods to determine the relative importance of PMC and OR in each of these phases of catalyst sintering. The evidence suggests that, in phase I, OR is responsible for the rapid loss of activity that occurs when particles are very small. Surprisingly, very little PMC is observed in this phase. Instead, the rapid loss of activity is caused by the disappearance of the smallest particles. These findings are in good agreement with representative atomistic simulations of sintering. In phase II, sintering slows down since the smallest particles have disappeared. We now see a combination of PMC and OR, but do not fully understand the relative contribution of each of these processes to the overall rates of sintering. In phase III, the particles have grown large and other parasitic phenomena, such as support restructuring, can become important, especially at high temperatures. Examining the evolution of particle size and surface area with time, we do not see a stable or equilibrium state, especially for catalysts operating at elevated temperatures. In conclusion, the recent literature, especially on in situ studies, shows that OR is the dominant process causing the growth of nanoparticle size. Consequently, this leads to the loss of surface area and activity. While particle migration could be controlled through suitable structuring of catalyst supports, it is more difficult to control the mobility of atomically dispersed species. These insights into the mechanisms of sintering could help to develop sinter-resistant catalysts, with the ultimate goal of designing catalysts that are self-healing.

Effective Thermal Conductivity of Graphite Materials with Cracks

NASA Astrophysics Data System (ADS)

Pestchaanyi, S. E.; Landman, I. S.

The dependence of effective thermal diffusivity on temperature caused by volumetric cracks is modelled for macroscopic graphite samples using the three-dimensional thermomechanics code Pegasus-3D. At high off-normal heat loads typical of the divertor armour, thermostress due to the anisotropy of graphite grains is much larger than that due to the temperature gradient. Numerical simulation demonstrated that the volumetric crack density both in fine grain graphites and in the CFC matrix depends mainly on the local sample temperature, not on the temperature gradient. This allows to define an effective thermal diffusivity for graphite with cracks. The results obtained are used to explain intense cracking and particle release from carbon based materials under electron beam heat load. Decrease of graphite thermal diffusivity with increase of the crack density explains particle release mechanism in the experiments with CFC where a clear energy threshold for the onset of particle release has been observed in J. Linke et al. Fusion Eng. Design, in press, Bazyler et al., these proceedings. Surface temperature measurement is necessary to calibrate the Pegasus-3D code for simulation of ITER divertor armour brittle destruction.

Strategies for the synthesis of supported gold palladium nanoparticles with controlled morphology and composition.

PubMed

Hutchings, Graham J; Kiely, Christopher J

2013-08-20

The discovery that supported gold nanoparticles are exceptionally effective catalysts for redox reactions has led to an explosion of interest in gold nanoparticles. In addition, incorporating a second metal as an alloy with gold can enhance the catalyst performance even more. The addition of small amounts of gold to palladium, in particular, and vice versa significantly enhances the activity of supported gold-palladium nanoparticles as redox catalysts through what researchers believe is an electronic effect. In this Account, we describe and discuss methodologies for the synthesis of supported gold-palladium nanoparticles and their use as heterogeneous catalysts. In general, three key challenges need to be addressed in the synthesis of bimetallic nanoparticles: (i) control of the particle morphology, (ii) control of the particle size distribution, and (iii) control of the nanoparticle composition. We describe three methodologies to address these challenges. First, we discuss the relatively simple method of coimpregnation. Impregnation allows control of particle morphology during alloy formation but does not control the particle compositions or the particle size distribution. Even so, we contend that this method is the best preparation method in the catalyst discovery phase of any project, since it permits the investigation of many different catalyst structures in one experiment, which may aid the identification of new catalysts. A second approach, sol-immobilization, allows enhanced control of the particle size distribution and the particle morphology, but control of the composition of individual nanoparticles is not possible. Finally, a modified impregnation method can allow the control of all three of these crucial parameters. We discuss the effect of the different methodologies on three redox reactions: benzyl alcohol oxidation, toluene oxidation, and the direct synthesis of hydrogen peroxide. We show that the coimpregnation method provides the best reaction selectivity for benzyl alcohol oxidation and the direct synthesis of hydrogen peroxide. However, because of the reaction mechanism, the sol-immobilzation method gives very active and selective catalysts for toluene oxidation. We discuss the possible nature of the preferred active structures of the supported nanoparticles for these reactions. This paper is based on the IACS Heinz Heinemann Award Lecture entitled "Catalysis using gold nanoparticles" which was given in Munich in July 2012.

Simple preparation of Fenton catalyst@bacterial cellulose for waste water treatment

NASA Astrophysics Data System (ADS)

Wibowo, Arie; Febi Indrawan, Radian; Triadhi, Untung; Hasdi Aimon, Akfiny; Iskandar, Ferry; Ardy, Husaini

2018-02-01

Heterogeneous fenton catalyst is one of the attractive technologies for destruction of persistent and non-biodegradable pollutant in wastewater, because it can be used in wide range of pH and recyclable. Herein, commercial bacterial celluloses (BCs) were used as an alternative support of fenton catalyst to improve their catalytic activity. Scanning Electron Microscope (SEM) observations indicated that the presence of BCs and decreasing precursor concentration might promote formation of smaller particle sizes of catalyst from 3.5 μm of bare catalyst to 0.7 μm of catalyst@BC. UV-vis measurement showed that fast degradation of dyes with half-time degradation at around 25 min was observed in sample using catalyst@BCs with precursor concentration of 0.01 M. Successful preparation of heterogeneous fenton catalyst with smaller particle size and better catalytic activity is important for their application in wastewater treatment.

Attrition and carbon formation on iron catalysts

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

Kohler, S.D.; Harrington, M.S.; Jackson, N.B.

1994-08-01

A serious engineering problem that needs to be addressed in the scale-up of slurry-phase, Fischer-Tropsch reactors is attrition of the precipitated iron catalyst. Attrition, which can break down the catalyst into particles too small to filter, results from both mechanical and chemical forces. This study examines the chemical causes of attrition in iron catalysts. A bench-scale, slurry-phase CSTR is used to simulate operating conditions that lead to attrition of the catalyst. The average particle size and size distribution of the catalyst samples are used to determine the effect of slurry temperature, reducing gas, gas flow rate and time upon attritionmore » of the catalyst. Carbon deposition, a possible contributing factor to attrition, has been examined using gravimetric analysis and TEM. Conditions affecting the rate of carbon deposition have been compared to those leading to attrition of the precipitated iron catalyst.« less

Catalytic Fast Pyrolysis of Cellulose Using Nano Zeolite and Zeolite/Matrix Catalysts in a GC/Micro-Pyrolyzer.

PubMed

Lee, Kyong-Hwan

2016-05-01

Cellulose, as a model compound of biomass, was catalyzed over zeolite (HY,.HZSM-5) and zeolite/matrix (HY/Clay, HM/Clay) in a GC/micro-pyrolyzer at 500 degrees C, to produce the valuable products. The catalysts used were pure zeolite and zeolite/matrix including 20 wt% matrix content, which were prepared into different particle sizes (average size; 0.1 mm, 1.6 mm) to study the effect of the particle size of the catalyst for the distribution of product yields. Catalytic pyrolysis had much more volatile products as light components and less content of sugars than pyrolysis only. This phenomenon was strongly influenced by the particle size of the catalyst in catalytic fast pyrolysis. Also, in zeolite and zeolite/matrix catalysts the zeolite type gave the dominant impact on the distribution of product yields.

Controllable synthesis of Co3O4 nanocrystals as efficient catalysts for oxygen reduction reaction

NASA Astrophysics Data System (ADS)

Li, Baoying; Zhang, Yihe; Du, Ruifeng; Liu, Lei; Yu, Xuelian

2018-03-01

The electrochemical oxygen reduction reaction (ORR) has received great attention due to its importance in fuel cells and metal-air batteries. Here, we present a simple approach to prepare non-noble metal catalyst-Co3O4 nanocrystals (NCs). The particle size and shape were simply controlled by different types and concentrations of metal precursor. Furthermore, different sizes and shapes of Co3O4 NCs are explored as electrocatalysts for ORR, and it has been observed that particles with a similar shape, and smaller particle size led to greater catalytic current densities because of the greater surface area. For particles with a comparable size, the shape or crystalline structure governed the activity of the electrocatalytic reactions. Most importantly, the 9 nm-Co3O4 were demonstrated to act as low-cost catalysts for the ORR with a similar performance to that of Pt catalysts.

Advanced STEM microanalysis of bimetallic nanoparticle catalysts

NASA Astrophysics Data System (ADS)

Lyman, Charles E.; Dimick, Paul S.

2012-05-01

Individual particles within bimetallic nanoparticle populations are not always identical, limiting the usefulness of bulk analysis techniques such as EXAFS. The scanning transmission electron microscope (STEM) is the only instrument able to characterize supported nanoparticle populations on a particle-by-particle basis. Quantitative elemental analyses of sub-5-nm particles reveal phase separations among particles and surface segregation within particles. This knowledge can lead to improvements in bimetallic catalysts. Advanced STEMs with field-emission guns, aberration-corrected optics, and efficient signal detection systems allow analysis of sub-nanometer particles.

Lagrangian Approach to Study Catalytic Fluidized Bed Reactors

NASA Astrophysics Data System (ADS)

Madi, Hossein; Hossein Madi Team; Marcelo Kaufman Rechulski Collaboration; Christian Ludwig Collaboration; Tilman Schildhauer Collaboration

2013-03-01

Lagrangian approach of fluidized bed reactors is a method, which simulates the movement of catalyst particles (caused by the fluidization) by changing the gas composition around them. Application of such an investigation is in the analysis of the state of catalysts and surface reactions under quasi-operando conditions. The hydrodynamics of catalyst particles within a fluidized bed reactor was studied to improve a Lagrangian approach. A fluidized bed methanation employed in the production of Synthetic Natural Gas from wood was chosen as the case study. The Lagrangian perspective was modified and improved to include different particle circulation patterns, which were investigated through this study. Experiments were designed to evaluate the concepts of the model. The results indicate that the setup is able to perform the designed experiments and a good agreement between the simulation and the experimental results were observed. It has been shown that fluidized bed reactors, as opposed to fixed beds, can be used to avoid the deactivation of the methanation catalyst due to carbon deposits. Carbon deposition on the catalysts tested with the Lagrangian approach was investigated by temperature programmed oxidation (TPO) analysis of ex-situ catalyst samples. This investigation was done to identify the effects of particles velocity and their circulation patterns on the amount and type of deposited carbon on the catalyst surface. Ecole Polytechnique Federale de Lausanne(EPFL), Paul Scherrer Institute (PSI)

Stabilization of Hydrogen Production via Methanol Steam Reforming in Microreactor by Al2O3 Nano-Film Enhanced Catalyst Adhesion.

PubMed

Jeong, Heondo; Na, Jeong-Geol; Jang, Min Su; Ko, Chang Hyun

2016-05-01

In hydrogen production by methanol steam reforming reaction with microchannel reactor, Al2O3 thin film formed by atomic layer deposition (ALD) was introduced on the surface of microchannel reactor prior to the coating of catalyst particles. Methanol conversion rate and hydrogen production rate, increased in the presence of Al2O3 thin film. Over-view and cross-sectional scanning electron microscopy study showed that the adhesion between catalyst particles and the surface of microchannel reactor enhanced due to the presence of Al2O3 thin film. The improvement of hydrogen production rate inside the channels of microreactor mainly came from the stable fixation of catalyst particles on the surface of microchannels.

A parametric study of the dynamic failure of energetic composites

NASA Astrophysics Data System (ADS)

Tanasoiu, Bogdan; Koslowski, Marisol

2017-09-01

Heating by frictional sliding of cracks is often considered to be one of the most important causes of localized melting and ignition in solid explosives. Furthermore, recent high speed X-ray phase contrast experiments on energetic composites under dynamic compression [Parab et al., Appl. Phys. Lett. 109(13) (2016)] show that most fracture events appear inside the particles. Initial cracks develop in regions where particles are close, and widespread fragmentation is observed in the interior of the particles as the stress waves propagate through the sample. However, most simulations have focused on interface debonding of energetic composites and, in general, do not include fracture of the particles explicitly. A phase field damage approach is used to model the dynamic response of a system of cyclotetramethylene-tetranitramine particles embedded in a Sylgard matrix. The simulations show several damage mechanisms observed in the experiments. The effects of the energy release rate and the initial crack distribution on the energy dissipation due to fracture are studied. The numerical results confirm that initial cracks play an important role in the evolution of damage, energy dissipation and consequently, the formation of hot-spots.

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.

Attrition of precipitated iron Fischer-Tropsch catalysts

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

Datye, A.K.; Reardon, J.; Hanprasopwattana, A.

1996-12-31

Precipitated Iron catalysts used in slurry phase bubble column reactors are known to undergo attrition during use. The attrition reduces the lifetime of the catalyst as well as causing problems in separating the product liquids from the catalyst. In this study, the authors have investigated the underlying mechanisms that lead to attrition in precipitated iron catalysts. They have discovered that attrition takes place on two length scales. On the macro scale, attrition is caused by the break-up of the weak agglomerates that constitute this catalyst into individual crystallites. Addition of binders such as kaolin does not help significantly in strengtheningmore » the catalyst particles. In addition, there is a second process leading to nanoscale attrition that is caused by the break-up of individual iron oxide crystallites into nano particles of iron carbide as the catalyst is activated for reaction. Design of attrition resistant F-T catalysts must consider these two modes of catalyst attrition. Preliminary work in the laboratory directed at improving the attrition resistance of precipitated iron catalysts will also be described in this paper.« less

Integrated current collector and catalyst support

DOEpatents

Bregoli, Lawrence J.

1985-10-22

An integrated current collecting electrode for a molten carbonate fuel cell includes a corrugated metal conductive strip positioned in contact with a catalyst layer. The corrugations of the metal strip form a plurality of gas channels immediately adjacent the surface of the catalyst through which a reactant gas flows. Each channel is filled with a particulate material to maintain separation between the metal strip and the catalyst in ensuring gas channel integrity. The catalyst may be in the form of a compacted, particulate material provided the particle size of the material within the gas channels is larger than that of the catalyst particles to prevent catalyst migration to the metal conductor and provide reactant gas access to the catalyst layer. The gas channels formed by the corrugations of the metal strip are arranged in an offset pattern along the direction of gas flow for improved reactant gas distribution to the catalyst layer. The particulate material positioned within the gas flow channels may be a ceramic conductor such as a perovskite or a spinel for enhanced current collection.

Integrated current collector and catalyst support

DOEpatents

Bregoli, L.J.

1984-10-17

An integrated current collecting electrode for a molten carbonate fuel cell includes a corrugated metal conductive strip positioned in contact with a catalyst layer. The corrugations of the metal strip form a plurality of gas channels immediately adjacent the surface of the catalyst through which a reactant gas flows. Each channel is filled with a particulate material to maintain separation between the metal strip and the catalyst in ensuring gas channel integrity. The catalyst may be in the form of a compacted, particulate material provided the particle size of the material within the gas channels is larger than that of the catalyst particles to prevent catalyst migration to the metal conductor and provide reactant gas access to the catalyst layer. The gas channels formed by the corrugations of the metal strip are arranged in an offset pattern along the direction of gas flow for improved reactant gas distribution to the catalyst layer. The particulate material positioned within the gas flow channels may be a ceramic conductor such as a perovskite or a spinel for enhanced current collection.

Direct observation of morphological evolution of a catalyst during carbon nanotube forest growth: new insights into growth and growth termination

NASA Astrophysics Data System (ADS)

Jeong, Seojeong; Lee, Jaegeun; Kim, Hwan-Chul; Hwang, Jun Yeon; Ku, Bon-Cheol; Zakharov, Dmitri N.; Maruyama, Benji; Stach, Eric A.; Kim, Seung Min

2016-01-01

In this study, we develop a new methodology for transmission electron microscopy (TEM) analysis that enables us to directly investigate the interface between carbon nanotube (CNT) arrays and the catalyst and support layers for CNT forest growth without any damage induced by a post-growth TEM sample preparation. Using this methodology, we perform in situ and ex situ TEM investigations on the evolution of the morphology of the catalyst particles and observe the catalyst particles to climb up through CNT arrays during CNT forest growth. We speculate that the lifted catalysts significantly affect the growth and growth termination of CNT forests along with Ostwald ripening and sub-surface diffusion. Thus, we propose a modified growth termination model which better explains various phenomena related to the growth and growth termination of CNT forests.In this study, we develop a new methodology for transmission electron microscopy (TEM) analysis that enables us to directly investigate the interface between carbon nanotube (CNT) arrays and the catalyst and support layers for CNT forest growth without any damage induced by a post-growth TEM sample preparation. Using this methodology, we perform in situ and ex situ TEM investigations on the evolution of the morphology of the catalyst particles and observe the catalyst particles to climb up through CNT arrays during CNT forest growth. We speculate that the lifted catalysts significantly affect the growth and growth termination of CNT forests along with Ostwald ripening and sub-surface diffusion. Thus, we propose a modified growth termination model which better explains various phenomena related to the growth and growth termination of CNT forests. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr05547d

Discerning the Location and Nature of Coke Deposition from Surface to Bulk of Spent Zeolite Catalysts

NASA Astrophysics Data System (ADS)

Devaraj, Arun; Vijayakumar, Murugesan; Bao, Jie; Guo, Mond F.; Derewinski, Miroslaw A.; Xu, Zhijie; Gray, Michel J.; Prodinger, Sebastian; Ramasamy, Karthikeyan K.

2016-11-01

The formation of carbonaceous deposits (coke) in zeolite pores during catalysis leads to temporary deactivation of catalyst, necessitating regeneration steps, affecting throughput, and resulting in partial permanent loss of catalytic efficiency. Yet, even to date, the coke molecule distribution is quite challenging to study with high spatial resolution from surface to bulk of the catalyst particles at a single particle level. To address this challenge we investigated the coke molecules in HZSM-5 catalyst after ethanol conversion treatment by a combination of C K-edge X-ray absorption spectroscopy (XAS), 13C Cross polarization-magic angle spinning nuclear magnetic resonance (CP-MAS NMR) spectroscopy, and atom probe tomography (APT). XAS and NMR highlighted the aromatic character of coke molecules. APT permitted the imaging of the spatial distribution of hydrocarbon molecules located within the pores of spent HZSM-5 catalyst from surface to bulk at a single particle level. 27Al NMR results and APT results indicated association of coke molecules with Al enriched regions within the spent HZSM-5 catalyst particles. The experimental results were additionally validated by a level-set-based APT field evaporation model. These results provide a new approach to investigate catalytic deactivation due to hydrocarbon coking or poisoning of zeolites at an unprecedented spatial resolution.

Discerning the Location and Nature of Coke Deposition from Surface to Bulk of Spent Zeolite Catalysts

PubMed Central

Devaraj, Arun; Vijayakumar, Murugesan; Bao, Jie; Guo, Mond F.; Derewinski, Miroslaw A.; Xu, Zhijie; Gray, Michel J.; Prodinger, Sebastian; Ramasamy, Karthikeyan K.

2016-01-01

The formation of carbonaceous deposits (coke) in zeolite pores during catalysis leads to temporary deactivation of catalyst, necessitating regeneration steps, affecting throughput, and resulting in partial permanent loss of catalytic efficiency. Yet, even to date, the coke molecule distribution is quite challenging to study with high spatial resolution from surface to bulk of the catalyst particles at a single particle level. To address this challenge we investigated the coke molecules in HZSM-5 catalyst after ethanol conversion treatment by a combination of C K-edge X-ray absorption spectroscopy (XAS), 13C Cross polarization-magic angle spinning nuclear magnetic resonance (CP-MAS NMR) spectroscopy, and atom probe tomography (APT). XAS and NMR highlighted the aromatic character of coke molecules. APT permitted the imaging of the spatial distribution of hydrocarbon molecules located within the pores of spent HZSM-5 catalyst from surface to bulk at a single particle level. 27Al NMR results and APT results indicated association of coke molecules with Al enriched regions within the spent HZSM-5 catalyst particles. The experimental results were additionally validated by a level-set–based APT field evaporation model. These results provide a new approach to investigate catalytic deactivation due to hydrocarbon coking or poisoning of zeolites at an unprecedented spatial resolution. PMID:27876869

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

Sulfidation of Co/Al[sub 2]O[sub 3] and CoMo/Al[sub 2]O[sub 3] catalysts studied by Moessbauer emission spectroscopy

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

Craje, M.W.J.; Kraan, A.M. van der; Beer, V.H.J. de

1993-10-01

The structure of hydrodesulfurization catalysts is relevant to many industries. The sulfidation of uncalcined and calcined alumina-supported cobalt and cobalt-molybdenum catalysts was systematically studied by means of in situ Moessbauer emission spectroscopy (MES) at room temperature. The spectra obtained during the stepwise sulfidation of the uncalcined catalysts clearly resemble those observed for carbon-supported ones. Hence, the interpretation of the spectra of the alumina-supported catalysts is based on the conclusions drawn from the MES studies of the carbon-supported catalysts, which are less complex because Co ions do not diffuse into the support. It is demonstrated that not only in sulfided CoMo/Al[submore » 2]O[sub 3], but also in sulfided Co/Al[sub 2]O[sub 3], catalysts Co-sulfide species with a [open quotes]Co-Mo-S[close quotes]-type quadrupole splitting can be formed. It is concluded that the Co-sulfide species formed in sulfided Co/Al[sub 2]O[sub 3] and CoMo/Al[sub 2]O[sub 3] catalysts are essentially the same, only the particle size and ordering of the Co-sulfide species may differ, as in the case of Co/C and CoMo/C catalysts. The function of the Mo, which is present as MoS[sub 2], is merely to stabilize very small Co-sulfide particles, which in the limit contain only one single Co atom. Furthermore, it turns out that the value of the electric quadrupole splitting (Q.S. value) of the Co-sulfide phase in the sulfided catalysts depends on the sulfiding temperature and Co content. This observation leads to the conclusion that large Q.S. values point to the presence of very small Co-sulfide entities or particles (the lower limit being [open quotes]particles[close quotes] containing only one Co atom, such as proposed in the [open quotes]Co-Mo-S[close quotes] model), whereas small Q.S. values point to the presence of large Co-sulfide particles (the upper limit being crystalline Co[sub 9]S[sub 8]). 28 refs., 7 figs., 6 tabs.« less

CO Sensing Performance of a Micro Thermoelectric Gas Sensor with AuPtPd/SnO₂ Catalyst and Effects of a Double Catalyst Structure with Pt/α-Al₂O₃.

PubMed

Goto, Tomoyo; Itoh, Toshio; Akamatsu, Takafumi; Shin, Woosuck

2015-12-15

The CO sensing properties of a micro thermoelectric gas sensor (micro-TGS) with a double AuPtPd/SnO₂ and Pt/α-Al₂O₃ catalyst were investigated. While several nanometer sized Pt and Pd particles were uniformly dispersed on SnO₂, the Au particles were aggregated as particles measuring >10 nm in diameter. In situ diffuse reflectance Fourier transform Infrared spectroscopy (DRIFT) analysis of the catalyst showed a CO adsorption peak on Pt and Pd, but no clear peak corresponding to the interaction between CO and Au was detected. Up to 200 °C, CO combustion was more temperature dependent than that of H₂, while H₂ combustion was activated by repeated exposure to H₂ gas during the periodic gas test. Selective CO sensing of the micro-TGS against H₂ was attempted using a double catalyst structure with 0.3-30 wt% Pt/α-Al₂O₃ as a counterpart combustion catalyst. The sensor output of the micro-TGS decreased with increasing Pt content in the Pt/α-Al₂O₃ catalyst, by cancelling out the combustion heat from the AuPtPd/SnO₂ catalyst. In addition, the AuPtPd/SnO₂ and 0.3 wt% Pt/α-Al₂O₃ double catalyst sensor showed good and selective CO detection. We therefore demonstrated that our micro-TGS with double catalyst structure is useful for controlling the gas selectivity of CO against H₂.

The preparation of nanosized polyethylene particles via novel heterogeneous non-metallocene catalyst (m-CH3PhO)TiCl3/CNTs/AlEt3

NASA Astrophysics Data System (ADS)

Wang, J.; Guo, J. P.; Yi, J. J.; Huang, Q. G.; Li, H. M.; Li, Y. F.; Gao, K. J.; Yang, W. T.

2014-08-01

This paper reports the preparation of coral-shaped topological morphology nascent polyethylene (PE) particles promoted by the novel heterogeneous non-metallocene catalyst (m-CH3PhO)TiCl3/carbon nanotubes (CNTs), with AlEt3 used as a cocatalyst. Scanning electron microscope (SEM), high resolution transmission electron microscope (HR-TEM) and inductively coupled plasma (ICP) emission spectroscopy were used to determine the morphology of the catalyst particles and the content of (m-CH3PhO)TiCl3. The carbon nanotube surface was treated with Grignard Reagent prior to reacting with (m-CH3PhO)TiCl3. The catalyst system could effectively catalyze ethylene polymerization and ethylene with 1- hexene copolymerization, the catalytic activity could reach up to 5.8 kg/((gTi)h). Morphology of the obtained polymer particles by SEM and HR-TEM technique revealed that the nascent polyethylene particles looked like coral shape in micro-size. The multiwalled carbon nanotubes (MWCNTs) supported catalysts polymerized ethylene to form polymer nanocomposite in situ. The microscopic examination of this nanocomposite revealed that carbon nanoparticles in PE matrix had a good distribution and the cryogenically fractured surface was ductile-like when polymerization time was 2 min.

Surface structural evolution of AuAg/TiO2 catalyst in the transformation of benzyl alcohol to sodium benzoate

NASA Astrophysics Data System (ADS)

Cui, Yuanyuan; Wang, Ying; Fan, Kangnian; Dai, Wei-Lin

2013-08-01

A series of AuAg/TiO2 catalysts calcined at different temperatures were used for single-pot, solvent-free synthesis of sodium benzoate and benzoic acid through the green oxidation of benzyl alcohol. The best catalytic performance, which produced a sodium benzoate yield of up to 85%, was obtained over the AuAg/TiO2 catalyst calcined at 623 K. Systematic characterizations including BET, XRD, TEM, XPS, and UV-vis DRS and ICP were carried out to investigate the influence of calcined temperature on the structural evolution of the bimetallic AuAg/TiO2 catalysts. TEM images showed that both low (473 K) and high calcinations temperatures (973 K) resulted in larger particles. The smallest particles (8.2 nm) were obtained at 623 K. This decrease in particle size may have been induced by the re-dispersion and interaction of the bimetallic species. XRD and XPS results showed that proper calcination temperature (623 K) could promote interactions between the bimetallic particles and the TiO2 support as well as the dispersion of active bimetallic species. The higher catalytic performance of the 623 K calcined catalyst could be attributed to the smaller particle size and the synergetic interaction between nano-bimetallic gold and silver species.

A novel "wastes-treat-wastes" technology: role and potential of spent fluid catalytic cracking catalyst assisted ozonation of petrochemical wastewater.

PubMed

Chen, Chunmao; Yu, Ji; Yoza, Brandon A; Li, Qing X; Wang, Gang

2015-04-01

Catalytic ozonation is a promising wastewater treatment technology. However, the high cost of the catalyst hinders its application. A novel "wastes-treat-wastes" technology was developed to reuse spent fluid catalytic cracking catalysts (sFCCc) for the ozonation of petrochemical wastewater in this study. Multivalent vanadium (V(4+) and V(5+)), iron (Fe(2+) and Fe(3+)) and nickel (Ni(2+)) oxides that are distributed on the surface of sFCCc and poisoned FCC catalysts are the catalytic components for ozonation. The sFCCc assisted catalytic ozonation (sFCCc-O) of nitrobenzene indicated that the sFCCc significantly promoted hydroxyl radical mediated oxidation. The degradation rate constant of nitrobenzene in sFCCc-O (0.0794 min(-1) at 298 K) was approximately doubled in comparison with that in single ozonation (0.0362 min(-1) at 298 K). The sFCCc-O of petrochemical wastewater increased chemical oxygen demand removal efficiency by three-fold relative to single ozonation. The number of oxygen-containing (Ox) polar contaminants in the effluent (253) from sFCCc-O treatment decreased to about 70% of the initial wastewater (353). The increased oxygen/carbon atomic ratio and decreased number of Ox polar contaminants indicated a high degree of degradation. The present study showed the role and potential of sFCCc for catalytic ozonation of petrochemical wastewater, particularly in an advantage of the cost-effectiveness through "wastes-treat-wastes". Copyright © 2015 Elsevier Ltd. All rights reserved.

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.

Apparatus and Process for Controlled Nanomanufacturing Using Catalyst Retaining Structures

NASA Technical Reports Server (NTRS)

Nguyen, Cattien (Inventor)

2013-01-01

An apparatus and method for the controlled fabrication of nanostructures using catalyst retaining structures is disclosed. The apparatus includes one or more modified force microscopes having a nanotube attached to the tip portion of the microscopes. An electric current is passed from the nanotube to a catalyst layer of a substrate, thereby causing a localized chemical reaction to occur in a resist layer adjacent the catalyst layer. The region of the resist layer where the chemical reaction occurred is etched, thereby exposing a catalyst particle or particles in the catalyst layer surrounded by a wall of unetched resist material. Subsequent chemical vapor deposition causes growth of a nanostructure to occur upward through the wall of unetched resist material having controlled characteristics of height and diameter and, for parallel systems, number density.

Fabrication of fuel cell electrodes and other catalytic structures

DOEpatents

Smith, J.L.

1987-02-11

A porous layer of catalyst material suitable for use as an electrode in a molten carbonate fuel cell includes elongated pores substantially extending across the layer thickness. The catalyst layer is prepared by depositing particulate catalyst material into polymeric flocking on a substrate surface by a procedure such as tape casting. The loaded substrate is heated in a series of steps with rising temperatures to set the tape, thermally decompose the substrate with flocking and sinter bond the catalyst particles into a porous catalytic layer with elongated pores across its thickness. Employed as an electrode, the elongated pores provide distribution of reactant gas into contact with catalyst particles wetted by molten electrolyte. 1 fig.

Fabrication of catalytic electrodes for molten carbonate fuel cells

DOEpatents

Smith, James L.

1988-01-01

A porous layer of catalyst material suitable for use as an electrode in a molten carbonate fuel cell includes elongated pores substantially extending across the layer thickness. The catalyst layer is prepared by depositing particulate catalyst material into polymeric flocking on a substrate surface by a procedure such as tape casting. The loaded substrate is heated in a series of steps with rising temperatures to set the tape, thermally decompose the substrate with flocking and sinter bond the catalyst particles into a porous catalytic layer with elongated pores across its thickness. Employed as an electrode, the elongated pores provide distribution of reactant gas into contact with catalyst particles wetted by molten electrolyte.

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

DEVELOPMENT OF ATTRITION RESISTANT IRON-BASED FISCHER-TROPSCH CATALYSTS

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

Adeyinka A. Adeyiga

2003-12-01

Fischer-Tropsch (FT) synthesis to convert syngas (CO + H{sub 2}) derived from natural gas or coal to liquid fuels and wax is a well-established technology. For low H{sub 2} to CO ratio syngas produced from CO{sub 2} reforming of natural gas or from gasification of coal, the use of Fe catalysts is attractive because of their high water gas shift activity in addition to their high FT activity. Fe catalysts are also attractive due to their low cost and low methane selectivity. Because of the highly exothermic nature of the FT reaction, there has been a recent move away frommore » fixed-bed reactors toward the development of slurry bubble column reactors (SBCRs) that employ 30 to 90 {micro}m catalyst particles suspended in a waxy liquid for efficient heat removal. However, the use of Fe FT catalysts in an SBCR has been problematic due to severe catalyst attrition resulting in fines that plug the filter employed to separate the catalyst from the waxy product. Fe catalysts can undergo attrition in SBCRs not only due to vigorous movement and collisions but also due to phase changes that occur during activation and reaction. The objectives of this research were to develop a better understanding of the parameters affecting attrition of Fe F-T catalysts suitable for use in SBCRs and to incorporate this understanding into the design of novel Fe catalysts having superior attrition resistance. The catalysts were prepared by co-precipitation, followed by binder addition and spray drying at 250 C in a 1 m diameter, 2 m tall spray dryer. The binder silica content was varied from 0 to 20 wt %. The results show that use of small amounts of precipitated SiO{sub 2} alone in spray-dried Fe catalysts can result in good attrition resistance. All catalysts investigated with SiO{sub 2} wt% {le} 12 produced fines less than 10 wt% during the jet cup attrition test, making them suitable for long-term use in a slurry bubble column reactor. Thus, concentration rather than type of SiO{sub 2} incorporated into catalyst has a more critical impact on catalyst attrition resistance of spray-dried Fe catalysts. Lower amounts of SiO{sub 2} added to a catalyst give higher particle densities and therefore higher attrition resistances. In order to produce a suitable SBCR catalyst, however, the amount of SiO{sub 2} added has to be optimized to provide adequate surface area, particle density, and attrition resistance. Two of the catalysts with precipitated and binder silica were tested in Texas A&M University's CSTR (Autoclave Engineers). Spray-dried catalysts with compositions 100 Fe/5 Cu/4.2 K/11 (P) SiO{sub 2} and 100 Fe/5 Cu/4.2 K/1.1 (B) SiO{sub 2} have excellent selectivity characteristics (low methane and high C{sub 5}{sup +} yields), but their productivity and stability (deactivation rate) need to be improved. Mechanical integrity (attrition strength) of these two catalysts was markedly dependent upon their morphological features. The attrition strength of the catalyst made out of largely spherical particles (1.1 (B) SiO{sub 2}) was considerably higher than that of the catalyst consisting of irregularly shaped particles (11 (P) SiO{sub 2}).« less

Pyrolysis of ground pine chip and ground pellet particles

DOE PAGES

Rezaei, Hamid; Yazdanpanah, Fahimeh; Lim, C. Jim; ...

2016-08-04

In addition to particle size, biomass density influences heat and mass transfer rates during the thermal treatment processes. In this research, thermal behaviour of ground pine chip particles and ground pine pellet particles in the range of 0.25–5 mm was investigated. A single particle from ground pellets was almost 3 to 4 times denser than a single particle from ground chips at a similar size and volume of particle. Temperature was ramped up from room temperature (~25 °C) to 600 °C with heating rates of 10, 20, 30, and 50 °C/min. Pellet particles took 25–88 % longer time to drymore » than the chip particles. Microscopic examination of 3 mm and larger chip particles showed cracks during drying. No cracks were observed for pellet particles. The mass loss due to treatment at temperatures higher than 200 °C was about 80% both for chip and pellet particles. It took 4 min for chip and pellet particles to lose roughly 63% of their dry mass at a heating rate of 50 °C/min. The SEM structural analysis showed enlarged pores and cracks in cell walls of the pyrolyzed wood chips. As a result, these pores were not observed in pyrolyzed pellet particles.« less

Sol-gel based oxidation catalyst and coating system using same

NASA Technical Reports Server (NTRS)

Leighty, Bradley D. (Inventor); Watkins, Anthony N. (Inventor); Patry, JoAnne L. (Inventor); Schryer, Jacqueline L. (Inventor); Oglesby, Donald M. (Inventor)

2010-01-01

An oxidation catalyst system is formed by particles of an oxidation catalyst dispersed in a porous sol-gel binder. The oxidation catalyst system can be applied by brush or spray painting while the sol-gel binder is in its sol state.

Low-Temperature Synthesis of Hierarchical Amorphous Basic Nickel Carbonate Particles for Water Oxidation Catalysis.

PubMed

Yang, Yisu; Liang, Fengli; Li, Mengran; Rufford, Thomas E; Zhou, Wei; Zhu, Zhonghua

2015-07-08

Amorphous nickel carbonate particles are catalysts for the oxygen evolution reaction (OER), which plays a critical role in the electrochemical splitting of water. The amorphous nickel carbonate particles can be prepared at a temperature as low as 60 °C by an evaporation-induced precipitation (EIP) method. The products feature hierarchical pore structures. The mass-normalized activity of the catalysts, measured at an overpotential of 0.35 V, was 55.1 A g(-1) , with a Tafel slope of only 60 mV dec(-1) . This catalytic activity is superior to the performance of crystalline NiOx particles and β-Ni(OH)2 particles, and compares favorably to state-of-the-art RuO2 catalysts. The activity of the amorphous nickel carbonate is remarkably stable during a 10 000 s chronoamperometry test. Further optimization of synthesis parameters reveals that the amorphous structure can be tuned by adjusting the H2 O/Ni ratio in the precursor mixture. These results suggest the potential application of easily prepared hierarchical basic nickel carbonate particles as cheap and robust OER catalysts with high activity. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Rock-Salt Growth-Induced (003) Cracking in a Layered Positive Electrode for Li-Ion Batteries

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

Zhang, Hanlei; Omenya, Fredrick; Yan, Pengfei

For the first time, the (003) cracking is observed and determined to be the major cracking mechanism for the primary particles of Ni-rich layered dioxides as the positive electrode for Li-ion batteries. Using transmission electron microscopy techniques, here we show that the propagation and fracturing of platelet-like rock-salt phase along the (003) plane of the layered oxide are the leading cause for the cracking of primary particles. The fracturing of the rock-salt platelet is induced by the stress discontinuity between the parent layered oxide and the rock-salt phase. The high nickel content is considered to be the key factor formore » the formation of the rock-salt platelet and thus the (003) cracking. The (003)-type cracking can be a major factor for the structural degradation and associated capacity fade of the layered positive electrode.« less

Resistance to Fracture, Fatigue and Stress-Corrosion of Al-Cu-Li-Zr Alloys

DTIC Science & Technology

1985-02-19

alloys , in both smooth and notch fatigue conditions, are compared in Figure 15 giving a summary of Mg- effect on S-N fatigue behavior. Several ...crack initiation of conventional aluminum alloys and reported that fatigue cracks were associated with cracked constituent particles in 2024 -T3... fatigue cracks. Kung & Fine (14) investigated surface crack initiation in a 2024 -T4 alloy . They observed that at high stresses most cracks formed

A facile self-assembly approach to prepare palladium/carbon nanotubes catalyst for the electro-oxidation of ethanol

NASA Astrophysics Data System (ADS)

Wen, Cuilian; Zhang, Xinyuan; Wei, Ying; Zhang, Teng; Chen, Changxin

2018-02-01

A facile self-assembly approach is reported to prepare palladium/carbon nanotubes (Pd/CNTs) catalyst for the electro-oxidation of ethanol. In this method, the Pd-oleate/CNTs was decomposed into the Pd/CNTs at an optimal temperature of 195 °C in air, in which no inert gas is needed for the thermal decomposition process due to the low temperature used and the decomposed products are also environmental friendly. The prepared Pd/CNTs catalyst has a high metallic Pd0 content and the Pd particles in the catalyst are disperse, uniform-sized with an average size of ˜2.1 nm, and evenly distributed on the CNTs. By employing our strategy, the problems including the exfoliation of the metal particles from the CNTs and the aggregation of the metal particles can be solved. Comparing with the commercial Pd/C one, the prepared Pd/CNTs catalyst exhibits a much higher electrochemical activity and stability for the electro-oxidation of ethanol in the direct ethanol fuel cells.

CO hydrogenation on PdCo/NaY catalysts: Effect of ion hydration on metal phases and selectivity

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

Yuangen Yin; Zongchao Zhang; Sachtler, W.M.H.

1993-02-01

Exposure of calcined PdCo/NaY catalyst precursors to water vapor, prior to reduction, strongly affects the CO hydrogenation activity and selectivity of the reduced bimetal catalysts. With samples that had been exposed to H[sub 2]O before reduction, the formation of hydrocarbons prevails; nonhydrated reference samples of the same overall composition are mainly selective for oxygenates. After 6 h of reaction time PdCo alloy particles of 5.8 nm are detected by XRD in H[sub 2]O-exposed catalysts, but in the reference samples the metal particles are below the limit of detection by XRD. The observed effects are attributed to the formation of mobilemore » aquo-complexes of metal ions; after reduction they are converted to larger alloy particles, richer on Co, than in the reference samples. Results obtained with NaOH-neutralized and Co-free Pd/NaY catalysts are also discussed. 23 refs., 13 figs., 1 tab.« less

Crack identification method in beam-like structures using changes in experimentally measured frequencies and Particle Swarm Optimization

NASA Astrophysics Data System (ADS)

Khatir, Samir; Dekemele, Kevin; Loccufier, Mia; Khatir, Tawfiq; Abdel Wahab, Magd

2018-02-01

In this paper, a technique is presented for the detection and localization of an open crack in beam-like structures using experimentally measured natural frequencies and the Particle Swarm Optimization (PSO) method. The technique considers the variation in local flexibility near the crack. The natural frequencies of a cracked beam are determined experimentally and numerically using the Finite Element Method (FEM). The optimization algorithm is programmed in MATLAB. The algorithm is used to estimate the location and severity of a crack by minimizing the differences between measured and calculated frequencies. The method is verified using experimentally measured data on a cantilever steel beam. The Fourier transform is adopted to improve the frequency resolution. The results demonstrate the good accuracy of the proposed technique.

Corrosion and corrosion fatigue of airframe aluminum alloys

NASA Technical Reports Server (NTRS)

Chen, G. S.; Gao, M.; Harlow, D. G.; Wei, R. P.

1994-01-01

Localized corrosion and corrosion fatigue crack nucleation and growth are recognized as degradation mechanisms that effect the durability and integrity of commercial transport aircraft. Mechanically based understanding is needed to aid the development of effective methodologies for assessing durability and integrity of airframe components. As a part of the methodology development, experiments on pitting corrosion, and on corrosion fatigue crack nucleation and early growth from these pits were conducted. Pitting was found to be associated with constituent particles in the alloys and pit growth often involved coalescence of individual particle-nucleated pits, both laterally and in depth. Fatigue cracks typically nucleated from one of the larger pits that formed by a cluster of particles. The size of pit at which fatigue crack nucleates is a function of stress level and fatigue loading frequency. The experimental results are summarized, and their implications on service performance and life prediction are discussed.

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.

4-Nitrophenol, 1-nitropyrene, and 9-nitroanthracene emissions in exhaust particles from diesel vehicles with different exhaust gas treatments

NASA Astrophysics Data System (ADS)

Inomata, Satoshi; Fushimi, Akihiro; Sato, Kei; Fujitani, Yuji; Yamada, Hiroyuki

2015-06-01

The dependence of nitro-organic compound emissions in automotive exhaust particles on the type of aftertreatment used was investigated. Three diesel vehicles with different aftertreatment systems (an oxidation catalyst, vehicle-DOC; a particulate matter and NOx reduction system, vehicle-DPNR; and a urea-based selective catalytic reduction system, vehicle-SCR) and a gasoline car with a three-way catalyst were tested. Nitro-polycyclic aromatic hydrocarbons (nitro-PAHs) and nitrophenols in the particles emitted were analyzed by thermal desorption gas chromatography/mass spectrometry and liquid chromatography/mass spectrometry. The secondary production of nitro-organic compounds on the filters used to collect particles and the adsorption of gaseous nitro-organic compounds by the filters were evaluated. Emissions of 1-nitropyrene, 9-nitroanthracene, and 4-nitrophenol in the diesel exhaust particles were then quantified. The NOx reduction process in vehicle-DPNR appeared to remove nitro-hydrocarbons efficiently but not to remove nitro-oxygenated hydrocarbons efficiently. The nitro-PAH emission factors were lower for vehicle-DOC when it was not fitted with a catalyst than when it was fitted with a catalyst. The 4-nitrophenol emission factors were also lower for vehicle-DOC with a catalyst than vehicle-DOC without a catalyst, suggesting that the oxidation catalyst was a source of both nitro-PAHs and 4-nitrophenol. The time-resolved aerosol mass spectrometry data suggested that nitro-organic compounds are mainly produced when an engine is working under load. The presence of 4-nitrophenol in the particles was not confirmed statistically because of interference from gaseous 4-nitrophenol. Systematic errors in the estimated amounts of gaseous 1-nitropyrene and 9-nitroanthracene adsorbed onto the filters and the estimated amounts of volatile nitro-organic compounds that evaporated during sampling and during post-sampling conditioning could not be excluded. An analytical method in which all gaseous compounds are absorbed before particles are collected, and in which the volatile compounds are derivatized, would improve the precision and the accuracy of the data.

Direct evidence of atomic-scale structural fluctuations in catalyst nanoparticles.

PubMed

Lin, Pin Ann; Gomez-Ballesteros, Jose L; Burgos, Juan C; Balbuena, Perla B; Natarajan, Bharath; Sharma, Renu

2017-05-01

Rational catalyst design requires an atomic scale mechanistic understanding of the chemical pathways involved in the catalytic process. A heterogeneous catalyst typically works by adsorbing reactants onto its surface, where the energies for specific bonds to dissociate and/or combine with other species (to form desired intermediate or final products) are lower. Here, using the catalytic growth of single-walled carbon nanotubes (SWCNTs) as a prototype reaction, we show that the chemical pathway may in-fact involve the entire catalyst particle, and can proceed via the fluctuations in the formation and decomposition of metastable phases in the particle interior. We record in situ and at atomic resolution, the dynamic phase transformations occurring in a Cobalt catalyst nanoparticle during SWCNT growth, using a state-of-the-art environmental transmission electron microscope (ETEM). The fluctuations in catalyst carbon content are quantified by the automated, atomic-scale structural analysis of the time-resolved ETEM images and correlated with the SWCNT growth rate. We find the fluctuations in the carbon concentration in the catalyst nanoparticle and the fluctuations in nanotube growth rates to be of complementary character. These findings are successfully explained by reactive molecular dynamics (RMD) simulations that track the spatial and temporal evolution of the distribution of carbon atoms within and on the surface of the catalyst particle. We anticipate that our approach combining real-time, atomic-resolution image analysis and molecular dynamics simulations will facilitate catalyst design, improving reaction efficiencies and selectivity towards the growth of desired structure.

New Method to Synthesize Highly Active and Durable Chemically Ordered fct-PtCo Cathode Catalyst for PEMFCs.

PubMed

Jung, Won Suk; Popov, Branko N

2017-07-19

In the bottom-up synthesis strategy performed in this study, the Co-catalyzed pyrolysis of chelate-complex and activated carbon black at high temperatures triggers the graphitization reaction which introduces Co particles in the N-doped graphitic carbon matrix and immobilizes N-modified active sites for the oxygen reduction reaction (ORR) on the carbon surface. In this study, the Co particles encapsulated within the N-doped graphitic carbon shell diffuse up to the Pt surface under the polymer protective layer and forms a chemically ordered face-centered tetragonal (fct) Pt-Co catalyst PtCo/CCCS catalyst as evidenced by structural and compositional studies. The fct-structured PtCo/CCCS at low-Pt loading (0.1 mg Pt cm -2 ) shows 6% higher power density than that of the state-of-the-art commercial Pt/C catalyst. After the MEA durability test of 30 000 potential cycles, the performance loss of the catalyst is negligible. The electrochemical surface area loss is less than 40%, while that of commercial Pt/C is nearly 80%. After the accelerated stress test, the uniform catalyst distribution is retained and the mean particle size increases approximate 1 nm. The results obtained in this study indicated that highly stable compositional and structural properties of chemically ordered PtCo/CCCS catalyst contribute to its exceptional catalyst durability.

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.

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

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.

Sub-nanometer surface chemistry and orbital hybridization in lanthanum-doped ceria nano-catalysts revealed by 3D electron microscopy.

PubMed

Collins, Sean M; Fernandez-Garcia, Susana; Calvino, José J; Midgley, Paul A

2017-07-14

Surface chemical composition, electronic structure, and bonding characteristics determine catalytic activity but are not resolved for individual catalyst particles by conventional spectroscopy. In particular, the nano-scale three-dimensional distribution of aliovalent lanthanide dopants in ceria catalysts and their effect on the surface electronic structure remains unclear. Here, we reveal the surface segregation of dopant cations and oxygen vacancies and observe bonding changes in lanthanum-doped ceria catalyst particle aggregates with sub-nanometer precision using a new model-based spectroscopic tomography approach. These findings refine our understanding of the spatially varying electronic structure and bonding in ceria-based nanoparticle aggregates with aliovalent cation concentrations and identify new strategies for advancing high efficiency doped ceria nano-catalysts.

Formation of alcohol conversion catalysts

DOEpatents

Wachs, Israel E.; Cai, Yeping

2001-01-01

The method of the present invention involves a composition containing an intimate mixture of (a) metal oxide support particles and (b) a catalytically active metal oxide from Groups VA, VIA, or VIIA, its method of manufacture, and its method of use for converting alcohols to aldehydes. During the conversion process, catalytically active metal oxide from the discrete catalytic metal oxide particles migrates to the oxide support particles and forms a monolayer of catalytically active metal oxide on the oxide support particle to form a catalyst composition having a higher specific activity than the admixed particle composition.

Growth kinetics and growth mechanism of ultrahigh mass density carbon nanotube forests on conductive Ti/Cu supports.

PubMed

Sugime, Hisashi; Esconjauregui, Santiago; D'Arsié, Lorenzo; Yang, Junwei; Makaryan, Taron; Robertson, John

2014-09-10

We evaluate the growth kinetics and growth mechanism of ultrahigh mass density carbon nanotube forests. They are synthesized by chemical vapor deposition at 450 °C using a conductive Ti/Cu support and Co-Mo catalyst system. We find that Mo stabilizes Co particles preventing lift off during the initial growth stage, thus promoting the growth of ultrahigh mass density nanotube forests by the base growth mechanism. The morphology of the forest gradually changes with growth time, mostly because of a structural change of the catalyst particles. After 100 min growth, toward the bottom of the forest, the area density decreases from ∼ 3-6 × 10(11) cm(-2) to ∼ 5 × 10(10) cm(-2) and the mass density decreases from 1.6 to 0.38 g cm(-3). We also observe part of catalyst particles detached and embedded within nanotubes. The progressive detachment of catalyst particles results in the depletion of the catalyst metals on the substrate surfaces. This is one of the crucial reasons for growth termination and may apply to other catalyst systems where the same features are observed. Using the packed forest morphology, we demonstrate patterned forest growth with a pitch of ∼ 300 nm and a line width of ∼ 150 nm. This is one of the smallest patterning of the carbon nanotube forests to date.

The effects of the catalytic converter and fuel sulfur level on motor vehicle particulate matter emissions: light duty diesel vehicles.

PubMed

Maricq, M Matti; Chase, Richard E; Xu, Ning; Laing, Paul M

2002-01-15

Wind tunnel measurements and direct tailpipe particulate matter (PM) sampling are utilized to examine how the combination of oxidation catalyst and fuel sulfur content affects the nature and quantity of PM emissions from the exhaust of a light duty diesel truck. When low sulfur fuel (4 ppm) is used, or when high sulfur (350 ppm)fuel is employed without an active catalyst present, a single log-normal distribution of exhaust particles is observed with a number mean diameter in the range of 70-83 nm. In the absence of the oxidation catalyst, the high sulfur level has at most a modest effect on particle emissions (<50%) and a minor effect on particle size (<5%). In combination with the active oxidation catalyst tested, high sulfur fuel can lead to a second, nanoparticle, mode, which appears at approximately 20 nm during high speed operation (70 mph), but is not present at low speed (40 mph). A thermodenuder significantly reduces the nanoparticle mode when set to temperatures above approximately 200 degrees C, suggesting that these particles are semivolatile in nature. Because they are observed only when the catalyst is present and the sulfur level is high, this mode likely originates from the nucleation of sulfates formed over the catalyst, although the composition may also include hydrocarbons.

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.

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

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.

78 FR 40954 - Airworthiness Directives; Various Restricted Category Helicopters

Federal Register 2010, 2011, 2012, 2013, 2014

2013-07-09

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Comparative assessment of synthetic strategies toward active platinum-rhodium-tin electrocatalysts for efficient ethanol electro-oxidation

NASA Astrophysics Data System (ADS)

Erini, Nina; Krause, Paul; Gliech, Manuel; Yang, Ruizhi; Huang, Yunhui; Strasser, Peter

2015-10-01

The present work explores the effect of autoclave-based autogenous-pressure vs. ambient pressure conditions on the synthesis and properties of carbon-supported Pt-Rh-Sn nanoparticle electrocatalysts. The Pt-Rh-Sn nanoparticles were characterized by X-ray spectroscopy, electron microscopy and mass spectroscopy and deployed as catalysts for the electrocatalytic ethanol oxidation reaction. Pt-Rh-Sn catalysts precipitated with carbon already present showed narrow particle size distribution around 7 nm, while catalysts supported on carbon after particle formation showed broader size distribution ranging from 8 to 16 nm, similar metal loadings between 40 and 48 wt.% and similar atomic ratios of Pt:Rh:Sn of 30:10:60. The highest ethanol oxidation activity at low overpotentials associated with exceptionally early ethanol oxidation onset potential was observed for ambient-pressure catalysts with the active ternary alloy phase formed in presence of the carbon supports. In contrast, catalysts prepared under ambient pressure in a two-step approach, involving alloy particle formation followed by particle separation and subsequent deposition on the carbon support, yielded the highest overall mass activities. Based on the observed synthesis-activity correlations, a comparative assessment is provided of the synthetic techniques at high vs. low pressures, and in presence and absence of carbon support. Plausible hypotheses in terms of particle dispersion and interparticle distance accounting for these observed differences are discussed.

Particle size dependence of CO tolerance of anode PtRu catalysts for polymer electrolyte fuel cells

NASA Astrophysics Data System (ADS)

Yamanaka, Toshiro; Takeguchi, Tatsuya; Wang, Guoxiong; Muhamad, Ernee Noryana; Ueda, Wataru

An anode catalyst for a polymer electrolyte fuel cell must be CO-tolerant, that is, it must have the function of hydrogen oxidation in the presence of CO, because hydrogen fuel gas generated by the steam reforming process of natural gas contains a small amount of CO. In the present study, PtRu/C catalysts were prepared with control of the degree of Pt-Ru alloying and the size of PtRu particles. This control has become possible by a new method of heat treatment at the final step in the preparation of catalysts. The CO tolerances of PtRu/C catalysts with the same degree of Pt-Ru alloying and with different average sizes of PtRu particles were thus compared. Polarization curves were obtained with pure H 2 and CO/H 2 (CO concentrations of 500-2040 ppm). It was found that the CO tolerance of highly dispersed PtRu/C (high dispersion (HD)) with small PtRu particles was much higher than that of poorly dispersed PtRu/C (low dispersion (LD)) with large metal particles. The CO tolerance of PtRu/C (HD) was higher than that of any commercial PtRu/C. The high CO tolerance of PtRu/C (HD) is thought to be due to efficient concerted functions of Pt, Ru, and their alloy.

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.

Constrained Geometry Organotitanium Catalysts Supported on Nanosized Silica for Ethylene (co)Polymerization.

PubMed

Li, Kuo-Tseng; Wu, Ling-Huey

2017-05-05

Supported olefin polymerization catalysts can prevent reactor-fouling problems and produce uniform polymer particles. Constrained geometry complexes (CGCs) have less sterically hindered active sites than bis-cyclopentadienyl metallocene catalysts. In the literature, micrometer-sized silica particles were used for supporting CGC catalysts, which might have strong mass transfer limitations. This study aims to improve the activity of supported CGC catalysts by using nanometer-sized silica. Ti[(C₅Me₄)SiMe₂(N t Bu)]Cl₂, a "constrained-geometry" titanium catalyst, was supported on MAO-treated silicas (nano-sized and micro-sized) by an impregnation method. Ethylene homo-polymerization and co-polymerization with 1-octene were carried out in a temperature range of 80-120 °C using toluene as the solvent. Catalysts prepared and polymers produced were characterized. For both catalysts and for both reactions, the maximum activities occurred at 100 °C, which is significantly higher than that (60 °C) reported before for supported bis-cyclopentadienyl metallocene catalysts containing zirconium, and is lower than that (≥140 °C) used for unsupported Ti[(C₅Me₄)SiMe₂(N t Bu)]Me₂ catalyst. Activities of nano-sized catalyst were 2.6 and 1.6 times those of micro-sized catalyst for homopolymerization and copolymerization, respectively. The former produced polymers with higher crystallinity and melting point than the latter. In addition, copolymer produced with nanosized catalyst contained more 1-octene than that produced with microsized catalyst.

In-vehicle measurement of ultrafine particles on compressed natural gas, conventional diesel, and oxidation-catalyst diesel heavy-duty transit buses.

PubMed

Hammond, Davyda; Jones, Steven; Lalor, Melinda

2007-02-01

Many metropolitan transit authorities are considering upgrading transit bus fleets to decrease ambient criteria pollutant levels. Advancements in engine and fuel technology have lead to a generation of lower-emission buses in a variety of fuel types. Dynamometer tests show substantial reductions in particulate mass emissions for younger buses (<10 years) over older models, but particle number reduction has not been verified in the research. Recent studies suggest that particle number is a more important factor than particle mass in determining health effects. In-vehicle particle number concentration measurements on conventional diesel, oxidation-catalyst diesel and compressed natural gas transit buses are compared to estimate relative in-vehicle particulate exposures. Two primary consistencies are observed from the data: the CNG buses have average particle count concentrations near the average concentrations for the oxidation-catalyst diesel buses, and the conventional diesel buses have average particle count concentrations approximately three to four times greater than the CNG buses. Particle number concentrations are also noticeably affected by bus idling behavior and ventilation options, such as, window position and air conditioning.

The application of aberration-corrected electron microscopy to the characterization of gold-based catalysts

NASA Astrophysics Data System (ADS)

Herzing, Andrew A.

Electron microscopy has long been used to study the morphology of heterogeneous catalysts. Recent advances in electron optics now allow for the correction of the inherent spherical aberration (Cs) produced by the objective lens in the scanning transmission electron microscope (STEM, resulting in a significantly improved spatial resolution as well as the ability to use a much larger probe-current than was previously possible. In this thesis, the combination of high-angle annular dark-field (HAADF) imaging and microanalysis by x-ray energy dispersive spectroscopy (XEDS) in an aberration-corrected STEM has been applied for the first time to the characterization of gold-based heterogeneous catalysts. Multi-variate statistical analysis (MSA) has been employed in order to further improve the STEM-XEDS spectrum image data acquired with this technique. In addition, supplemental analysis using electron-energy loss spectroscopy (EELS) and energy-filtered transmission electron microscopy (EFTEM) in an aberration-corrected instrument has also been attempted. These techniques have proven extremely valuable in providing complimentary information to more traditional catalyst characterization techniques such as x-ray photoelectron spectroscopy and x-ray diffraction in four specific problems relating to catalysis. Firstly, the atomic-scale resolution of Cs-corrected HAADF imaging has been utilized to study Au/FeOx catalysts in order to determine the size and structure of the Au clusters present on the support surface. It was discovered that, while both inactive and active catalysts for low-temperature CO oxidation contained large Au particles (> 5 nm) and individual Au atoms, the active catalyst also contained sub-nm clusters comprised of only a few Au atoms. Secondly, novel CeO2 support materials for Au and Au-Pd catalysts were synthesized by precipitation with supercritical CO2. These supports were found to produce significantly more active catalysts than those based on CeO2 prepared using more traditional methods. The combination of STEM-HAADF imaging and XEDS mapping has been used to characterize these catalysts and a strong correlation between the catalytic activity and the enhanced degree of metal dispersion over the support is demonstrated. Thirdly, a systematic series of Au-Pd/Al2O3 catalysts has been studied in order to characterize the effects of various heat treatments on the development of core-shell morphologies within the bi-metallic particles and its subsequent effect on their catalytic performance for H2O 2 synthesis. STEM-XEDS spectrum imaging was employed in order to determine the degree of alloying and segregation behavior within the individual Au-Pd particles as a function of calcination/reduction temperature. It was found that the as prepared catalyst contained homogeneous Au-Pd alloy particles and that a Pd-rich shell/Au-rich core morphology gradually developed upon calcination. Subsequent reduction of the catalyst caused a large fraction of the particles to invert and form Pd-rich core/Au-rich shell structures. These changes are related to both the activity and stability of the catalyst. Finally, the washing of activated carbon support materials in acid was found to be extremely beneficial for producing Au-Pd catalysts for the direct synthesis of H2O2. STEM-HAADF imaging revealed that the acid-washing treatment increased the dispersion of the metal on the carbon supports. Aberration-corrected STEM-XEDS spectrum imaging demonstrated a strong size dependence of the Au-Pd particle composition. Crucially, the acid-washing pre-treatment enhanced the alloying of Au and Pd by suppressing the formation of large (> 25 nm) Au-rich particles. In summary, the application of aberration-corrected HAADF imaging and STEM-XEDS spectrum imaging to the characterization of Au-based catalysts has enhanced the understanding of the structural and chemical features that determine their catalytic behavior. Specifically, they have allowed us to achieve the following: (a) image individual metal atoms and clusters of just a few atoms dispersed in a real, high surface area catalyst, (b) detect and follow the development of core-shell structures in Au-Pd bi-metallic catalysts, (c) determine composition/size correlations in Au-Pd catalysts, (d) detect minor alloying elements in bi-metallic catalysts, (e) and chemically map atomic or near atomic dispersions of metals on oxide supports.

Electrode assembly for use in a solid polymer electrolyte fuel cell

DOEpatents

Raistrick, Ian D.

1989-01-01

A gas reaction fuel cell may be provided with a solid polymer electrolyte membrane. Porous gas diffusion electrodes are formed of carbon particles supporting a catalyst which is effective to enhance the gas reactions. The carbon particles define interstitial spaces exposing the catalyst on a large surface area of the carbon particles. A proton conducting material, such as a perfluorocarbon copolymer or ruthenium dioxide contacts the surface areas of the carbon particles adjacent the interstitial spaces. The proton conducting material enables protons produced by the gas reactions adjacent the supported catalyst to have a conductive path with the electrolyte membrane. The carbon particles provide a conductive path for electrons. A suitable electrode may be formed by dispersing a solution containing a proton conducting material over the surface of the electrode in a manner effective to coat carbon surfaces adjacent the interstitial spaces without impeding gas flow into the interstitial spaces.

Purification process for vertically aligned carbon nanofibers

NASA Technical Reports Server (NTRS)

Nguyen, Cattien V.; Delziet, Lance; Matthews, Kristopher; Chen, Bin; Meyyappan, M.

2003-01-01

Individual, free-standing, vertically aligned multiwall carbon nanotubes or nanofibers are ideal for sensor and electrode applications. Our plasma-enhanced chemical vapor deposition techniques for producing free-standing and vertically aligned carbon nanofibers use catalyst particles at the tip of the fiber. Here we present a simple purification process for the removal of iron catalyst particles at the tip of vertically aligned carbon nanofibers derived by plasma-enhanced chemical vapor deposition. The first step involves thermal oxidation in air, at temperatures of 200-400 degrees C, resulting in the physical swelling of the iron particles from the formation of iron oxide. Subsequently, the complete removal of the iron oxide particles is achieved with diluted acid (12% HCl). The purification process appears to be very efficient at removing all of the iron catalyst particles. Electron microscopy images and Raman spectroscopy data indicate that the purification process does not damage the graphitic structure of the nanotubes.

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.

Preparation of a Bimetal Using Mechanical Alloying for Environmental or Industrial Use

NASA Technical Reports Server (NTRS)

Quinn, Jacqueline; Geiger, Cherie; Clausen, Christian

2013-01-01

Following the 1976 Toxic Substances Control Act ban on their manufacture, PCBs remain an environmental threat. PCBs are known to bio-accumulate and concentrate in fatty tissues. Further complications arise from the potential for contamination of commercial mixtures with other more toxic chlorinated compounds such as polychlorinated dibenzodioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs). Until recently, only one option was available for the treatment of PCB-contaminated materials: incineration. This may prove to be more detrimental to the environment than the PCBs themselves due to the potential for formation of PCDDs. Metals have been used for the past ten years for the remediation of halogenated solvents and other contaminants in the environment; however, zero-valent metals alone do not possess the activity required to dehalogenate PCBs. Palladium has been shown to act as an excellent catalyst for the dechlorination of PCBs with active metals. This invention is a method for the production of a palladium/magnesium bimetal capable of dechlorinating PCBs using mechanical milling/mechanical alloying. Other base metals and catalysts may also be alloyed together (e.g., nickel or zinc) to create a similarly functioning catalyst system. Several bimetal catalyst systems currently can be used for processes such as hydrogen peroxide synthesis, oxidation of ethane, selective oxidation, hydrogenation, and production of syngas for further conversion to clean fuels. The processes for making these bimetal catalysts often involve vapor deposition. This technology provides an alternative to vapor deposition that may provide equally active catalysts. A hydrogenation catalyst including a base material coated with a catalytic metal is made using mechanical milling techniques. The hydrogenation catalysts are used as an excellent catalyst for the dehalogenation of contaminated compounds and the remediation of other industrial compounds. The mechanical milling technique is simpler and cheaper than previously used methods for producing hydrogenation catalysts. Preferably, the hydrogenation catalyst is a bimetallic particle formed from a zero-valent iron or zero-valent magnesium particle coated with palladium that is impregnated onto a high-surface-area graphite support. The zero-valent metal particles should be microscale or nanoscale zero-valent magnesium or zero-valent iron particles. Other zero-valent metal particles and combinations may be used. Additionally, the base material may be selected from a variety of minerals including, but not limited to, alumina and zeolites. The catalytic metal is preferably selected from the group consisting of noble metals and transition metals, preferably palladium. The mechanical milling process includes milling the base material with a catalytic metal impregnated into a high-surface-area support to form the hydrogenation catalyst. In a preferred mechanical milling process, a zero-valent metal particle is provided as the base material, preferably having a particle size of less than about 10 microns, preferably 0.1 to 10 microns or smaller, prior to milling. The catalytic metal is supported on a conductive carbon support structure prior to milling. For example, palladium may be impregnated on a graphite support. Other support structures such as semiconductive metal oxides may also be used.

Mesoporous inorganic salts with crystal defects: unusual catalysts and catalyst supports† †Electronic supplementary information (ESI) available: Scheme S1 contains reaction equation, Fig. S1–S7 contain solubility test, XRD, SEM, TEM, micropore size distribution and reaction conversion. See DOI: 10.1039/c4sc03736g Click here for additional data file.

PubMed Central

Kang, Xinchen; Shang, Wenting; Zhu, Qinggong; Zhang, Jianling; Wu, Zhonghua; Li, Zhihong; Xing, Xueqing

2015-01-01

We proposed a strategy to synthesize mesoporous inorganic salt particles using the special properties of ionic liquid (IL) mixtures, and hollow mesoporous LaF3, NdF3, and YF3 particles were synthesized and characterized using different techniques. The size of the mesopores in the salt particles was about 4 nm, and the materials were full of crystal defects. The LaF3, NdF3 and YF3 particles were used as the catalysts for the cyanosilylation reaction of benzaldehyde using trimethylsilyl cyanide, and Ru/LaF3 and Ru/NdF3, in which Ru nanocatalysts were supported on the LaF3 and NdF3 particles with mesopores, were used to catalyze hydrogenations of benzene to cyclohexane and levulinic acid (LA) to γ-valerolactone (GVL). It was discovered that the activities of these catalysts were unprecedentedly high for these reactions. Detailed study showed that both the crystal defects and the mesopores in the salt particles played crucial roles for the extremely high catalytic activity. PMID:29308132

Nickel/ruthenium catalyst and method for aqueous phase reactions

DOEpatents

Elliott, D.C.; Sealock, J.L.

1998-09-29

A method of hydrogenation is described using a catalyst in the form of a plurality of porous particles wherein each particle is a support having nickel metal catalytic phase or reduced nickel deposited thereon in a first dispersed phase and an additional ruthenium metal deposited onto the support in a second dispersed phase. The additional ruthenium metal is effective in retarding or reducing agglomeration or sintering of the nickel metal catalytic phase thereby increasing the life time of the catalyst during hydrogenation reactions. 2 figs.

Method for producing iron-based catalysts

DOEpatents

Farcasiu, Malvina; Kaufman, Phillip B.; Diehl, J. Rodney; Kathrein, Hendrik

1999-01-01

A method for preparing an acid catalyst having a long shelf-life is provided comprising doping crystalline iron oxides with lattice-compatible metals and heating the now-doped oxide with halogen compounds at elevated temperatures. The invention also provides for a catalyst comprising an iron oxide particle having a predetermined lattice structure, one or more metal dopants for said iron oxide, said dopants having an ionic radius compatible with said lattice structure; and a halogen bound with the iron and the metal dopants on the surface of the particle.

Nickel/ruthenium catalyst and method for aqueous phase reactions

DOEpatents

Elliott, Douglas C.; Sealock, John L.

1998-01-01

A method of hydrogenation using a catalyst in the form of a plurality of porous particles wherein each particle is a support having nickel metal catalytic phase or reduced nickel deposited thereon in a first dispersed phase and an additional ruthenium metal deposited onto the support in a second dispersed phase. The additional ruthenium metal is effective in retarding or reducing agglomeration or sintering of the nickel metal catalytic phase thereby increasing the life time of the catalyst during hydrogenation reactions.

Catalyst and method for aqueous phase reactions

DOEpatents

Elliott, Douglas C.; Hart, Todd R.

1999-01-01

The present invention is a catalyst in the form of a plurality of porous particles wherein each particle is a support having nickel metal catalytic phase or reduced nickel deposited thereon in a first dispersed phase and an additional metal deposited onto the support in a second dispersed phase. The additional metal is effective in retarding or reducing agglomeration or sintering of the nickel metal catalytic phase without substantially affecting the catalytic activity, thereby increasing the life time of the catalyst.

Catalytic copyrolysis of particle board and polypropylene over Al-MCM-48

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

Kim, Hannah; Choi, Suek Ju; Kim, Ji Man

Highlights: • Al-MCM-48 was used for catalytic copyrolysis of particle board and polypropylene. • Catalytic produced mainly hydrocarbons. • The hydrocarbons produced were mainly in the diesel range. - Abstract: Particle board and polypropylene (PP) at a mixing ratio of 1:1 were copyrolyzed over two Al-MCM-48 catalysts with Si/Al ratios of 20 and 80. The catalyst characteristics were examined by measuring the Brunauer-Emmett-Teller surface area, temperature programmed desorption of ammonia, and X-ray diffraction. The main pyrolysis products of particle board were oxygenates, acids, and phenolics, whereas a large quantity of hydrocarbons within the diesel fuel range was produced from copyrolysismore » with polypropylene. The catalytic copyrolysis of particle board and PP over the Al-MCM-48 catalysts produced bio-oil with a much larger hydrocarbon content than that from the catalytic pyrolysis of particle board only. The hydrocarbons produced were mainly in the diesel range, highlighting the potential for the production of high-quality fuel.« less

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...

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.

Platinum particle size and support effects in NO(x) mediated carbon oxidation over platinum catalysts.

PubMed

Villani, Kenneth; Vermandel, Walter; Smets, Koen; Liang, Duoduo; van Tendeloo, Gustaaf; Martens, Johan A

2006-04-15

Platinum metal was dispersed on microporous, mesoporous, and nonporous support materials including the zeolites Na-Y, Ba-Y, Ferrierite, ZSM-22, ETS-10, and AIPO-11, alumina, and titania. The oxidation of carbon black loosely mixed with catalyst powder was monitored gravimetrically in a gas stream containing nitric oxide, oxygen, and water. The carbon oxidation activity of the catalysts was found to be uniquely related to the Pt dispersion and little influenced by support type. The optimum dispersion is around 3-4% corresponding to relatively large Pt particle sizes of 20-40 nm. The carbon oxidation activity reflects the NO oxidation activity of the platinum catalyst, which reaches an optimum in the 20-40 nm Pt particle size range. The lowest carbon oxidation temperatures were achieved with platinum loaded ZSM-22 and AIPO-11 zeolite crystallites bearing platinum of optimum dispersion on their external surfaces.

Catalyst containing oxygen transport membrane

DOEpatents

Lane, Jonathan A.; Wilson, Jamie R.; Christie, Gervase Maxwell; Petigny, Nathalie; Sarantopoulos, Christos

2017-02-07

A composite oxygen transport membrane having a dense layer, a porous support layer and an intermediate porous layer located between the dense layer and the porous support layer. Both the dense layer and the intermediate porous layer are formed from an ionic conductive material to conduct oxygen ions and an electrically conductive material to conduct electrons. The porous support layer has a high permeability, high porosity, and a microstructure exhibiting substantially uniform pore size distribution as a result of using PMMA pore forming materials or a bi-modal particle size distribution of the porous support layer materials. Catalyst particles selected to promote oxidation of a combustible substance are located in the intermediate porous layer and in the porous support adjacent to the intermediate porous layer. The catalyst particles can be formed by wicking a solution of catalyst precursors through the porous support toward the intermediate porous layer.

Suppression of oxygen reduction reaction activity on Pt-based electrocatalysts from ionomer incorporation

NASA Astrophysics Data System (ADS)

Shinozaki, Kazuma; Morimoto, Yu; Pivovar, Bryan S.; Kocha, Shyam S.

2016-09-01

The impact of Nafion on the oxygen reduction reaction (ORR) activity is studied for Pt/C and Pt-alloy/C catalysts using thin-film rotating disk electrode (TF-RDE) methods in 0.1 M HClO4. Ultrathin uniform catalyst layers and standardized activity measurement protocols are employed to obtain accurate and reproducible ORR activity. Nafion lowers the ORR activity which plateaus with increasing loading on Pt catalysts. Pt particle size is found not to have significant influence on the extent of the SA decrease upon Nafion incorporation. Catalysts using high surface area carbon (HSC) support exhibit attenuated activity loss resulting from lower ionomer coverage on catalyst particles located within the deep pores. The impact of metallic composition on the activity loss due to Nafion incorporation is also discussed.

Autothermal reforming of propane over Mg-Al hydrotalcite-like catalysts.

PubMed

Lim, You-Soon; Park, Nam-Cook; Shin, Jae-Soon; Kim, Jong-Ho; Moon, Dong-Ju; Kim, Young-Chul

2008-10-01

The performance of hydrotalcite-like catalysts in propane autothermal reforming for hydrogen production was studied in fixed-bed flow reactor. Hydrotalcite-like catalysts were synthesized by coprecipitation and modified co-precipitation by the impregnation method and those were promoted by the addition of noble metals. Reaction test results indicated that hydrotalcite-like catalysts of modified method were showed higher H2-yield than co-precipitation method because surface Ni particles of catalysts by modified method were more abundant. When added noble metals, the activity was enhanced because the size of nickel particles was decreased and degree of dispersion was increased. Also the carbon deposit is low after the reaction. When solvent of solution was changed, activity was increased. It is because degree of dispersion was increased.

CO Sensing Performance of a Micro Thermoelectric Gas Sensor with AuPtPd/SnO2 Catalyst and Effects of a Double Catalyst Structure with Pt/α-Al2O3

PubMed Central

Goto, Tomoyo; Itoh, Toshio; Akamatsu, Takafumi; Shin, Woosuck

2015-01-01

The CO sensing properties of a micro thermoelectric gas sensor (micro-TGS) with a double AuPtPd/SnO2 and Pt/α-Al2O3 catalyst were investigated. While several nanometer sized Pt and Pd particles were uniformly dispersed on SnO2, the Au particles were aggregated as particles measuring >10 nm in diameter. In situ diffuse reflectance Fourier transform Infrared spectroscopy (DRIFT) analysis of the catalyst showed a CO adsorption peak on Pt and Pd, but no clear peak corresponding to the interaction between CO and Au was detected. Up to 200 °C, CO combustion was more temperature dependent than that of H2, while H2 combustion was activated by repeated exposure to H2 gas during the periodic gas test. Selective CO sensing of the micro-TGS against H2 was attempted using a double catalyst structure with 0.3–30 wt% Pt/α-Al2O3 as a counterpart combustion catalyst. The sensor output of the micro-TGS decreased with increasing Pt content in the Pt/α-Al2O3 catalyst, by cancelling out the combustion heat from the AuPtPd/SnO2 catalyst. In addition, the AuPtPd/SnO2 and 0.3 wt% Pt/α-Al2O3 double catalyst sensor showed good and selective CO detection. We therefore demonstrated that our micro-TGS with double catalyst structure is useful for controlling the gas selectivity of CO against H2. PMID:26694397

On-line crack prognosis in attachment lug using Lamb wave-deterministic resampling particle filter-based method

NASA Astrophysics Data System (ADS)

Yuan, Shenfang; Chen, Jian; Yang, Weibo; Qiu, Lei

2017-08-01

Fatigue crack growth prognosis is important for prolonging service time, improving safety, and reducing maintenance cost in many safety-critical systems, such as in aircraft, wind turbines, bridges, and nuclear plants. Combining fatigue crack growth models with the particle filter (PF) method has proved promising to deal with the uncertainties during fatigue crack growth and reach a more accurate prognosis. However, research on prognosis methods integrating on-line crack monitoring with the PF method is still lacking, as well as experimental verifications. Besides, the PF methods adopted so far are almost all sequential importance resampling-based PFs, which usually encounter sample impoverishment problems, and hence performs poorly. To solve these problems, in this paper, the piezoelectric transducers (PZTs)-based active Lamb wave method is adopted for on-line crack monitoring. The deterministic resampling PF (DRPF) is proposed to be used in fatigue crack growth prognosis, which can overcome the sample impoverishment problem. The proposed method is verified through fatigue tests of attachment lugs, which are a kind of important joint component in aerospace systems.

Rapid and Efficient Collection of Platinum from Karstedt's Catalyst Solution via Ligands-Exchange-Induced Assembly.

PubMed

Yang, Gonghua; Wei, Yanlong; Huang, Zhenzhu; Hu, Jiwen; Liu, Guojun; Ou, Ming; Lin, Shudong; Tu, Yuanyuan

2018-02-21

Reported herein is a novel strategy for the rapid and efficient collection of platinum from Karstedt's catalyst solution. By taking advantage of a ligand-exchange reaction between alkynols and the 1,3-divinyltetramethyldisiloxane ligand (M Vi M Vi ) that coordinated with platinum (Pt(0)), the Karstedt's catalyst particles with a size of approximately 2.5 ± 0.7 nm could be reconstructed and assembled into larger particles with a size of 150 ± 35 nm due to the hydrogen bonding between the hydroxyl groups of the alkynol. In addition, because the silicone-soluble M Vi M Vi ligand of the Karstedt's catalyst was replaced by water-soluble alkynol ligands, the resultant large particles were readily dispersed in water, resulting in rapid, efficient, and complete collection of platinum from the Karstedt's catalyst solutions with platinum concentrations in the range from ∼20 000 to 0.05 ppm. Our current strategy not only was used for the rapid and efficient collection of platinum from the Karstedt's catalyst solutions, but it also enabled the precise evaluation of the platinum content in the Karstedt's catalysts, even if this platinum content was extremely low (i.e., 0.05 ppm). Moreover, these platinum specimens that were efficiently collected from the Karstedt's catalyst solutions could be directly used for the evaluation of platinum without the need for pretreatment processes, such as calcination and digestion with hydrofluoric acid, that were traditionally used prior to testing via inductively coupled plasma mass spectrometry in conventional methods.

Macro and micro mechanics behavior of granite after heat treatment by cluster model in particle flow code

NASA Astrophysics Data System (ADS)

Tian, Wen-Ling; Yang, Sheng-Qi; Huang, Yan-Hua

2018-02-01

In this paper, a cluster model in particle flow code was used to simulate granite specimens after heat treatment under uniaxial compression. The results demonstrated that micro-cracks are randomly distributed in the specimen when the temperature is below 300 {°}C, and have partial coalescence when the temperature is up to 450 {°}C, then form macro-cracks when the temperature is above 600 {°}C. There is more inter-granular cracking than intra-granular cracking, and their ratio increases with increasing temperature. The micro-cracks are almost constant when the temperature decreases from 900 {°}C to room temperature, except for quartz α -β phase transition temperature (573 {°}C). The fracture evolution process is obviously affected by these cracks, especially at 600-900 {°}C. Elevated temperature leads to easily developed displacement between the grains, and the capacity to store strain energy becomes weaker, corresponding to the plasticity of granite after heat treatment.

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

An Integrated Computational and Experimental Approach Toward the Design of Materials for Fuel Cell Systems

DTIC Science & Technology

2012-10-01

13 Based on the limited work done, the best reported ORR chalcogenide electrocatalysts for PEMFC applications can be ranked as follows: MoRuSe... PEMFC catalysts is the durability of the catalyst particles. Particle size distribution tends to shift towards larger particles during the...the design of new materials for applications in PEMFCs . Reference: A more detailed treatment of the topics of this section, Experimental Target 11

Crack identification and evolution law in the vibration failure process of loaded coal

NASA Astrophysics Data System (ADS)

Li, Chengwu; Ai, Dihao; Sun, Xiaoyuan; Xie, Beijing

2017-08-01

To study the characteristics of coal cracks produced in the vibration failure process, we set up a static load and static and dynamic combination load failure test simulation system, prepared with different particle size, formation pressure, and firmness coefficient coal samples. Through static load damage testing of coal samples and then dynamic load (vibration exciter) and static (jack) combination destructive testing, the crack images of coal samples under the load condition were obtained. Combined with digital image processing technology, an algorithm of crack identification with high precision and in real-time is proposed. With the crack features of the coal samples under different load conditions as the research object, we analyzed the distribution of cracks on the surface of the coal samples and the factors influencing crack evolution using the proposed algorithm and a high-resolution industrial camera. Experimental results showed that the major portion of the crack after excitation is located in the rear of the coal sample where the vibration exciter cannot act. Under the same disturbance conditions, crack size and particle size exhibit a positive correlation, while crack size and formation pressure exhibit a negative correlation. Soft coal is more likely to lead to crack evolution than hard coal, and more easily causes instability failure. The experimental results and crack identification algorithm provide a solid basis for the prevention and control of instability and failure of coal and rock mass, and they are helpful in improving the monitoring method of coal and rock dynamic disasters.

CO2 hydrogenation to methanol on supported Au catalysts under moderate reaction conditions: support and particle size effects.

PubMed

Hartadi, Yeusy; Widmann, Daniel; Behm, R Jürgen

2015-02-01

The potential of metal oxide supported Au catalysts for the formation of methanol from CO2 and H2 under conditions favorable for decentralized and local conversion, which could be concepts for chemical energy storage, was investigated. Significant differences in the catalytic activity and selectivity of Au/Al2 O3 , Au/TiO2 , AuZnO, and Au/ZrO2 catalysts for methanol formation under moderate reaction conditions at a pressure of 5 bar and temperatures between 220 and 240 °C demonstrate pronounced support effects. A high selectivity (>50 %) for methanol formation was obtained only for Au/ZnO. Furthermore, measurements on Au/ZnO samples with different Au particle sizes reveal distinct Au particle size effects: although the activity increases strongly with the decreasing particle size, the selectivity decreases. The consequences of these findings for the reaction mechanism and for the potential of Au/ZnO catalysts for chemical energy storage and a "green" methanol technology are discussed. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Improvement of Flame-made ZnO Nanoparticulate Thick Film Morphology for Ethanol Sensing

PubMed Central

Liewhiran, Chaikarn; Phanichphantandast, Sukon

2007-01-01

ZnO nanoparticles were produced by flame spray pyrolysis using zinc naphthenate as a precursor dissolved in toluene/acetonitrile (80/20 vol%). The particles properties were analyzed by XRD, BET. The ZnO particle size and morphology was observed by SEM and HR-TEM revealing spheroidal, hexagonal, and rod-like morphologies. The crystallite sizes of ZnO spheroidal and hexagonal particles ranged from 10-20 nm. ZnO nanorods were ranged from 10-20 nm in width and 20-50 nm in length. Sensing films were produced by mixing the nanoparticles into an organic paste composed of terpineol and ethyl cellulose as a vehicle binder. The paste was doctor-bladed onto Al2O3 substrates interdigitated with Au electrodes. The morphology of the sensing films was analyzed by optical microscopy and SEM analysis. Cracking of the sensing films during annealing process was improved by varying the heating conditions. The gas sensing of ethanol (25-250 ppm) was studied at 400 °C in dry air containing SiC as the fluidized particles. The oxidation of ethanol on the surface of the semiconductor was confirmed by mass spectroscopy (MS). The effect of micro-cracks was quantitatively accounted for as a provider of extra exposed edges. The sensitivity decreased notably with increasing crack of sensing films. It can be observed that crack widths were reduced with decreasing heating rates. Crack-free of thick (5 μm) ZnO films evidently showed higher sensor signal and faster response times (within seconds) than cracked sensor. The sensor signal increased and the response time decreased with increasing ethanol concentration.

A jellium model of a catalyst particle in carbon nanotube growth

NASA Astrophysics Data System (ADS)

Artyukhov, Vasilii I.; Liu, Mingjie; Penev, Evgeni S.; Yakobson, Boris I.

2017-06-01

We show how a jellium model can represent a catalyst particle within the density-functional theory based approaches to the growth mechanism of carbon nanotubes (CNTs). The advantage of jellium is an abridged, less computationally taxing description of the multi-atom metal particle, while at the same time in avoiding the uncertainty of selecting a particular atomic geometry of either a solid or ever-changing liquid catalyst particle. A careful choice of jellium sphere size and its electron density as a descriptive parameter allows one to calculate the CNT-metal interface energies close to explicit full atomistic models. Further, we show that using jellium permits computing and comparing the formation of topological defects (sole pentagons or heptagons, the culprits of growth termination) as well as pentagon-heptagon pairs 5|7 (known as chirality-switching dislocation).

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.

Electrochemical and Structural Study of a Chemically Dealloyed PtCu Oxygen Reduction Catalyst

PubMed Central

Dutta, Indrajit; Carpenter, Michael K; Balogh, Michael P; Ziegelbauer, Joseph M; Moylan, Thomas E; Atwan, Mohammed H; Irish, Nicholas P

2013-01-01

A carbon-supported, dealloyed platinum-copper (Pt-Cu) oxygen reduction catalyst was prepared using a multi-step synthetic procedure. Material produced at each step was characterized using high angle annular dark field scanning transmission electron microscopy (HAADF-STEM), electron energy loss spectroscopy (EELS) mapping, x-ray absorption spectroscopy (XAS), x-ray diffraction (XRD), and cyclic voltammetry (CV), and its oxygen reduction reaction (ORR) activity was measured by a thin-film rotating disk electrode (TF-RDE) technique. The initial synthetic step, a co-reduction of metal salts, produced a range of poorly crystalline Pt, Cu, and Pt-Cu alloy nanoparticles that nevertheless exhibited good ORR activity. Annealing this material alloyed the metals and increased particle size and crystallinity. TEM shows the annealed catalyst to include particles of various sizes, large (>25 nm), medium (12–25 nm), and small (<12 nm). Most of the small and medium-sized particles exhibited a partial or complete coreshell (Cu-rich core and Pt shell) structure with the smaller particles typically having more complete shells. The appearance of Pt shells after annealing indicates that they are formed by a thermal diffusion mechanism. Although the specific activity of the catalyst material was more than doubled by annealing, the concomitant decrease in Pt surface area resulted in a drop in its mass activity. Subsequent dealloying of the catalyst by acid treatment to partially remove the copper increased the Pt surface area by changing the morphology of the large and some medium particles to a “Swiss cheese” type structure having many voids. The smaller particles retained their core-shell structure. The specific activity of the catalyst material was little reduced by dealloying, but its mass activity was more than doubled due to the increase in surface area. The possible origins of these results are discussed in this report. PMID:23807900

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

Variation of stresses ahead of the internal cracks in ReNi{sub 5} powders during hydrogen charging and discharging cycles

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

Biner, S.B.

1998-07-01

In this study, the evolution of the stress-states ahead of the penny shaped internal cracks in both spherical and disk shaped ReNi{sub 5} particles during hydrogen charging and discharging cycles were investigated using coupled diffusion/deformation FEM analyses. The results indicate that large tensile stresses, on the order of 20--50% of the modulus of elasticity, develop in the particles. The disk shaped particles, in addition to having faster charging/discharging cycles, may offer better resistance to fracture than the spherical particles.

The Dependence of CNT Aerogel Synthesis on Sulfur-driven Catalyst Nucleation Processes and a Critical Catalyst Particle Mass Concentration.

PubMed

Hoecker, Christian; Smail, Fiona; Pick, Martin; Weller, Lee; Boies, Adam M

2017-11-06

The floating catalyst chemical vapor deposition (FC-CVD) process permits macro-scale assembly of nanoscale materials, enabling continuous production of carbon nanotube (CNT) aerogels. Despite the intensive research in the field, fundamental uncertainties remain regarding how catalyst particle dynamics within the system influence the CNT aerogel formation, thus limiting effective scale-up. While aerogel formation in FC-CVD reactors requires a catalyst (typically iron, Fe) and a promotor (typically sulfur, S), their synergistic roles are not fully understood. This paper presents a paradigm shift in the understanding of the role of S in the process with new experimental studies identifying that S lowers the nucleation barrier of the catalyst nanoparticles. Furthermore, CNT aerogel formation requires a critical threshold of Fe x C y  > 160 mg/m 3 , but is surprisingly independent of the initial catalyst diameter or number concentration. The robustness of the critical catalyst mass concentration principle is proved further by producing CNTs using alternative catalyst systems; Fe nanoparticles from a plasma spark generator and cobaltocene and nickelocene precursors. This finding provides evidence that low-cost and high throughput CNT aerogel routes may be achieved by decoupled and enhanced catalyst production and control, opening up new possibilities for large-scale CNT synthesis.

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.

Impacts of continuously regenerating trap and particle oxidation catalyst on the NO2 and particulate matter emissions emitted from diesel engine.

PubMed

Liu, Zhihua; Ge, Yunshan; Tan, Jianwei; He, Chao; Shah, Asad Naeem; Ding, Yan; Yu, Linxiao; Zhao, Wei

2012-01-01

Two continuously regenerating diesel particulate filter (CRDPF) with different configurations and one particles oxidation catalyst (POC) were employed to perform experiments in a controlled laboratory setting to evaluate their effects on NO2, smoke and particle number emissions. The results showed that the application of the after-treatments increased the emission ratios of NO2/NOx significantly. The results of smoke emissions and particle number (PN) emissions indicated that both CRDPFs had sufficient capacity to remove more than 90% of total particulate matter (PM) and more than 97% of solid particles. However, the POC was able to remove the organic components of total PM, and only partially to remove the carbonaceous particles with size less than 30 nm. The negligible effects of POC on larger particles were observed due to its honeycomb structure leads to an inadequate residence time to oxidize the solid particles or trap them. The particles removal efficiencies of CRDPFs had high degree of correlations with the emission ratio of NO2/NOx. The PN emission results from two CRDPFs indicated that more NO2 generating in diesel oxidation catalyst section could obtain the higher removal efficiency of solid particles. However this also increased the risk of NO2 exposure in atmosphere.

Diameter modulation of vertically aligned single-walled carbon nanotubes.

PubMed

Xiang, Rong; Einarsson, Erik; Murakami, Yoichi; Shiomi, Junichiro; Chiashi, Shohei; Tang, Zikang; Maruyama, Shigeo

2012-08-28

We demonstrate wide-range diameter modulation of vertically aligned single-walled carbon nanotubes (SWNTs) using a wet chemistry prepared catalyst. In order to ensure compatibility to electronic applications, the current minimum mean diameter of 2 nm for vertically aligned SWNTs is challenged. The mean diameter is decreased to about 1.4 nm by reducing Co catalyst concentrations to 1/100 or by increasing Mo catalyst concentrations by five times. We also propose a novel spectral analysis method that allows one to distinguish absorbance contributions from the upper, middle, and lower parts of a nanotube array. We use this method to quantitatively characterize the slight diameter change observed along the array height. On the basis of further investigation of the array and catalyst particles, we conclude that catalyst aggregation-rather than Ostwald ripening-dominates the growth of metal particles.

Synthesis of Highly Dispersed and Highly Stable Supported Au–Pt Bimetallic Catalysts by a Two-Step Method

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

Wang, Xiaofeng; Zhao, Haiyan; Wu, Tianpin

2016-11-01

Highly dispersed and highly stable supported bimetallic catalysts were prepared using a two-step process. Pt nanoparticles (NPs) were first deposited on porous γ-Al2O3 particles by atomic layer deposition (ALD). Au NPs were synthesized by using gold(III) chloride as the Au precursor, and then immobilized on ALD Pt/γ-Al2O3 particles. The Au–Pt bimetallic catalysts were highly active and highly stable in a vigorously stirred liquid phase reaction of glucose oxidation.

Enhanced catalytic activity of the nanostructured Co-W-B film catalysts for hydrogen evolution from the hydrolysis of ammonia borane.

PubMed

Li, Chao; Wang, Dan; Wang, Yan; Li, Guode; Hu, Guijuan; Wu, Shiwei; Cao, Zhongqiu; Zhang, Ke

2018-08-15

In this work, nanostructured Co-W-B films are successfully synthesized on the foam sponge by electroless plating method and employed as the catalysts with enhanced catalytic activity towards hydrogen evolution from the hydrolysis of ammonia borane (NH 3 BH 3 , AB) at room temperature. The particle size of the as-prepared Co-W-B film catalysts is varied by adjusting the depositional pH value to identify the most suitable particle size for hydrogen evolution of AB hydrolysis. The Co-W-B film catalyst with the particle size of about 67.3 nm shows the highest catalytic activity and can reach a hydrogen generation rate of 3327.7 mL min -1 g cat -1 at 298 K. The activation energy of the hydrolysis reaction of AB is determined to be 32.2 kJ mol -1 . Remarkably, the as-obtained Co-W-B film is also a reusable catalyst preserving 78.4% of their initial catalytic activity even after 5 cycles in hydrolysis of AB at room temperature. Thus, the enhanced catalytic activity illustrates that the Co-W-B film is a promising catalyst for AB hydrolytic dehydrogenation in fuel cells and the related fields. Copyright © 2018 Elsevier Inc. All rights reserved.

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.

Selective catalysts and their preparation for catalytic hydrocarbon synthesis

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

Iglesia, E.; Vroman, H.; Soled, S.

1991-07-30

This patent describes a method for preparing a supported cobalt catalyst particle. It comprises contacting a support particle with a molten cobalt salt, for a period sufficient to impregnate substantially all of the molten cobalt salt on the support to a depth of less than about 200 {mu}m; drying the supported cobalt salt obtained; reducing the cobalt of the supported cobalt salt to metallic cobalt by heating the salt in the presence of H{sub 2}, wherein the heating is conducted at a rate of less than about 1{degrees} C./min. up to a maximum temperature ranging from about 100{degrees} C. tomore » about 500{degrees} C., to produce a supported cobalt catalyst particle.« less

Covalent Immobilization of (-)-Riboflavin on Polymer Functionalized Silica Particles: Application in the Photocatalytic E→Z Isomerization of Polarized Alkenes.

PubMed

Metternich, Jan B; Sagebiel, Sven; Lückener, Anne; Lamping, Sebastian; Ravoo, Bart Jan; Gilmour, Ryan

2018-03-20

The covalent immobilization of the biomimetic, photo-organocatalyst (-)-riboflavin on silica micro- and nanoparticles via atom transfer radical polymerization (ATRP) is disclosed. Given the effectiveness of (-)-riboflavin as a versatile, environmentally benign photocatalyst, an immobilization strategy based on acrylate-linker modification of the catalyst core and controlled polymerization on initiator pre-functionalized silica particles has been developed. Validation of this approach is demonstrated in the E→Z isomerization of a benchmark cinnamonitrile (Z/E up to 88:12) with 0.97 mol % catalyst loading. Characterization of the immobilized photocatalyst supports covalent embedding of the catalyst in the polymeric brushes on the silica particle surface. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Liquid phase catalytic hydrodebromination of tetrabromobisphenol A on supported Pd catalysts

NASA Astrophysics Data System (ADS)

Wu, Ke; Zheng, Mengjia; Han, Yuxiang; Xu, Zhaoyi; Zheng, Shourong

2016-07-01

Tetrabromobisphenol A (TBBPA) is a widely used brominated flame retardant and reductive debromination is an effective method for the abatement of TBBPA pollution. In this study, Pd catalysts supported on TiO2, CeO2, Al2O3 and SiO2 were prepared by the impregnation (the resulting catalyst denoted as im-Pd/support), deposition-precipitation (the resulting catalyst denoted as dp-Pd/support), and photo-deposition (the resulting catalyst denoted as pd-Pd/support) methods. The catalysts were characterized by N2 adsorption-desorption isotherm, X-ray diffraction, transmission electron microscopy, measurement of zeta potential, CO chemisorption, and X-ray photoelectron spectroscopy. The results showed that at an identical Pd loading amount (2.0 wt.%) Pd particle size in dp-Pd/TiO2 was much smaller than those in im-Pd/TiO2 and pd-Pd/TiO2. Pd particle size of the dp-Pd/TiO2 catalyst increased with Pd loading amount. Additionally, Pd particles in the dp-Pd/TiO2 catalysts were positively charged due to the strong metal-support interaction, whereas the cationization effect was gradually attenuated with the increase of Pd loading amount. For the liquid phase catalytic hydrodebromination (HDB) of TBBPA, tri-bromobisphenol A (tri-BBPA), di-bromobisphenol A (di-BBPA), and mono-bromobisphenol A (mono-BBPA) were identified as the intermediate products, indicative of a stepwise debromination process. The catalytic HDB of TBBPA followed the Langmuir-Hinshelwood model, reflecting an adsorption enhanced catalysis mechanism. At an identical Pd loading amount, the Pd catalyst supported on TiO2 exhibited a much higher catalytic activity than those on other supports. Furthermore, dp-Pd/TiO2 was found to be more active than im-Pd/TiO2 and pd-Pd/TiO2.

To alloy or not to alloy? Cr modified Pt/C cathode catalysts for PEM fuel cells.

PubMed

Wells, Peter P; Qian, Yangdong; King, Colin R; Wiltshire, Richard J K; Crabb, Eleanor M; Smart, Lesley E; Thompsett, David; Russell, Andrea E

2008-01-01

The cathode electrocatalysts for proton exchange membrane (PEM) fuel cells are commonly platinum and platinum based alloy nanoparticles dispersed on a carbon support. Control over the particle size and composition has, historically, been attained empirically, making systematic studies of the effects of various structural parameters difficult. The controlled surface modification methodology used in this work has enabled the controlled modification of carbon supported Pt nanoparticles by Cr so as to yield nanoalloy particles with defined compositions. Subsequent heat treatment in 5% H2 in N2 resulted in the formation of a distinct Pt3Cr alloy phase which was either restricted to the surface of the particles or present throughout the bulk of the particle structure. Measurement of the oxygen reduction activity of the catalysts was accomplished using the rotating thin film electrode method and the activities obtained were related to the structure of the nanoalloy catalyst particles, largely determined using Cr K edge and Pt L3 edge XAS.

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.

Bubbling bed catalytic hydropyrolysis process utilizing larger catalyst particles and smaller biomass particles featuring an anti-slugging reactor

DOEpatents

Marker, Terry L; Felix, Larry G; Linck, Martin B; Roberts, Michael J

2014-09-23

This invention relates to a process for thermochemically transforming biomass or other oxygenated feedstocks into high quality liquid hydrocarbon fuels. In particular, a catalytic hydropyrolysis reactor, containing a deep bed of fluidized catalyst particles is utilized to accept particles of biomass or other oxygenated feedstocks that are significantly smaller than the particles of catalyst in the fluidized bed. The reactor features an insert or other structure disposed within the reactor vessel that inhibits slugging of the bed and thereby minimizes attrition of the catalyst. Within the bed, the biomass feedstock is converted into a vapor-phase product, containing hydrocarbon molecules and other process vapors, and an entrained solid char product, which is separated from the vapor stream after the vapor stream has been exhausted from the top of the reactor. When the product vapor stream is cooled to ambient temperatures, a significant proportion of the hydrocarbons in the product vapor stream can be recovered as a liquid stream of hydrophobic hydrocarbons, with properties consistent with those of gasoline, kerosene, and diesel fuel. Separate streams of gasoline, kerosene, and diesel fuel may also be obtained, either via selective condensation of each type of fuel, or via later distillation of the combined hydrocarbon liquid.

Bubbling bed catalytic hydropyrolysis process utilizinig larger catalyst particles and small biomass particles featuring an anti-slugging reactor

DOEpatents

Marker, Terry L.; Felix, Larry G.; Linck, Martin B.; Roberts, Michael J.

2016-12-06

This invention relates to a process for thermochemically transforming biomass or other oxygenated feedstocks into high quality liquid hydrocarbon fuels. In particular, a catalytic hydropyrolysis reactor, containing a deep bed of fluidized catalyst particles is utilized to accept particles of biomass or other oxygenated feedstocks that are significantly smaller than the particles of catalyst in the fluidized bed. The reactor features an insert or other structure disposed within the reactor vessel that inhibits slugging of the bed and thereby minimizes attrition of the catalyst. Within the bed, the biomass feedstock is converted into a vapor-phase product, containing hydrocarbon molecules and other process vapors, and an entrained solid char product, which is separated from the vapor stream after the vapor stream has been exhausted from the top of the reactor. When the product vapor stream is cooled to ambient temperatures, a significant proportion of the hydrocarbons in the product vapor stream can be recovered as a liquid stream of hydrophobic hydrocarbons, with properties consistent with those of gasoline, kerosene, and diesel fuel. Separate streams of gasoline, kerosene, and diesel fuel may also be obtained, either via selective condensation of each type of fuel, or via later distillation of the combined hydrocarbon liquid.

Caramel popcorn shaped silicon particle with carbon coating as a high performance anode material for Li-ion batteries.

PubMed

He, Meinan; Sa, Qina; Liu, Gao; Wang, Yan

2013-11-13

Silicon is a very promising anode material for lithium ion batteries. It has a 4200 mAh/g theoretical capacity, which is ten times higher than that of commercial graphite anodes. However, when lithium ions diffuse to Si anodes, the volume of Si will expand to almost 400% of its initial size and lead to the crack of Si. Such a huge volume change and crack cause significant capacity loss. Meanwhile, with the crack of Si particles, the conductivity between the electrode and the current collector drops. Moreover, the solid electrolyte interphase (SEI), which is generated during the cycling, reduces the discharge capacity. These issues must be addressed for widespread application of this material. In this work, caramel popcorn shaped porous silicon particles with carbon coating are fabricated by a set of simple chemical methods as active anode material. Si particles are etched to form a porous structure. The pores in Si provide space for the volume expansion and liquid electrolyte diffusion. A layer of amorphous carbon is formed inside the pores, which gives an excellent isolation between the Si particle and electrolyte, so that the formation of the SEI layer is stabilized. Meanwhile, this novel structure enhances the mechanical properties of the Si particles, and the crack phenomenon caused by the volume change is significantly restrained. Therefore, an excellent cycle life under a high rate for the novel Si electrode is achieved.

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

Parab, Niranjan D.; Hudspeth, Matthew; Claus, Ben

Granular materials are widely used to resist impact and blast. Under these dynamic loadings, the constituent particles in the granular system fracture. To study the fracture mechanisms in brittle particles under dynamic compressive loading, a high speed X-ray phase contrast imaging setup was synchronized with a Kolsky bar apparatus. Controlled compressive loading was applied on two contacting particles using the Kolsky bar apparatus and fracture process was captured using the high speed X-ray imaging setup. Five different particles were investigated: soda-lime glass, polycrystalline silica (silicon dioxide), polycrystalline silicon, barium titanate glass, and yttrium stabilized zirconia. For both soda lime glassmore » and polycrystalline silica particles, one of the particles fragmented explosively, thus breaking into many small pieces. For Silicon and barium titanate glass particles, a finite number of cracks were observed in one of the particles causing it to fracture. For yttrium stabilized zirconia particles, a single meridonial crack developed in one of the particles, breaking it into two parts.« less

Alignment mechanism of carbon nanofibers produced by plasma-enhanced chemical-vapor deposition

NASA Astrophysics Data System (ADS)

Merkulov, Vladimir I.; Melechko, Anatoli V.; Guillorn, Michael A.; Lowndes, Douglas H.; Simpson, Michael L.

2001-10-01

We report experimental evidence showing a direct correlation between the alignment of carbon nanofibers (CNFs) prepared by plasma-enhanced chemical-vapor deposition and the location of the catalyst particle during CNF growth. In particular, we find that CNFs that have a catalyst particle at the tip (i.e., growth proceeds from the tip) align along the electric-field lines, whereas CNFs with the particle at the base (i.e., growth proceeds from the base) grow in random orientations. We propose a model that explains the alignment process as a result of a feedback mechanism associated with a nonuniform stress (part tensile, part compressive) that is created across the interface of the catalyst particle with the CNF due to electrostatic forces. Furthermore, we propose that the alignment seen recently in some dense CNF films is due to a crowding effect and is not directly the result of electrostatic forces.

Microcalorimetric, {sup 13}C NMR spectroscopic, and reaction kinetic studies of silica- and L-zeolite-supported platinum catalysts for n-hexane conversion

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

Sharma, S.B.; Ouraipryvan, P.; Nair, H.A.

Reaction kinetics measurement of n-hexane conversion over 4% Pt/SiO{sub 2} and 1% Pt/SiO{sub 2} and 1% Pt/K(Ba)-L catalysts were made at a pressure of 3 atm and temperatures from 698 to 750 K. The rates of benzene and methylcyclopentane formation decrease with time during reaction over Pt/SiO{sub 2}, while 1% Pt/K(Ba)-L does not deactivate significantly. Microcalorimetric measurements at 353 K show that the heat of carbon monoxide adsorption is the same on freshly reduced Pt/SiO{sub 2} and Pt/K(Ba)-L catalysts; however, carbonaceous species that accumulate on Pt/SiO{sub 2} during n-hexane conversion decrease the total number of adsorption sites and the numbermore » of sites that adsorb carbon monoxide strongly. The 1% Pt/K(Ba)-L catalyst retains the adsorptive properties of the freshly reduced catalyst. Nuclear magnetic resonance studies of {sup 13}CO adsorption show that cluster-sized platinum particles are more resistant to deactivation by self-poisoning reactions than larger platinum particles. The greater catalyst stability and higher steady-state activity of L-zeolite-supported platinum catalysts may be attributed to the ability of L-zeolite to stabilize cluster-sized particles under reaction conditions. Differences in dehydrocyclization activity between catalysts may be related to differences in the number of strong adsorption sites that are present under reaction conditions. 31 refs., 7 figs., 4 tabs.« less

Pt based PEMFC catalysts prepared from colloidal particle suspensions--a toolbox for model studies.

PubMed

Speder, Jozsef; Altmann, Lena; Roefzaad, Melanie; Bäumer, Marcus; Kirkensgaard, Jacob J K; Mortensen, Kell; Arenz, Matthias

2013-03-14

A colloidal synthesis approach is presented that allows systematic studies of the properties of supported proton exchange membrane fuel cell (PEMFC) catalysts. The applied synthesis route is based on the preparation of monodisperse nanoparticles in the absence of strong binding organic stabilizing agents. No temperature post-treatment of the catalyst is required rendering the synthesis route ideally suitable for comparative studies. We report work concerning a series of catalysts based on the same colloidal Pt nanoparticle (NP) suspension, but with different high surface area (HSA) carbon supports. It is shown that for the prepared catalysts the carbon support has no catalytic co-function, but carbon pre-treatment leads to enhanced sticking of the Pt NPs on the support. An unwanted side effect, however, is NP agglomeration during synthesis. By contrast, enhanced NP sticking without agglomeration can be accomplished by the addition of an ionomer to the NP suspension. The catalytic activity of the prepared catalysts for the oxygen reduction reaction is comparable to industrial catalysts and no influence of the particle size is found in the range of 2-5 nm.

A novel method for synthesis of phosphomolybdic acid-modified Pd/C catalysts for oxygen reduction reaction

NASA Astrophysics Data System (ADS)

Zhu, Mingyuan; Gao, Xiaoling; Luo, Guangqin; Dai, Bin

2013-03-01

This manuscript reports a convenient method for immobilizing phosphomolybdic acid (HPMo) on polyaniline (PAN-) functionalized carbon supports. The obtained HPMo-PAN-C sample is used as the support to prepare a Pd/HPMo-PAN-C catalyst. The samples are characterized by Fourier transform infrared spectroscopy, transmission electron microscopy and X-ray diffraction analysis. The results suggest that HPMo retains its Keggin structure and that the presence of HPMo reduces the average particle size of the Pd nano-particles in the obtained Pd/HPMo-PAN-C catalyst. Electro-chemical measurements in 0.5 M HClO4 solution reveal that the Pd/HPMo-PAN-C catalyst has higher catalytic activity for oxygen reduction reactions than does a Pd/C catalyst prepared using a similar procedure. The stability of the Pd/HPMo-PAN-C catalyst is evaluated by multiple-cycle voltammetry techniques; the mass catalytic activity decreases by only 10% after 100 scanning cycles.

Efficient low-temperature soot combustion by bimetallic Ag-Cu/SBA-15 catalysts.

PubMed

Wen, Zhaojun; Duan, Xinping; Hu, Menglin; Cao, Yanning; Ye, Linmin; Jiang, Lilong; Yuan, Youzhu

2018-02-01

In this study, the effects of copper (Cu) additive on the catalytic performance of Ag/SBA-15 in complete soot combustion were investigated. The soot combustion performance of bimetallic Ag-Cu/SBA-15 catalysts was higher than that of monometallic Ag and Cu catalysts. The optimum catalytic performance was acquired with the 5Ag 1 -Cu 0.1 /SBA-15 catalyst, on which the soot combustion starts at T ig =225°C with a T 50 =285°C. The temperature for 50% of soot combustion was lower than that of conventional Ag-based catalysts to more than 50°C (Aneggi et al., 2009). Physicochemical characterizations of the catalysts indicated that addition of Cu into Ag could form smaller bimetallic Ag-Cu nanolloy particles, downsizing the mean particle size from 3.7nm in monometallic catalyst to 2.6nm in bimetallic Ag-Cu catalyst. Further experiments revealed that Ag and Cu species elicited synergistic effects, subsequently increasing the content of surface active oxygen species. As a result, the structure modifications of Ag by the addition of Cu strongly intensified the catalytic performance. Copyright © 2017. Published by Elsevier B.V.

Crack Initiation and Growth Behavior of Cold-Sprayed Ni Particles on IN718 Alloy

NASA Astrophysics Data System (ADS)

Cavaliere, P.; Silvello, A.

2017-04-01

Cold spray processing parameters, governing particle velocity and impact energy, are analyzed in the present paper for pure Ni sprayed on IN718 substrates. Finite element modeling (FEM) was used to calculate the particle impact velocity and temperature as a function of gas temperature and pressure and particle density and dimensions. Experimental evidence underlines the possibility of performing repairing through cold spray thanks to the good level of adhesion achievable by employing optimal combinations of materials and spray processing parameters. In the present paper, the potential repairing of cracked superalloys sheets, by employing cold spray technology, is presented. 30° surface V-notched IN718 panels have been repaired by using pure Ni cold-sprayed powders. The bending behavior of the repaired sheets was analyzed by FEM and mechanical testing in order to compare the properties with those belonging to the unrepaired panels. Simulations and mechanical results showed a reduction in the stress intensity factor, a modification of the crack initiation site and a crack retardation in the repaired structures if compared with the unrepaired ones. The K factor was quantified; the resistance of repaired panels was increased of more than eight times in the case of repairing with Ni cold spray particles. Geometrical and mechanical properties of the coating-substrate interfaces, such as adhesion strength and residual stresses influencing the coatings behavior, were largely analyzed.

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.

Salinity effects on the dynamics and patterns of desiccation cracks

NASA Astrophysics Data System (ADS)

Shokri, N.; Zhou, P.

2012-12-01

Cracking arising from desiccation is a ubiquitous phenomenon encountered in various industrial and geo-environmental applications including drying of clayey soil, cement, ceramics, gels, and many more colloidal suspensions. Presence of cracks in muddy sediments modifies the characteristics of the medium such as pore structure, porosity, and permeability which in turn influence various flow and transport processes. Thus it remains a topic of great interest in many disciplines to describe the dynamics of desiccation cracking under various boundary conditions. To this end, we conducted a comprehensive study to investigate effects of NaCl concentrations on cracking dynamics and patterns during desiccation of Bentonite. Mixtures of Bentonite and NaCl solutions were prepared with NaCl concentration varying from 2 to 10 percent in 0.5 percent increment (totally 17 configurations). The slurry was placed in a Petri dish mounted on a digital balance to record the evaporation dynamics. The atmospheric conditions were kept constant using an environmental chamber. An automatic camera was used to record the dynamics of macro-cracks (mm scale) at the surface of desiccating clay each minute. The obtained results illustrate the significant effects of salt concentration on the initiation, propagation, morphology and general dynamics of macro-cracks. We found that higher salt concentrations results in larger macro cracks' lengths attributed to the effects of NaCl on compressing the electric double layer of particles at increasing electrolyte concentrations which reduce considerably the repulsive forces among the particles and causing instability of the slurry and flocculation of the colloidal particles. Rheological measurements by means of a stress controlled rheometer revealed that the yield stress of the slurry decreases as NaCl concentration increases which may indicate aggregation of larger units in the slurry as a result of flocculation causing larger cracks' lengths due to drying. At the end of each round of the experiment, a detailed visualization was conducted using Scanning Electron Microscopy to investigate the patterns and morphology of cracks at micro-scale as influenced by the salt concentration. Our results provide new insights and finding about the effects of salt concentrations on desiccation cracks at different scales ranging from a few mm to few microns.

External Catalyst Breakup Phenomena

DTIC Science & Technology

1976-06-01

catalyst particle can cause high internal pressures which result in particle destruction. Analytical results suggest rhat erosion effects from solid...mechanisms. * Pressure Forces. High G loadings and bed pressure drops should be avoided. Bed pre-loads should be kept at a minimum value. Thruster...5.2.7.1 Failure Theories ............................ 243 5.2.7.2 Maximum Tension Stress Criterion ............ 244 5.2.7.3 Distortion Energy Approach

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.

Variation of stresses ahead of the internal cracks in ReNi{sub 5} powders during hydrogen charging and discharging cycles

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

Biner, S.B.

1997-12-31

In this study, the evolution of the stress-states ahead of the penny shaped internal cracks in both spherical and disk shaped ReNi{sub 5} particles where Re denotes the rare earths La, Ce, and Misch-metals during hydrogen charging and discharging cycles were investigated using coupled diffusion/deformation FEM analyses. The results indicate that large tensile stresses, on the order of 20--30% of the modulus of elasticity, develop in the particles. The disk shaped particles, in addition to having faster charging/discharging cycles, may offer better resistance to fracture than the spherical particles.

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

Metal (Fe, Co, Ni) supported on different aluminas as Fischer-Tropsch catalyst

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

Dahlan; Marsih, I. Nyoman, E-mail: nyoman@chem.itb.ac.id; Ismunandar

2015-09-30

This research aimed to compare the physico-chemical properties of the same metal M (M = iron, cobalt, nickel) supported on aluminas with different morphology and pore size as Fischer-Tropsch catalyst. The aluminas applied as support were alumina synthesized through hydrothermal process, alumina formed by pretreatment of catapal and commercial alumina which named as Ahy, Aca, and Aco respectively. Ahy has uniform morphology of nanotubes while Aca and Aco showed non-uniform morphology of particle lumps. The particle lumps of Aca were larger than those of Aco. Ahy, Aca, and Aco respectively has average pore diameter of 2.75, 2.86 and 2.9 nm. Metalsmore » were deposited on the supports by incipient-wetness impregnation method. The catalysts were characterized by XRD, H{sub 2}-TPR, and H{sub 2} chemisorption. Catalyst acitivity test for Fischer-Tropsch reaction was carried out in a micro reactor at 200 °C and 1 atm, and molar ratio of H{sub 2}/CO = 2:1. The metal oxide particle size increased in the order M/Aco < M/Aca < M/Ahy. The catalysts reducibility also increased according to the order M/Aco < M/Aca < M/Ahy suggesting that the larger metal oxide particles are more reducible. The number of active site was not proportional to the reducibility because during the reduction, larger metal oxide particles were converted into larger metal particles. On the other hand, the number of active sites was inversely proportional to the particle sizes. The number of active site increased in the order M/Ahy < M/Aco < M/Aca. The catalytic activity also increased in the following order M/Ahy < M/Aco < M/Aca. The activity per active site increased according to the order M/Aca < M/Aco < M/Ahy meaning that for M/Ahy, a little increase in active site will lead to a significance increase in catalytic activity. It showed that Ahy has potential for the better support.« less

Surface folding in metals: a mechanism for delamination wear in sliding

PubMed Central

Mahato, Anirban; Guo, Yang; Sundaram, Narayan K.; Chandrasekar, Srinivasan

2014-01-01

Using high-resolution, in situ imaging of a hard, wedge-shaped model asperity sliding against a metal surface, we demonstrate a new mechanism for particle formation and delamination wear. Damage to the residual surface is caused by the occurrence of folds on the free surface of the prow-shaped region ahead of the wedge. This damage manifests itself as shallow crack-like features and surface tears, which are inclined at very acute angles to the surface. The transformation of folds into cracks, tears and particles is directly captured. Notably, a single sliding pass is sufficient to damage the surface, and subsequent passes result in the generation of platelet-like wear particles. Tracking the folding process at every stage from surface bumps to folds to cracks/tears/particles ensures that there is no ambiguity in capturing the mechanism of wear. Because fold formation and consequent delamination are quite general, our findings have broad applicability beyond wear itself, including implications for design of surface generation and conditioning processes. PMID:25197251

Investigation of internal elements impaction on particles circulation in a fluidized bed reactor

NASA Astrophysics Data System (ADS)

Solovev, S. A.; Soloveva, O. V.; Antipin, A. V.; Shamsutdinov, E. V.

2018-01-01

A numerical study of the fluidized bed apparatus in the presence of various internal elements is carried out. A chemical reaction for temperature-dependent processes with heat absorption is considered. The task of incoming heated catalyst granules to the reactor is investigated. The main emphasis is focused on the circulation flows of the catalyst particles, heating of the reactor, and the efficiency of the chemical reaction. The analysis of the impact of various design elements on the efficiency of the reactor is carried out. The influence of feeding heated catalyst device design on the effectiveness of whole reactor heating is educed. The influence of the presence of fine particles on the efficiency of the reaction for different reactor design features is also educed.

Iron on mixed zirconia-titania substrate Fischer-Tropsch catalyst and method of making same

DOEpatents

Dyer, Paul N.; Nordquist, Andrew F.; Pierantozzi, Ronald

1986-01-01

A Fischer-Tropsch catalyst comprising iron co-deposited with or deposited on particles comprising a mixture of zirconia and titania, preferably formed by co-precipitation of compounds convertible to zirconia and titania, such as zirconium and titanium alkoxide. The invention also comprises the method of making this catalyst and an improved Fischer-Tropsch reaction process in which the catalyst is utilized.

F-T process using an iron on mixed zirconia-titania supported catalyst

DOEpatents

Dyer, Paul N.; Nordquist, Andrew F.; Pierantozzi, Ronald

1987-01-01

A Fischer-Tropsch catalyst comprising iron co-deposited with or deposited on particles comprising a mixture of zirconia and titania, preferably formed by co-precipitation of compounds convertible to zirconia and titania, such as zirconium and titanium alkoxide. The invention also comprises the method of making this catalyst and an improved Fischer-Tropsch reaction process in which the catalyst is utilized.

An analytical approach for the calculation of stress-intensity factors in transformation-toughened ceramics

NASA Astrophysics Data System (ADS)

Müller, W. H.

1990-12-01

Stress-induced transformation toughening in Zirconia-containing ceramics is described analytically by means of a quantitative model: A Griffith crack which interacts with a transformed, circular Zirconia inclusion. Due to its volume expansion, a ZrO2-particle compresses its flanks, whereas a particle in front of the crack opens the flanks such that the crack will be attracted and finally absorbed. Erdogan's integral equation technique is applied to calculate the dislocation functions and the stress-intensity-factors which correspond to these situations. In order to derive analytical expressions, the elastic constants of the inclusion and the matrix are assumed to be equal.

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

Qiusheng, Y., E-mail: qsyan@gdut.edu.cn; Senkai, C., E-mail: senkite@sina.com; Jisheng, P., E-mail: panjisheng@gdut.edu.cn

Different machining processes were used in the single crystal SiC wafer machining. SEM was used to observe the surface morphology and a cross-sectional cleavages microscopy method was used for subsurface cracks detection. Surface and subsurface cracks characteristics of single crystal SiC wafer in abrasive machining were analysed. The results show that the surface and subsurface cracks system of single crystal SiC wafer in abrasive machining including radial crack, lateral crack and the median crack. In lapping process, material removal is dominated by brittle removal. Lots of chipping pits were found on the lapping surface. With the particle size becomes smaller,more » the surface roughness and subsurface crack depth decreases. When the particle size was changed to 1.5µm, the surface roughness Ra was reduced to 24.0nm and the maximum subsurface crack was 1.2µm. The efficiency of grinding is higher than lapping. Plastic removal can be achieved by changing the process parameters. Material removal was mostly in brittle fracture when grinding with 325# diamond wheel. Plow scratches and chipping pits were found on the ground surface. The surface roughness Ra was 17.7nm and maximum subsurface crack depth was 5.8 µm. When grinding with 8000# diamond wheel, the material removal was in plastic flow. Plastic scratches were found on the surface. A smooth surface of roughness Ra 2.5nm without any subsurface cracks was obtained. Atomic scale removal was possible in cluster magnetorheological finishing with diamond abrasive size of 0.5 µm. A super smooth surface eventually obtained with a roughness of Ra 0.4nm without any subsurface crack.« less

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

Catalysts for low temperature oxidation

DOEpatents

Toops, Todd J.; Parks, III, James E.; Bauer, John C.

2016-03-01

The invention provides a composite catalyst containing a first component and a second component. The first component contains nanosized gold particles. The second component contains nanosized platinum group metals. The composite catalyst is useful for catalyzing the oxidation of carbon monoxide, hydrocarbons, oxides of nitrogen, and other pollutants at low temperatures.

Electron microscopy study of Pd, Ag, and Cs in carbon areas in the locally corroded SiC layer in a neutron-irradiated TRISO fuel particle

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

Wen, Haiming; van Rooyen, Isabella J.; Hunn, John D.

Here, a detailed electron microscopy study was performed on focused ion beam-prepared lamellae from different locations relative to a crack across the inner pyrolytic carbon layer of a neutron-irradiated tristructural isotropic-coated particle. The distribution and composition of fission products across the inner pyrolytic carbon and silicon carbide (SiC) layers were studied. Previously, this crack was identified in the particle that released significant inventory fractions of cesium and silver during irradiation and displayed localized palladium pileup with SiC degradation. In this study, carbon areas were found in the SiC layer close to the crack tip and they had precipitates that consistedmore » mostly of palladium silicides or palladium, with silver and/or cadmium frequently identified. Results confirmed that areas in the SiC layer close to the crack tip with localized accumulation of palladium were corroded by palladium, forming pure carbon areas and palladium silicide that provided pathways for silver, cadmium and cesium migration.« less

Electron microscopy study of Pd, Ag, and Cs in carbon areas in the locally corroded SiC layer in a neutron-irradiated TRISO fuel particle

DOE PAGES

Wen, Haiming; van Rooyen, Isabella J.; Hunn, John D.; ...

2018-05-07

Here, a detailed electron microscopy study was performed on focused ion beam-prepared lamellae from different locations relative to a crack across the inner pyrolytic carbon layer of a neutron-irradiated tristructural isotropic-coated particle. The distribution and composition of fission products across the inner pyrolytic carbon and silicon carbide (SiC) layers were studied. Previously, this crack was identified in the particle that released significant inventory fractions of cesium and silver during irradiation and displayed localized palladium pileup with SiC degradation. In this study, carbon areas were found in the SiC layer close to the crack tip and they had precipitates that consistedmore » mostly of palladium silicides or palladium, with silver and/or cadmium frequently identified. Results confirmed that areas in the SiC layer close to the crack tip with localized accumulation of palladium were corroded by palladium, forming pure carbon areas and palladium silicide that provided pathways for silver, cadmium and cesium migration.« less

Physico-Chemical Characterization of Fine and Ultrafine Particles Emitted during Diesel Particulate Filter Active Regeneration of Euro5 Diesel Vehicles.

PubMed

R'Mili, Badr; Boréave, Antoinette; Meme, Aurelie; Vernoux, Philippe; Leblanc, Mickael; Noël, Ludovic; Raux, Stephane; D'Anna, Barbara

2018-03-06

Diesel particulate filters (DPFs) are commonly employed in modern passenger cars to comply with current particulate matter (PM) emission standards. DPFs requires periodic regeneration to remove the accumulated matter. During the process, high-concentration particles, in both nucleation and accumulation modes, are emitted. Here, we report new information on particle morphology and chemical composition of fine (FPs) and ultrafine particles (UFPs) measured downstream of the DPF during active regeneration of two Euro 5 passenger cars. The first vehicle was equipped with a close-coupled diesel oxidation catalyst (DOC) and noncatalyzed DPF combined with fuel borne catalyst and the second one with DOC and a catalyzed-diesel particle filter (CDPF). Differences in PM emission profiles of the two vehicles were related to different after treatment design, regeneration strategies, and vehicle characteristics and mileage. Particles in the nucleation mode consisted of ammonium bisulfate, sulfate and sulfuric acid, suggesting that the catalyst desulfation is the key process in the formation of UFPs. Larger particles and agglomerates, ranging from 90 to 600 nm, consisted of carbonaceous material (soot and soot aggregates) coated by condensable material including organics, ammonium bisulfate and sulfuric acid. Particle emission in the accumulation mode was due to the reduced filtration efficiency (soot cake oxidation) throughout the regeneration process.

Pt/glassy carbon model catalysts prepared from PS-b-P2VP micellar templates.

PubMed

Gu, Yunlong; St-Pierre, Jean; Ploehn, Harry J

2008-11-04

Poly(styrene)-block-poly(2-vinylpyridine) (PS-b-P2VP) diblock copolymer was used as a micellar template to fabricate arrays of Pt nanoparticles on mica and glassy carbon (GC) supports. Polymer micellar deposition yields Pt nanoparticles with tunable particle size and surface number density on both mica and GC. After deposition of precursor-loaded micelles onto GC, oxygen plasma etching removes the polymer shell, followed by thermal treatment with H2 gas to reduce the Pt. Etching conditions were optimized to maximize removal of the polymer while minimizing damage to the GC. Arrays of Pt nanoparticles with controlled size and surface number density can be prepared on mica (for particle size characterization) and GC to make Pt/GC model catalysts. These model catalysts were characterized by tapping mode atomic force microscopy, X-ray photoelectron spectroscopy, and cyclic voltammetry to measure activity for oxidation of carbon monoxide or methanol. Cyclic voltammetry results demonstrate the existence of a correlation between Pt particle size and electrocatalytic properties including onset potential, tolerance of carbonaceous adsorbates, and intrinsic activity (based on active Pt area from CO stripping voltammetry). Results obtained with Pt/GC model catalysts duplicate prior results obtained with Pt/porous carbon catalysts therefore validating the synthesis approach and offering a new, tunable platform to study catalyst structure and other effects such as aging on proton exchange membrane fuel cell (PEMFC) reactions.

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.

Understanding the crack formation of graphite particles in cycled commercial lithium-ion batteries by focused ion beam - scanning electron microscopy

NASA Astrophysics Data System (ADS)

Lin, Na; Jia, Zhe; Wang, Zhihui; Zhao, Hui; Ai, Guo; Song, Xiangyun; Bai, Ying; Battaglia, Vincent; Sun, Chengdong; Qiao, Juan; Wu, Kai; Liu, Gao

2017-10-01

The structure degradation of commercial Lithium-ion battery (LIB) graphite anodes with different cycling numbers and charge rates was investigated by focused ion beam (FIB) and scanning electron microscopy (SEM). The cross-section image of graphite anode by FIB milling shows that cracks, resulted in the volume expansion of graphite electrode during long-term cycling, were formed in parallel with the current collector. The crack occurs in the bulk of graphite particles near the lithium insertion surface, which might derive from the stress induced during lithiation and de-lithiation cycles. Subsequently, crack takes place along grain boundaries of the polycrystalline graphite, but only in the direction parallel with the current collector. Furthermore, fast charge graphite electrodes are more prone to form cracks since the tensile strength of graphite is more likely to be surpassed at higher charge rates. Therefore, for LIBs long-term or high charge rate applications, the tensile strength of graphite anode should be taken into account.

Surface and subsurface cracks characteristics of single crystal SiC wafer in surface machining

NASA Astrophysics Data System (ADS)

Qiusheng, Y.; Senkai, C.; Jisheng, P.

2015-03-01

Different machining processes were used in the single crystal SiC wafer machining. SEM was used to observe the surface morphology and a cross-sectional cleavages microscopy method was used for subsurface cracks detection. Surface and subsurface cracks characteristics of single crystal SiC wafer in abrasive machining were analysed. The results show that the surface and subsurface cracks system of single crystal SiC wafer in abrasive machining including radial crack, lateral crack and the median crack. In lapping process, material removal is dominated by brittle removal. Lots of chipping pits were found on the lapping surface. With the particle size becomes smaller, the surface roughness and subsurface crack depth decreases. When the particle size was changed to 1.5µm, the surface roughness Ra was reduced to 24.0nm and the maximum subsurface crack was 1.2µm. The efficiency of grinding is higher than lapping. Plastic removal can be achieved by changing the process parameters. Material removal was mostly in brittle fracture when grinding with 325# diamond wheel. Plow scratches and chipping pits were found on the ground surface. The surface roughness Ra was 17.7nm and maximum subsurface crack depth was 5.8 µm. When grinding with 8000# diamond wheel, the material removal was in plastic flow. Plastic scratches were found on the surface. A smooth surface of roughness Ra 2.5nm without any subsurface cracks was obtained. Atomic scale removal was possible in cluster magnetorheological finishing with diamond abrasive size of 0.5 µm. A super smooth surface eventually obtained with a roughness of Ra 0.4nm without any subsurface crack.

Detection and Sizing of Fatigue Cracks in Steel Welds with Advanced Eddy Current Techniques

NASA Astrophysics Data System (ADS)

Todorov, E. I.; Mohr, W. C.; Lozev, M. G.

2008-02-01

Butt-welded specimens were fatigued to produce cracks in the weld heat-affected zone. Advanced eddy current (AEC) techniques were used to detect and size the cracks through a coating. AEC results were compared with magnetic particle and phased-array ultrasonic techniques. Validation through destructive crack measurements was also conducted. Factors such as geometry, surface treatment, and crack tightness interfered with depth sizing. AEC inspection techniques have the potential of providing more accurate and complete sizing flaw data for manufacturing and in-service inspections.

Attrition Resistant Iron-Based Catalysts For F-T SBCRs

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

Adeyinka A. Adeyiga

2006-01-31

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-(FE) 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 withmore » the use of 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. Under a previous Department of Energy (DOE)/University Research Grant (UCR) grant, Hampton University reported, for the first time, the development of demonstrably attrition-resistant Fe F-T synthesis catalysts having good activity, selectivity, and attrition resistance. These catalysts were prepared by spray drying Fe catalysts with potassium (K), copper (Cu), and silica (SiO{sub 2}) as promoters. SiO{sub 2} was also used as a binder for spray drying. These catalysts were tested for activity and selectivity in a laboratory-scale fixed-bed reactor. Fundamental understanding of attrition is being addressed by incorporating suitable binders into the catalyst recipe. This has resulted in the preparation of a spray dried HPR-43 catalyst having average particle size (aps) of 70 {micro}m with high attrition resistance. This HPR-43 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+} selectivity of >78% and methane selectivity of less than 5% at an {alpha} of 0.9. Research is proposed to enable further development and optimization of these catalysts by (1) better understanding the role and interrelationship of various catalyst composition and preparation parameters on attrition resistance, activity, and selectivity of these catalysts, (2) the presence of sulfide ions on a precipitated iron catalyst, and (3) the effect of water on sulfided iron F-T catalysts for its activity, selectivity, and attrition. Catalyst preparations will be based on spray drying. The research employed, among other measurements, attrition testing and F-T synthesis at high pressure. Catalyst activity and selectivity is evaluated using a small fixed-bed reactor and a continuous stirred tank reactor (CSTR). The catalysts were prepared by co-precipitation, followed by binder addition and spray drying at 250 C in a 1-m-diameter, 2-m-tall spray dryer. The binder silica content was varied from 0 to 20 wt%. The results show that the use of small amounts of precipitated SiO{sub 2} alone in spray-dried Fe catalysts can result in good attrition resistance. All catalysts investigated with SiO2 wt% {le} 12 produced fines less than 10 wt% during the jet cup attrition test, making them suitable for long-term use in a slurry bubble column reactor. Thus, concentration rather than the type of SiO{sub 2} incorporated into catalyst has a more critical impact on catalyst attrition resistance of spray-dried Fe catalysts. Lower amounts of SiO{sub 2} added to a catalyst give higher particle densities and therefore higher attrition resistances. In order to produce a suitable SBCR catalyst, however, the amount of SiO{sub 2} added has to be optimized to provide adequate surface area, particle density, and attrition resistance. Two of the catalysts with precipitated and binder silica were tested in Texas A&M University's CSTR (Autoclave Engineers). The two catalysts were also tested at The Center for Applied Energy Research in Lexington, Kentucky of the University of Kentucky. Spray-dried catalysts with compositions 100 Fe/5 Cu/4.2 K/11 (P) SiO{sub 2} and 100 Fe/5 Cu/4.2 K/1.1 (B) SiO{sub 2} have excellent selectivity characteristics (low methane and high C{sub 5+} yields), but their productivity and stability (deactivation rate) need to be improved. Mechanical integrity (attrition strength) of these two catalysts was markedly dependent upon their morphological features. The attrition strength of the catalyst made out of largely spherical particles (1.1 (B) SiO{sub 2}) was considerably higher than that of the catalyst consisting of irregularly shaped particles (11 (P) SiO{sub 2}).« less

Characterization of Cracking Mechanisms of Carbon Anodes Used in Aluminum Industry by Optical Microscopy and Tomography

NASA Astrophysics Data System (ADS)

Amrani, Salah; Kocaefe, Duygu; Kocaefe, Yasar; Bhattacharyay, Dipankar; Bouazara, Mohamed; Morais, Brigitte

2016-10-01

The objective of this work is to understand the different mechanisms of crack formation in dense anodes used in the aluminum industry. The first approach used is based on the qualitative characterization of the surface cracks and the depth of these cracks. The second approach, which constitutes a quantitative characterization, is carried out by determining the distribution of the crack width along its length as well as the percentage of the surface containing cracks. A qualitative analysis of crack formation was also carried out using 3D tomography. It was observed that mixing and forming conditions have a significant effect on crack formation in green anodes. The devolatilization of pitch during baking causes the formation and propagation of cracks in baked anodes in which large particles control the direction of crack propagation.

Carbon nanotubes grown on bulk materials and methods for fabrication

DOEpatents

Menchhofer, Paul A [Clinton, TN; Montgomery, Frederick C [Oak Ridge, TN; Baker, Frederick S [Oak Ridge, TN

2011-11-08

Disclosed are structures formed as bulk support media having carbon nanotubes formed therewith. The bulk support media may comprise fibers or particles and the fibers or particles may be formed from such materials as quartz, carbon, or activated carbon. Metal catalyst species are formed adjacent the surfaces of the bulk support material, and carbon nanotubes are grown adjacent the surfaces of the metal catalyst species. Methods employ metal salt solutions that may comprise iron salts such as iron chloride, aluminum salts such as aluminum chloride, or nickel salts such as nickel chloride. Carbon nanotubes may be separated from the carbon-based bulk support media and the metal catalyst species by using concentrated acids to oxidize the carbon-based bulk support media and the metal catalyst species.

Dye-sensitized MIL-101 metal organic frameworks loaded with Ni/NiOx nanoparticles for efficient visible-light-driven hydrogen generation

NASA Astrophysics Data System (ADS)

Liu, Xin-Ling; Wang, Rong; Zhang, Ming-Yi; Yuan, Yu-Peng; Xue, Can

2015-10-01

The Ni/NiOx particles were in situ photodeposited on MIL-101 metal organic frameworks as catalysts for boosting H2 generation from Erythrosin B dye sensitization under visible-light irradiation. The highest H2 production rate of 125 μmol h-1 was achieved from the system containing 5 wt. % Ni-loaded MIL-101 (20 mg) and 30 mg Erythrosin B dye. Moreover, the Ni/NiOx catalysts show excellent stability for long-term photocatalytic reaction. The enhancement on H2 generation is attributed to the efficient charge transfer from photoexcited dye to the Ni catalyst via MIL-101. Our results demonstrate that the economical Ni/NiOx particles are durable and active catalysts for photocatalytic H2 generation.

Single Atomic Iron Catalysts for Oxygen Reduction in Acidic Media: Particle Size Control and Thermal Activation

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

Zhang, Hanguang; Hwang, Sooyeon; Wang, Maoyu

To significantly reduce the cost of proton exchange membrane (PEM) fuel cells, current Pt must be replaced by platinum-metal-group (PGM)-free catalysts for the oxygen reduction reaction (ORR) in acid. We report here a new class of high-performance atomic iron dispersed carbon catalysts through controlled chemical doping of iron ions into zinc-zeolitic imidazolate framework (ZIF), a type of metal-organic framework (MOF). The novel synthetic chemistry enables accurate size control of Fe-doped ZIF catalyst particles with a wide range from 20 to 1000 nm without changing chemical properties, which provides a great opportunity to increase the density of active sites that ismore » determined by the particle size. We elucidated the active site formation mechanism by correlating the chemical and structural changes with thermal activation process for the conversion from Fe-N4 complex containing hydrocarbon networks in ZIF to highly active FeNx sites embedded into carbon. A temperature of 800oC was identified as the critical point to start forming pyridinic nitrogen doping at the edge of the graphitized carbon planes. Further increasing heating temperature to 1100oC leads to increase of graphitic nitrogen, generating possible synergistic effect with FeNx sites to promote ORR activity. The best performing catalyst, which has well-defined particle size around 50 nm and abundance of atomic FeNx sites embedded into carbon structures, achieve a new performance milestone for the ORR in acid including a half-wave potential of 0.85 V vs RHE and only 20 mV loss after 10,000 cycles in O2 saturated H2SO4 electrolyte. The new class PGM-free catalyst with approaching activity to Pt holds great promise for future PEM fuel cells.« less

Effects of copper-precursors on the catalytic activity of Cu/graphene catalysts for the selective catalytic oxidation of ammonia

NASA Astrophysics Data System (ADS)

Li, Jingying; Tang, Xiaolong; Yi, Honghong; Yu, Qingjun; Gao, Fengyu; Zhang, Runcao; Li, Chenlu; Chu, Chao

2017-08-01

Different copper-precursors were used to prepare Cu/graphene catalysts by an impregnation method. XRD, Raman spectra, TEM, BET, XPS, H2-TPR, NH3-TPD, DRIFTS and catalytic activity test were used to characterize and study the effect of precursors on the catalytic activity of Cu/graphene catalysts for NH3-SCO reaction. The large specific surface area of Cu/graphene catalysts and high dispersion of the metal particles on the graphene caused the well catalytic activity of NH3-SCO reaction. Compared to Cu/GE(AC), Cu/GE(N) showed better catalytic performance, and the complete NH3 removal efficiency was obtained at 250 °C with N2 selectivity of 85%. The copper-precursors had influence on the distribution of surface Cu species and further affected the catalytic activity of Cu/GE catalysts. The more amount of surface Cu species and highly dispersed CuO particles on the graphene surface formed by using copper nitrate as precursor could significantly improve the reducibility of catalysts and enhance NH3 adsorption, thereby improving the catalytic activity of Cu/graphene catalyst.

Synthesis of Copper-Based Nanostructured Catalysts on SiO2-Al2O3, SiO2-TiO2, and SiO2-ZrO2 Supports for NO Reduction.

PubMed

Namkhang, Pornpan; Kongkachuichay, Paisan

2015-07-01

The selective catalytic reduction of NO over a series of Cu-based catalysts supported on modified silica including SiO2-Al2O3, SiO2-TiO2, and SiO2-ZrO2 prepared via a sol-gel process and a flame spray pyrolysis (FSP) was studied. The prepared catalysts were characterized by means of TEM, XRD, XRF, TPR, and nitrogen physisorption measurement techniques, to determine particle diameter, morphology, crystallinity, phase composition, copper reducibility, surface area, and pore size of catalysts. The particles obtained from sol-gel method were almost spherical while the particles obtained from the FSP were clearly spherical and non-porous nanosized particles. The effects of Si:Al, Si:Ti, and Si:Zr molar ratio of precursor were identified as the domain for different crystalline phase of materials. It was clearly seen that a high SiO2 content inhibited the crystallization of materials. The BET surface area of catalysts obtained from sol-gel method was higher than that from the FSP and it shows that surface area increased with increasing SiO2 molar ratio due to high surface area from SiO2. The catalyst performances were tested for the selective catalytic reduction of NO with H2. It was found that the catalyst prepared over 7 wt% Cu on Si02-Al2O3 support was the most active compared with the others which converted NO as more than 70%. Moreover, the excess copper decreased the performance of NO reduction, due to the formation of CuO agglomeration covered on the porous silica as well as the alumina surface, preventing the direct contact of CO2 and AL2O3.

Highly selective oxidation of styrene to benzaldehyde over a tailor-made cobalt oxide encapsulated zeolite catalyst.

PubMed

Liu, Jiangyong; Wang, Zihao; Jian, Panming; Jian, Ruiqi

2018-05-01

A tailor-made catalyst with cobalt oxide particles encapsulated into ZSM-5 zeolites (Co 3 O 4 @HZSM-5) was prepared via a hydrothermal method with the conventional impregnated Co 3 O 4 /SiO 2 catalyst as the precursor and Si source. Various characterization results show that the Co 3 O 4 @HZSM-5 catalyst has well-organized structure with Co 3 O 4 particles compatibly encapsulated in the zeolite crystals. The Co 3 O 4 @HZSM-5 catalyst was employed as an efficient catalyst for the selective oxidation of styrene to benzaldehyde with hydrogen peroxide as a green and economic oxidant. The effect of various reaction conditions including reaction time, reaction temperature, different kinds of solvents, styrene/H 2 O 2 molar ratio and catalyst dosage on the catalytic performance were systematically investigated. Under the optimized reaction condition, the yield of benzaldehyde can achieve 78.9% with 96.8% styrene conversion and 81.5% benzaldehyde selectivity. Such an excellent catalytic performance can be attributed to the synergistic effect between the confined reaction environment and the proper acidic property. In addition, the reaction mechanism with Co 3 O 4 @HZSM-5 as the catalyst for the selective oxidation of styrene to benzaldehyde was reasonably proposed. Copyright © 2018 Elsevier Inc. All rights reserved.

In situ X-ray absorption fine structure analysis of redox reactions of nickel species with variable particle sizes supported on silica

NASA Astrophysics Data System (ADS)

Yamamoto, Yusaku; Suzuki, Atsushi; Tsutsumi, Naoki; Katagiri, Masaki; Yamashita, Shohei; Niwa, Yasuhiro; Katayama, Misaki; Inada, Yasuhiro

2018-02-01

The chemical states of Ni species were systematically investigated using an in situ XAFS technique for a series of SiO2-supported Ni catalysts with different Ni particle sizes. The Ni particles were refined by varying the Ni loading in the range between 0.10 and 5 wt% and by adding citric acid into the precursor solution. An in situ observation cell for fluorescence-yield XAFS measurements was developed for the dilute Ni catalysts. The chemical state of the supported Ni species converted between Ni(0) and NiO, and no other stable species were formed during the temperature-programmed oxidation and reduction processes. Refinement of the Ni particles resulted in decreasing the oxidation temperature and increasing the reduction temperature. These shifts were explained by the affinity of NiO to SiO2, and more effective stabilization was thus anticipated for flattened small NiO particles with an increased contact area. In addition, the inhomogeneous distribution of small Ni particles observed for dilute catalysts was explained in terms of the precursor solution volume when nuclei of the precursor compound precipitated on SiO2 during the drying process.

Effect of pretreating of host oil on coprocessing

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

Hajdu, P.E.; Tierney, J.W.; Wender, I.

1995-12-31

The principal objective of this research was to determine if coprocessing performance (i.e., coal conversion and oil yield) could be significantly improved by pretreating the heavy resid prior to reacting it with coal. For this purpose, two petroleum vacuum resids (1000{degrees}F+), one from the Amoco Co. and another from the Citgo Co., were used as such and after they had been pretreated by catalytic hydrogenation and hydrocracking reactions. The pretreatments were aimed at improving the host oil by; (1) converting any aromatic structures in the petroleum to hydroaromatic compounds capable of donating hydrogen, (2) cracking the heavy oil to lowermore » molecular weight material that might serve as a better solvent, (3) reducing the coking propensity of the heavy oil through the hydrogenation of polynuclear aromatic compounds, and (4) removing metals and heteroatoms that might poison a coprocessing catalyst. Highly dispersed catalysts, including fine particle Fe- and Mo-based, and dicobalt octacarbonyl, Co{sub 2}(CO){sub 8}, were used in this study. The untreated and pretreated resids were extensively characterized in order to determine chemical changes brought about by the pretreatments. The modified heavy oils were then coprocessed with an Illinois No. 6 coal as well as with a Wyodak coal, and compared to coprocessing with untreated resids under the same hydroliquefaction conditions. The amount of oil derived from coal was estimated by measuring the level of phenolic oxygen (derived mainly from coal) present in the oil products. Results are presented and discussed.« less

Investigation of the degradation of different nickel anode types for alkaline fuel cells (AFCs)

NASA Astrophysics Data System (ADS)

Gülzow, E.; Schulze, M.; Steinhilber, G.

Alkaline fuel cells (AFCs) have the opportunity of becoming important for mobile energy systems as, in contrast to other low temperature fuel cells, the alkaline type requires neither noble metal catalysts nor an expensive polymer electrolyte. In AFCs, nickel is used as anode catalyst in gas diffusion electrodes. The metal catalyst was mixed with polytetraflourethylene (PTFE) as organic binder in a knife mile and rolled onto a metal web in a calendar to prepare the electrode. After an activation process with hydrogen evolution at 5 mA/cm 2 for 18 h, the electrodes were stressed at constant loading in a half cell equipment. During the fuel cell operation, the electrochemical performance decreased due to changes of the polymer (PTFE) and of the metal particles in the electrode, which is described in detail in another paper. In this study, three types of electrodes were investigated. The first type of electrode is composed of pure Raney-nickel and PTFE powder, the nickel particles in the second electrode type were selected according to particle size and in the third electrode copper powder was added to the nickel powder not selected by size. The size selected nickel particles show a better electrochemical performance related to the non-selected catalyst, but due to the electrochemically induced disintegration of the nickel particles the electrochemical performance decreases stronger. The copper powder in the third electrode is added to improve the electronic conductivity of the nickel catalyst, but the copper is not stable under the electrochemical conditions in fuel cell operation. With all three anode types long-term experiments have been performed. The electrodes have been characterized after the electrochemical stressing to investigate the degradation processes.

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

Performance Testing of Hot-Mix Asphalt Aggregates

DOT National Transportation Integrated Search

1999-12-01

Hot mix asphalt (HMA) pavements are subject to thermal cracking, fatigue cracking, rutting, stripping, raveling, and freeze-thaw damage. Some of these distresses are directly affected by the choice of aggregates. Particle shape, surface texture, part...

Enamel subsurface damage due to tooth preparation with diamonds.

PubMed

Xu, H H; Kelly, J R; Jahanmir, S; Thompson, V P; Rekow, E D

1997-10-01

In clinical tooth preparation with diamond burs, sharp diamond particles indent and scratch the enamel, causing material removal. Such operations may produce subsurface damage in enamel. However, little information is available on the mechanisms and the extent of subsurface damage in enamel produced during clinical tooth preparation. The aim of this study, therefore, was to investigate the mechanisms of subsurface damage produced in enamel during tooth preparation by means of diamond burs, and to examine the dependence of such damage on enamel rod orientation, diamond particle size, and removal rate. Subsurface damage was evaluated by a bonded-interface technique. Tooth preparation was carried out on two enamel rod orientations, with four clinical diamond burs (coarse, medium, fine, and superfine) used in a dental handpiece. The results of this study showed that subsurface damage in enamel took the form of median-type cracks and distributed microcracks, extending preferentially along the boundaries between the enamel rods. Microcracks within individual enamel rods were also observed. The median-type cracks were significantly longer in the direction parallel to the enamel rods than perpendicular to the rods. Preparation with the coarse diamond bur produced cracks as deep as 84 +/- 30 microns in enamel. Finishing with fine diamond burs was effective in crack removal. The crack lengths in enamel were not significantly different when the removal rate was varied. Based on these results, it is concluded that subsurface damage in enamel induced by tooth preparation takes the form of median-type cracks as well as inter- and intra-rod microcracks, and that the lengths of these cracks are sensitive to diamond particle size and enamel rod orientation, but insensitive to removal rate.

Synthesis and Hydrodeoxygenation Properties of Ruthenium Phosphide Catalysts

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

Bowker, Richard H.; Smith, Mica C.; Pease, Melissa

2011-07-01

Ru2P/SiO2 and RuP/SiO2 catalysts were prepared by the temperature-programmed reduction (TPR) of uncalcined precursors containing hypophosphite ion (H2PO2-) as the phosphorus source. The Ru2P/SiO2 and RuP/SiO2 catalysts had small average particle sizes (~4 nm) and high CO chemisorption capacities (90-110 umol/g). The Ru phosphide catalysts exhibited similar or higher furan (C4H4O) hydrodeoxygenation (HDO) activities than did a Ru/SiO2 catalyst, and the phosphide catalysts favored C4 hydrocarbon products while the Ru metal catalyst produced primarily C3 hydrocarbons.

Methods of producing epoxides from alkenes using a two-component catalyst system

DOEpatents

Kung, Mayfair C.; Kung, Harold H.; Jiang, Jian

2013-07-09

Methods for the epoxidation of alkenes are provided. The methods include the steps of exposing the alkene to a two-component catalyst system in an aqueous solution in the presence of carbon monoxide and molecular oxygen under conditions in which the alkene is epoxidized. The two-component catalyst system comprises a first catalyst that generates peroxides or peroxy intermediates during oxidation of CO with molecular oxygen and a second catalyst that catalyzes the epoxidation of the alkene using the peroxides or peroxy intermediates. A catalyst system composed of particles of suspended gold and titanium silicalite is one example of a suitable two-component catalyst system.

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.

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.

Particle size reduction of propellants by cryocycling

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

Whinnery, L.; Griffiths, S.; Lipkin, J.

1995-05-01

Repeated exposure of a propellant to liquid nitrogen causes thermal stress gradients within the material resulting in cracking and particle size reduction. This process is termed cryocycling. The authors conducted a feasibility study, combining experiments on both inert and live propellants with three modeling approaches. These models provided optimized cycle times, predicted ultimate particle size, and allowed crack behavior to be explored. Process safety evaluations conducted separately indicated that cryocycling does not increase the sensitivity of the propellants examined. The results of this study suggest that cryocycling is a promising technology for the demilitarization of tactical rocket motors.

Particle shape effect on erosion of optical glass substrates due to microparticles

NASA Astrophysics Data System (ADS)

Waxman, Rachel; Gray, Perry; Guven, Ibrahim

2018-03-01

Impact experiments using sand particles and soda lime glass spheres were performed on four distinct glass substrates. Sand particles were characterized using optical and scanning electron microscopy. High-speed video footage from impact tests was used to calculate incoming and rebound velocities of the individual impact events, as well as the particle volume and two-dimensional sphericity. Furthermore, video analysis was used in conjunction with optical and scanning electron microscopy to relate the incoming velocity and particle shape to subsequent fractures, including both radial and lateral cracks. Indentation theory [Marshall et al., J. Am. Ceram. Soc. 65, 561-566 (1982)] was applied and correlated with lateral crack lengths. Multi-variable power law regression was performed, incorporating the particle shape into the model and was shown to have better fit to damage data than the previous indentation model.

Rupture in cemented granular media: application to wheat endosperm

NASA Astrophysics Data System (ADS)

Topin, V.; Delenne, J.-Y.; Radjai, F.

2009-06-01

The mechanical origin of the wheat hardness used to classify wheat flours is an open issue. Wheat endosperm can be considered as a cemented granular material, consisting of densely packed solid particles (the starch granules) and a pore-filling solid matrix (the protein) sticking to the particles. We use the lattice element method to investigate cemented granular materials with a texture close to that of wheat endosperm and with variable matrix volume fraction and particle-matrix adherence. From the shape of the probability density of vertical stresses we distinguish weak, intermediate and strong stresses. The large stresses occur mostly at the contact zones as in noncohesive granular media with a decreasing exponential distribution. The weak forces reflect the arching effect. The intermediate stresses belong mostly to the bulk of the particles and their distribution is well fit to a Gaussian distribution. We also observe that the stress chains are essentially guided by the cementing matrix in tension and by the particulate backbone in compression. Crack formation is analyzed in terms of particle damage as a function of matrix volume fraction and particle-matrix adherence. Our data provide evidence for three regimes of crack propagation depending on the crack path through the material. We find that particle damage scales well with the relative toughness of the particle-matrix interface. The interface toughness appears therefore to be strongly correlated with particle damage and determines transition from soft to hard behavior in wheat endosperm.

Comparison of preparation techniques for CoFeNb/CNTs catalyst

NASA Astrophysics Data System (ADS)

Hamid, Hami Haslinda; Zabidi, Noor Asmawati Mohd; Gholami, Zahra; Shaharun, Maizatul Shima

2016-11-01

CoFe-based catalysts were prepared using reverse-microemulsion and co-impregnation method. Effect of different preparation techniques on morphology and physiochemical properties of the FTS catalyst CoFeNb/CNTs was investigated. TEM analyses show that the morphological properties of catalysts were affected by preparation techniques. Reverse-micremulsion and co-impregnation method resulted in average particle size of 5.61 nm and 6.20 nm respectively. CoFe-impregnation catalyst is reducible at lower temperature compared to that of reverse-microemulsion catalyst. Acid and thermal treatment of CNTs created defects onto CNTs-support.

Growth of vertically aligned single-walled carbon nanotubes with metallic chirality through faceted FePt-Au catalysts

NASA Astrophysics Data System (ADS)

Ohashi, Toshiyuki; Iwama, Hiroki; Shima, Toshiyuki

2016-02-01

Direct synthesis of vertically aligned metallic single-walled carbon nanotubes (m-SWCNT forests) is a difficult challenge. We have successfully synthesized m-SWCNT forests using faceted iron platinum-gold catalysts epitaxially grown on a single crystalline magnesium oxide substrate. The metallic content of the forests estimated by Raman spectroscopy reaches 90%. From the standpoint of growth rate of the forests, the growth mechanism is probably based on the catalyst of solid state. It is suggested that preferential growth of m-SWCNTs is achieved when both factors are satisfied, namely, {111} dominant octahedral facet and ideal size (fine particles) of FePt particles.

Finite element analysis of Al 2024/Cu-Al-Ni shape memory alloy composites with defects/cracks

NASA Astrophysics Data System (ADS)

Kotresh, M.; Benal, M. M., Dr; Siddalinga Swamy, N. H., Dr

2018-02-01

In this work, a numerical approach to predict the stress field behaviour of defect/crack in shape memory alloy (SMA) particles reinforced composite known as the adaptive composite is presented. Simulation is based on the finite element method. The critical stress field approach was used to determine the stresses around defect/crack. Thereby stress amplification issue is being resolved. In this paper, the effect volume % of shape memory alloy and shape memory effect of reinforcement for as-cast and SME trained composites are examined and discussed. Shape memory effect known as training is achieved by pre-straining of reinforcement particles by equivalent changes in their expansion coefficients.

Decolorization of Methylene Blue by Persulfate Activated with FeO Magnetic Particles.

PubMed

Hung, Chang-Mao; Chen, Chiu-Wen; Liu, Yi-Yuan; Dong, Cheng-Di

2016-08-01

In this study, the degradation of methylene blue (MB) was conducted to evaluate the feasibility of using persulfate oxidation activated with iron oxide (FeO) magnetic particles. The results demonstrated that the decolorization rate of MB increased with increasing FeO concentration, exhibiting maximum efficiency at pH0 3.0. The kinetics of MB was studied in the binary FeO catalyst and persulfate oxidation system. The surface properties of FeO before and after reaction was analyzed using cyclic voltammogram (CV), three-dimensional excitation-emission fluorescence matrix (EEFM) spectroscopy, zeta potential, particle size distribution measurements, X-ray diffraction (XRD) and environmental scanning electron microscopy-energy dispersive X-ray spectrometry (ESEM-EDS). The CV data indicated that a reversible redox reaction holds the key to explaining the significant activity of the catalyst. EEFM was used to evaluate the catalyst yield of FeO by fluorescence intensity plots with excitation/emission at 220/300 nm and 260/300 nm. The XRD and ESEM-EDS results confirmed the presence of FeO in the catalyst.

Revealing the Dynamics of Platinum Nanoparticle Catalysts on Carbon in Oxygen and Water Using Environmental TEM

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

Luo, Langli; Engelhard, Mark H.; Shao, Yuyan

Deactivation of supported metal nanoparticle catalysts, especially in relevant gas condition, is a critical challenge for many technological applications, including heterogeneous catalysis, electrocatalysis, fuel cells, biomedical imaging and drug delivery. It has been far more commonly realized that deactivation of catalysts stems from surface area loss due to particle coarsening, however, for which the mechanism remains largely unclear. Herein, we use aberration corrected environmental transmission electron microscopy, at atomic level, to in-situ observe the dynamics of Pt catalyst in fuel cell relevant gas conditions. Particles migration and coalescence is observed to be the dominant coarsening process. As compared with themore » case of H2O, O2 promotes Pt nanoparticle migration on carbon surface. Surprisingly, coating Pt/carbon with a nanofilm of electrolyte (Nafion ionomer) leads to a faster migration of Pt in H2O than in O2, a consequence of Nafion-carbon interface water “lubrication” effect. Atomically, the particles coalescence is featured by re-orientation of particles towards lattice matching, a process driven by orientation dependent van der Waals force. These results provide direct observations of dynamics of metal nanoparticles at critical surface/interface under relevant conditions and yield significant insights into the multi-phase interaction in related technological processes.« less

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

James K. Neathery; Gary Jacobs; Amitava Sarkar

In the previous reporting period, modifications were completed for integrating a continuous wax filtration system for a 4 liter slurry bubble column reactor. During the current reporting period, a shakedown of the system was completed. Several problems were encountered with the progressive cavity pump used to circulate the wax/catalyst slurry though the cross-flow filter element and reactor. During the activation of the catalyst with elevated temperature (> 270 C) the elastomer pump stator released sulfur thereby totally deactivating the iron-based catalyst. Difficulties in maintaining an acceptable leak rate from the pump seal and stator housing were also encountered. Consequently, themore » system leak rate exceeded the expected production rate of wax; therefore, no online filtration could be accomplished. Work continued regarding the characterization of ultra-fine catalyst structures. The effect of carbidation on the morphology of iron hydroxide oxide particles was the focus of the study during this reporting period. Oxidation of Fe (II) sulfate results in predominantly {gamma}-FeOOH particles which have a rod-shaped (nano-needles) crystalline structure. Carbidation of the prepared {gamma}-FeOOH with CO at atmospheric pressure produced iron carbides with spherical layered structure. HRTEM and EDS analysis revealed that carbidation of {gamma}-FeOOH particles changes the initial nano-needles morphology and generates ultrafine carbide particles with irregular spherical shape.« less

Catalysts to reduce NO.sub.x in an exhaust gas stream and methods of preparation

DOEpatents

Koermer, Gerald S [Basking Ridge, NJ; Moini, Ahmad [Princeton, NJ; Furbeck, Howard [Hamilton, NJ; Castellano, Christopher R [Ringoes, NJ

2012-05-08

Catalysts, systems and methods are described to reduce NO.sub.x emissions of an internal combustion engine. In one embodiment, an emissions treatment system for an exhaust stream is provided having a catalyst comprising silver on a particulate alumina support, the silver having a diameter of less than about 20 nm. Methods of manufacturing catalysts are described in which ionic silver is impregnated on particulate hydroxylated alumina particles.

Formation of Platinum Catalyst on Carbon Black Using an In-Liquid Plasma Method for Fuel Cells.

PubMed

Show, Yoshiyuki; Ueno, Yutaro

2017-01-31

Platinum (Pt) catalyst was formed on the surface of carbon black using an in-liquid plasma method. The formed Pt catalyst showed the average particle size of 4.1 nm. This Pt catalyst was applied to a polymer electrolyte membrane fuel cell (PEMFC). The PEMFC showed an open voltage of 0.85 V and a maximum output power density of 216 mW/cm2.

Formation of Platinum Catalyst on Carbon Black Using an In-Liquid Plasma Method for Fuel Cells

PubMed Central

Show, Yoshiyuki; Ueno, Yutaro

2017-01-01

Platinum (Pt) catalyst was formed on the surface of carbon black using an in-liquid plasma method. The formed Pt catalyst showed the average particle size of 4.1 nm. This Pt catalyst was applied to a polymer electrolyte membrane fuel cell (PEMFC). The PEMFC showed an open voltage of 0.85 V and a maximum output power density of 216 mW/cm2. PMID:28336864

A Geometric Approach to Modeling Microstructurally Small Fatigue Crack Formation. 2; Simulation and Prediction of Crack Nucleation in AA 7075-T651

NASA Technical Reports Server (NTRS)

Hochhalter, Jake D.; Littlewood, David J.; Christ, Robert J., Jr.; Veilleux, M. G.; Bozek, J. E.; Ingraffea, A. R.; Maniatty, Antionette M.

2010-01-01

The objective of this paper is to develop further a framework for computationally modeling microstructurally small fatigue crack growth in AA 7075-T651 [1]. The focus is on the nucleation event, when a crack extends from within a second-phase particle into a surrounding grain, since this has been observed to be an initiating mechanism for fatigue crack growth in this alloy. It is hypothesized that nucleation can be predicted by computing a non-local nucleation metric near the crack front. The hypothesis is tested by employing a combination of experimentation and nite element modeling in which various slip-based and energy-based nucleation metrics are tested for validity, where each metric is derived from a continuum crystal plasticity formulation. To investigate each metric, a non-local procedure is developed for the calculation of nucleation metrics in the neighborhood of a crack front. Initially, an idealized baseline model consisting of a single grain containing a semi-ellipsoidal surface particle is studied to investigate the dependence of each nucleation metric on lattice orientation, number of load cycles, and non-local regularization method. This is followed by a comparison of experimental observations and computational results for microstructural models constructed by replicating the observed microstructural geometry near second-phase particles in fatigue specimens. It is found that orientation strongly influences the direction of slip localization and, as a result, in uences the nucleation mechanism. Also, the baseline models, replication models, and past experimental observation consistently suggest that a set of particular grain orientations is most likely to nucleate fatigue cracks. It is found that a continuum crystal plasticity model and a non-local nucleation metric can be used to predict the nucleation event in AA 7075-T651. However, nucleation metric threshold values that correspond to various nucleation governing mechanisms must be calibrated.

Pt-free carbon-based fuel cell catalyst prepared from spherical polyimide for enhanced oxygen diffusion

PubMed Central

Nabae, Yuta; Nagata, Shinsuke; Hayakawa, Teruaki; Niwa, Hideharu; Harada, Yoshihisa; Oshima, Masaharu; Isoda, Ayano; Matsunaga, Atsushi; Tanaka, Kazuhisa; Aoki, Tsutomu

2016-01-01

The development of a non-precious metal (NPM) fuel cell catalyst is extremely important to achieve globalization of polymer electrolyte fuel cells due to the cost and scarcity of platinum. Here, we report on a NPM cathode catalyst prepared by the pyrolysis of spherical polyimide nanoparticles that contain small amounts of Fe additive. 60 nm diameter Fe-containing polyimide nanoparticles were successfully synthesized by the precipitation polymerization of pyromellitic acid dianhydride and 1,3,5-tris(4-aminophenyl)benzene with Fe(acac)3 (acac = acetylacetonate) as an additive. The particles were subsequently carbonized by multistep pyrolysis to obtain the NPM catalyst while retaining the small particle size. The catalyst has good performance and promising durability for fuel cell applications. The fuel cell performance under a 0.2 MPa air atmosphere at 80 °C of 1.0 A cm−2 at 0.46 V is especially remarkable and better than that previously reported. PMID:26987682

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.

Study to improve the quality of a Mexican straight run gasoil over NiMo/γ-Al 2O 3 catalysts

NASA Astrophysics Data System (ADS)

Domínguez-Crespo, M. A.; Díaz-García, L.; Arce-Estrada, E. M.; Torres-Huerta, A. M.; Cortéz-De la Paz, M. T.

2006-11-01

Four NiMo catalyst supported on Al 2O 3 with different textural properties have been studied in the hydrodesulfurization (HDS), hydrodenitrogenation (HDN) and hydrodearomatization (HDA) of a Mexican straight run gasoil (SRGO). All reactions were carried out at three different temperatures 613, 633, and 653 K. Alumina supports were analysed by pyridine FTIR-TPD and nitrogen physisorption in order to determine their surface acidity and textural properties, respectively. TPR studies of the NiMo catalysts were analysed to correlate their hydrogenating properties. Metallic particles were characterized (after sulfidation) using transmission electron microscopy (TEM). Catalytic activities are discussed in relation to the physicochemical properties of NiMo catalysts. The importance of textural properties on coke deposition has been emphasized. The results of catalytic activity of these materials varied depending on dispersed MoS particles and pore distribution in final catalysts. The optimum pore diameter was found around 80 Å for HDS and HDN.

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.

Facile solid-state synthesis of highly dispersed Cu nanospheres anchored on coal-based activated carbons as an efficient heterogeneous catalyst for the reduction of 4-nitrophenol

NASA Astrophysics Data System (ADS)

Wang, Shan; Gao, Shasha; Tang, Yakun; Wang, Lei; Jia, Dianzeng; Liu, Lang

2018-04-01

Coal-based activated carbons (AC) were acted as the support, Cu/AC catalysts were synthesized by a facile solid-state reaction combined with subsequent heat treatment. In Cu/AC composites, highly dispersed Cu nanospheres were anchored on AC. The catalytic activity for 4-nitrophenol (4-NP) was investigated, the effects of activation temperature and copper loading on the catalytic performance were studied. The catalysts exhibited very high catalytic activity and moderate chemical stability due to the unique characteristics of the particle-assembled nanostructures, the high surface area and the porous structure of coal-based AC and the good dispersion of metal particles. Design and preparation of non-noble metal composite catalysts provide a new direction for improving the added value of coal.

Catalyst containing oxygen transport membrane

DOEpatents

Christie, Gervase Maxwell; Wilson, Jamie Robyn; van Hassel, Bart Antonie

2012-12-04

A composite oxygen transport membrane having a dense layer, a porous support layer and an intermediate porous layer located between the dense layer and the porous support layer. Both the dense layer and the intermediate porous layer are formed from an ionic conductive material to conduct oxygen ions and an electrically conductive material to conduct electrons. The porous support layer has a high permeability, high porosity, and a high average pore diameter and the intermediate porous layer has a lower permeability and lower pore diameter than the porous support layer. Catalyst particles selected to promote oxidation of a combustible substance are located in the intermediate porous layer and in the porous support adjacent to the intermediate porous layer. The catalyst particles can be formed by wicking a solution of catalyst precursors through the porous support toward the intermediate porous layer.

Analysis of shape memory alloy sensory particles for damage detection via substructure and continuum damage modeling

NASA Astrophysics Data System (ADS)

Bielefeldt, Brent R.; Benzerga, A. Amine; Hartl, Darren J.

2016-04-01

The ability to monitor and predict the structural health of an aircraft is of growing importance to the aerospace industry. Currently, structural inspections and maintenance are based upon experiences with similar aircraft operating in similar conditions. While effective, these methods are time-intensive and unnecessary if the aircraft is not in danger of structural failure. It is imagined that future aircraft will utilize non-destructive evaluation methods, allowing for the near real-time monitoring of structural health. A particularly interesting method involves utilizing the unique transformation response of shape memory alloy (SMA) particles embedded in an aircraft structure. By detecting changes in the mechanical and/or electromagnetic responses of embedded particles, operators could detect the formation or propagation of fatigue cracks in the vicinity of these particles. This work focuses on a finite element model of SMA particles embedded in an aircraft wing using a substructure modeling approach in which degrees of freedom are retained only at specified points of connection to other parts or the application of boundary conditions, greatly reducing computational cost. Previous work evaluated isolated particle response to a static crack to numerically demonstrate and validate this damage detection method. This paper presents the implementation of a damage model to account for crack propagation and examine for the first time the effect of particle configuration and/or relative placement with respect to the ability to detect damage.

Selective hydrodechlorination of 1,2-dichloroethane catalyzed by trace Pd decorated Ag/Al2O3 catalysts prepared by galvanic replacement

NASA Astrophysics Data System (ADS)

Sun, Jingya; Han, Yuxiang; Fu, Heyun; Wan, Haiqin; Xu, Zhaoyi; Zheng, Shourong

2018-01-01

Ag catalysts decorated by trace Pd supported on γ-Al2O3 with different structure and chemical properties were prepared using a combined impregnation and galvanic replacement method. For comparison, monometallic Ag/γ-Al2O3 and Pd/γ-Al2O3 catalysts were prepared using the impregnation method. Gas-phase catalytic hydrodechlorination of 1,2-dichloroethane to ethylene was investigated on those catalysts. The structures and chemical compositions of bimetallic Pd-Ag particles in the catalysts were controlled by adjusting Pd replacement amount. The as-prepared catalysts were characterized by X-ray diffraction, transmission electron microscopy, UV-vis diffuse reflectance spectroscopy, X-ray photoelectron spectroscopy, and in-situ FTIR spectroscopy of CO adsorption. The results demonstrated that contiguous Pd sites dominated in the monometallic Pd/γ-Al2O3 catalyst, while Pd atoms were separately decorated on the surface of Ag particles in the bimetallic Pd-Ag/γ-Al2O3 catalysts when Pd replacement amount was below 0.30 wt.%. At Pd replacement amount of 0.30 wt.%, Pd ensembles with contiguous Pd sites developed in the bimetallic catalyst. Thus, monometallic Pd/γ-Al2O3 catalyst displayed negligible ethylene selectivity toward the catalytic hydrodechlorination of 1,2-dichloroethane, while bimetallic Pd-Ag/γ-Al2O3 catalyst with a Pd replacement amount of 0.13 wt.% exhibited 94.6% of ethylene selectivity. Furthermore, selectivity to incompletely dechlorinated byproduct chloroethylene decreased with Pd replacement amount, due to the enhanced decoration effect of Pd on large Ag ensembles. Findings in this work provide a promising bimetallic catalyst prepared by galvanic replacement for the selective catalytic hydrodechlorination of 1,2-dichloroethane.

Highly active self-immobilized FI-Zr catalysts in a PCP framework for ethylene polymerization.

PubMed

Li, He; Xu, Bo; He, Jianghao; Liu, Xiaoming; Gao, Wei; Mu, Ying

2015-12-04

A series of zirconium-based porous coordination polymers (PCPs) containing FI catalysts in the frameworks have been developed and studied as catalysts for ethylene polymerization. These PCPs exhibit good catalytic activities and long life times, producing polyethylenes with high molecular weights and bimodal molecular weight distribution in the form of particles.

Progress of a Cross-Correlation Based Optical Strain Measurement Technique for Detecting Radial Growth on a Rotating Disk

NASA Technical Reports Server (NTRS)

Clem, Michelle M.; Woike, Mark R.; Abdul-Aziz, Ali

2014-01-01

The Aeronautical Sciences Project under NASA's Fundamental Aeronautics Program is interested in the development of novel measurement technologies, such as optical surface measurements for the in situ health monitoring of critical constituents of the internal flow path. In situ health monitoring has the potential to detect flaws, i.e. cracks in key components, such as engine turbine disks, before the flaws lead to catastrophic failure. The present study, aims to further validate and develop an optical strain measurement technique to measure the radial growth and strain field of an already cracked disk, mimicking the geometry of a sub-scale turbine engine disk, under loaded conditions in the NASA Glenn Research Center's High Precision Rotordynamics Laboratory. The technique offers potential fault detection by imaging an applied high-contrast random speckle pattern under unloaded and loaded conditions with a CCD camera. Spinning the cracked disk at high speeds (loaded conditions) induces an external load, resulting in a radial growth of the disk of approximately 50.0-µm in the flawed region and hence, a localized strain field. When imaging the cracked disk under static conditions, the disk will be undistorted; however, during rotation the cracked region will grow radially, thus causing the applied particle pattern to be 'shifted'. The resulting particle displacements between the two images is measured using the two-dimensional cross-correlation algorithms implemented in standard Particle Image Velocimetry (PIV) software to track the disk growth, which facilitates calculation of the localized strain field. A random particle distribution is adhered onto the surface of the cracked disk and two bench top experiments are carried out to evaluate the technique's ability to measure the induced particle displacements. The disk is shifted manually using a translation stage equipped with a fine micrometer and a hotplate is used to induce thermal growth of the disk, causing the particles to become shifted. For both experiments, reference and test images are acquired before and after the induced shifts, respectively, and then processed using PIV software. The controlled manual translation of the disk resulted in detection of the particle displacements accurate to 1.75% of full scale and the thermal expansion experiment resulted in successful detection of the disk's thermal growth as compared to the calculated thermal expansion results. After validation of the technique through the induced shift experiments, the technique is implemented in the Rotordynamics Lab for preliminary assessment in a simulated engine environment. The discussion of the findings and plans for future work to improve upon the results are addressed in the paper.

Comparison of primary and secondary particle formation from natural gas engine exhaust and of their volatility characteristics

NASA Astrophysics Data System (ADS)

Alanen, Jenni; Simonen, Pauli; Saarikoski, Sanna; Timonen, Hilkka; Kangasniemi, Oskari; Saukko, Erkka; Hillamo, Risto; Lehtoranta, Kati; Murtonen, Timo; Vesala, Hannu; Keskinen, Jorma; Rönkkö, Topi

2017-07-01

Natural gas usage in the traffic and energy production sectors is a growing trend worldwide; thus, an assessment of its effects on air quality, human health and climate is required. Engine exhaust is a source of primary particulate emissions and secondary aerosol precursors, which both contribute to air quality and can cause adverse health effects. Technologies, such as cleaner engines or fuels, that produce less primary and secondary aerosols could potentially significantly decrease atmospheric particle concentrations and their adverse effects. In this study, we used a potential aerosol mass (PAM) chamber to investigate the secondary aerosol formation potential of natural gas engine exhaust. The PAM chamber was used with a constant UV-light voltage, which resulted in relatively long equivalent atmospheric ages of 11 days at most. The studied retro-fitted natural gas engine exhaust was observed to form secondary aerosol. The mass of the total aged particles, i.e., particle mass measured downstream of the PAM chamber, was 6-268 times as high as the mass of the emitted primary exhaust particles. The secondary organic aerosol (SOA) formation potential was measured to be 9-20 mg kgfuel-1. The total aged particles mainly consisted of organic matter, nitrate, sulfate and ammonium, with the fractions depending on exhaust after-treatment and the engine parameters used. Also, the volatility, composition and concentration of the total aged particles were found to depend on the engine operating mode, catalyst temperature and catalyst type. For example, a high catalyst temperature promoted the formation of sulfate particles, whereas a low catalyst temperature promoted nitrate formation. However, in particular, the concentration of nitrate needed a long time to stabilize - more than half an hour - which complicated the conclusions but also indicates the sensitivity of nitrate measurements on experimental parameters such as emission source and system temperatures. Sulfate was measured to have the highest evaporation temperature, and nitrate had the lowest. The evaporation temperature of ammonium depended on the fractions of nitrate and sulfate in the particles. The average volatility of the total aged particles was measured to be lower than that of primary particles, indicating better stability of the aged natural gas engine-emitted aerosol in the atmosphere. According to the results of this study, the exhaust of a natural gas engine equipped with a catalyst forms secondary aerosol when the atmospheric ages in a PAM chamber are several days long. The secondary aerosol matter has different physical characteristics from those of primary particulate emissions.

Understanding the crack formation of graphite particles in cycled commercial lithium-ion batteries by focused ion beam - scanning electron microscopy

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

Lin, Na; Jia, Zhe; Wang, Zhihui

Here in this paper, the structure degradation of commercial Lithium-ion battery (LIB) graphite anodes with different cycling numbers and charge rates was investigated by focused ion beam (FIB) and scanning electron microscopy (SEM). The cross-section image of graphite anode by FIB milling shows that cracks, resulted in the volume expansion of graphite electrode during long-term cycling, were formed in parallel with the current collector. The crack occurs in the bulk of graphite particles near the lithium insertion surface, which might derive from the stress induced during lithiation and de-lithiation cycles. Subsequently, crack takes place along grain boundaries of the polycrystallinemore » graphite, but only in the direction parallel with the current collector. Furthermore, fast charge graphite electrodes are more prone to form cracks since the tensile strength of graphite is more likely to be surpassed at higher charge rates. Therefore, for LIBs long-term or high charge rate applications, the tensile strength of graphite anode should be taken into account.« less

Understanding the crack formation of graphite particles in cycled commercial lithium-ion batteries by focused ion beam - scanning electron microscopy

DOE PAGES

Lin, Na; Jia, Zhe; Wang, Zhihui; ...

2017-10-01

Here in this paper, the structure degradation of commercial Lithium-ion battery (LIB) graphite anodes with different cycling numbers and charge rates was investigated by focused ion beam (FIB) and scanning electron microscopy (SEM). The cross-section image of graphite anode by FIB milling shows that cracks, resulted in the volume expansion of graphite electrode during long-term cycling, were formed in parallel with the current collector. The crack occurs in the bulk of graphite particles near the lithium insertion surface, which might derive from the stress induced during lithiation and de-lithiation cycles. Subsequently, crack takes place along grain boundaries of the polycrystallinemore » graphite, but only in the direction parallel with the current collector. Furthermore, fast charge graphite electrodes are more prone to form cracks since the tensile strength of graphite is more likely to be surpassed at higher charge rates. Therefore, for LIBs long-term or high charge rate applications, the tensile strength of graphite anode should be taken into account.« less

Static and dynamic structural characterization of nanomaterial catalysts

NASA Astrophysics Data System (ADS)

Masiel, Daniel Joseph

Heterogeneous catalysts systems are pervasive in industry, technology and academia. These systems often involve nanostructured transition metal particles that have crucial interfaces with either their supports or solid products. Understanding the nature of these interfaces as well as the structure of the catalysts and support materials themselves is crucial for the advancement of catalysis in general. Recent developments in the field of transmission electron microscopy (TEM) including dynamic transmission electron microscopy (DTEM), electron tomography, and in situ techniques stand poised to provide fresh insight into nanostructured catalyst systems. Several electron microscopy techniques are applied in this study to elucidate the mechanism of silica nanocoil growth and to discern the role of the support material and catalyst size in carbon dioxide and steam reforming of methane. The growth of silica nanocoils by faceted cobalt nanoparticles is a process that was initially believed to take place via a vapor-liquid-solid growth mechanism similar to other nanowire growth techniques. The extensive TEM work described here suggests that the process may instead occur via transport of silicate and silica species over the nanoparticle surface. Electron tomography studies of the interface between the catalyst particles and the wire indicate that they grow from edges between facets. Studies on reduction of the Co 3O4 nanoparticle precursors to the faceted pure cobalt catalysts were carried out using DTEM and in situ heating. Supported catalyst systems for methane reforming were studied using dark field scanning TEM to better understand sintering effects and the increased activity of Ni/Co catalysts supported by carbon nanotubes. Several novel electron microscopy techniques are described including annular dark field DTEM and a metaheuristic algorithm for solving the phase problem of coherent diffractive imaging. By inserting an annular dark field aperture into the back focal plane of the objective lens in a DTEM, time-resolved dark field images can be produced that have vastly improved contrast for supported catalyst materials compared to bright field DTEM imaging. A new algorithm called swarm optimized phase retrieval is described that uses a population-based approach to solve for the missing phases of diffraction data from discrete particles.

Probing platinum degradation in polymer electrolyte membrane fuel cells by synchrotron X-ray microscopy.

PubMed

Berejnov, Viatcheslav; Martin, Zulima; West, Marcia; Kundu, Sumit; Bessarabov, Dmitri; Stumper, Jürgen; Susac, Darija; Hitchcock, Adam P

2012-04-14

Synchrotron-based scanning transmission X-ray spectromicroscopy (STXM) was used to characterize the local chemical environment at and around the platinum particles in the membrane (PTIM) which form in operationally tested (end-of-life, EOL) catalyst coated membranes (CCMs) of polymer electrolyte membrane fuel cells (PEM-FC). The band of metallic Pt particles in operationally tested CCM membranes was imaged using transmission electron microscopy (TEM). The cathode catalyst layer in the beginning-of-life (BOL) CCMs was fabricated using commercially available catalysts created from Pt precursors with and without nitrogen containing ligands. The surface composition of these catalyst powders was measured by X-ray Photoelectron Spectroscopy (XPS). The local chemical environment of the PTIM in EOL CCMs was found to be directly related to the Pt precursor used in CCM fabrication. STXM chemical mapping at the N 1s edge revealed a characteristic spectrum at and around the dendritic Pt particles in CCMs fabricated with nitrogen containing Pt-precursors. This N 1s spectrum was identical to that of the cathode and different from the membrane. For CCM samples fabricated without nitrogen containing Pt-precursors the N 1s spectrum at the Pt particles was indistinguishable from that of the adjacent membrane. We interpret these observations to indicate that nitrogenous ligands in the nitrogen containing precursors, or decomposition product(s) from that source, are transported together with the dissolved Pt from the cathode into the membrane as a result of the catalyst degradation process. This places constraints on possible mechanisms for the PTIM band formation process.

Process for carbonaceous material conversion and recovery of alkali metal catalyst constituents held by ion exchange sites in conversion residue

DOEpatents

Sharp, David W.

1980-01-01

In a coal gasification operation or similar conversion process carried out in the presence of an alkali metal-containing catalyst wherein solid particles containing alkali metal residues are produced, alkali metal constituents are recovered for the particles by contacting or washing them with an aqueous solution containing calcium or magnesium ions in an alkali metal recovery zone at a low temperature, preferably below about 249.degree. F. During the washing or leaching process, the calcium or magnesium ions displace alkali metal ions held by ion exchange sites in the particles thereby liberating the ions and producing an aqueous effluent containing alkali metal constituents. The aqueous effluent from the alkali metal recovery zone is then recycled to the conversion process where the alkali metal constituents serve as at least a portion of the alkali metal constituents which comprise the alkali metal-containing catalyst.

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.

Photocatalytic hydrogen generation from water under visible light using core/shell nano-catalysts.

PubMed

Wang, X; Shih, K; Li, X Y

2010-01-01

A microemulsion technique was employed to synthesize nano-sized photocatalysts with a core (CdS)/shell (ZnS) structure. The primary particles of the photocatalysts were around 10 nm, and the mean size of the catalyst clusters in water was about 100 nm. The band gaps of the catalysts ranged from 2.25 to 2.46 eV. The experiments of photocatalytic H(2) generation showed that the catalysts (CdS)(x)/(ZnS)(1-x) with x ranging from 0.1 to 1 were able to produce hydrogen from water photolysis under visible light. The catalyst with x=0.9 had the highest rate of hydrogen production. The catalyst loading density also influenced the photo-hydrogen production rate, and the best catalyst concentration in water was 1 g L(-1). The stability of the nano-catalysts in terms of size, morphology and activity was satisfactory during an extended test period for a specific hydrogen production rate of 2.38 mmol g(-1) L(-1) h(-1) and a quantum yield of 16.1% under visible light (165 W Xe lamp, lambda>420 nm). The results demonstrate that the (CdS)/(ZnS) core/shell nano-particles are a novel photo-catalyst for renewable hydrogen generation from water under visible light. This is attributable to the large band-gap ZnS shell that separates the electron/hole pairs generated by the CdS core and hence reduces their recombinations.

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.

Electrocatalytic properties of graphite nanofibers-supported platinum catalysts for direct methanol fuel cells.

PubMed

Park, Soo-Jin; Park, Jeong-Min; Seo, Min-Kang

2009-09-01

Graphite nanofibers (GNFs) treated at various temperatures were used as carbon supports to improve the efficiency of PtRu catalysts. The electrochemical properties of the PtRu/GNFs catalysts were then investigated to evaluate their potential for application in DMFCs. The results indicated that the particle size and dispersibility of PtRu in the catalysts were changed by heat treatment, and the electrochemical activity of the catalysts was improved. Consequently, it was found that heat treatments could have an influence on the surface and structural properties of GNFs, resulting in enhancing an electrocatalytic activity of the catalysts for DMFCs.

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

Enhancement of Treatment Efficiency of Recalcitrant Wastewater Containing Textile Dyes Using a Newly Developed Iron Zeolite Socony Mobil-5 Heterogeneous Catalyst

PubMed Central

Ahmad, Mushtaq; Asghar, Anam; Abdul Raman, Abdul Aziz; Wan Daud, Wan Mohd Ashri

2015-01-01

Fenton oxidation, an advanced oxidation process, is an efficient method for the treatment of recalcitrant wastewaters. Unfortunately, it utilizes H2O2 and iron-based homogeneous catalysts, which lead to the formation of high volumes of sludge and secondary pollutants. To overcome these problems, an alternate option is the usage of heterogeneous catalyst. In this study, a heterogeneous catalyst was developed to provide an alternative solution for homogeneous Fenton oxidation. Iron Zeolite Socony Mobile-5 (Fe-ZSM-5) was synthesized using a new two-step process. Next, the catalyst was characterized by scanning electron microscopy, energy-dispersive X-ray spectroscopy, fourier transform infrared spectroscopy, and Brunauer-Emmett-Teller analysis and tested against a model wastewater containing the azo dye Acid Blue 113. Results showed that the loading of iron particles reduced the surface area of the catalyst from 293.59 to 243.93 m2/g; meanwhile, the average particle size of the loaded material was 12.29 nm. Furthermore, efficiency of the developed catalyst was evaluated by performing heterogeneous Fenton oxidation. Taguchi method was coupled with principal component analysis in order to assess and optimize mineralization efficiency. Experimental results showed that under optimized conditions, over 99.7% degradation and 77% mineralization was obtained, with a 90% reduction in the consumption of the developed catalyst. Furthermore, the developed catalyst was stable and reusable, with less than 2% leaching observed under optimized conditions. Thus, the present study proved that newly developed catalyst has enhanced the oxidation process and reduced the chemicals consumption. PMID:26517827

Enhancement of Treatment Efficiency of Recalcitrant Wastewater Containing Textile Dyes Using a Newly Developed Iron Zeolite Socony Mobil-5 Heterogeneous Catalyst.

PubMed

Ahmad, Mushtaq; Asghar, Anam; Abdul Raman, Abdul Aziz; Wan Daud, Wan Mohd Ashri

2015-01-01

Fenton oxidation, an advanced oxidation process, is an efficient method for the treatment of recalcitrant wastewaters. Unfortunately, it utilizes H2O2 and iron-based homogeneous catalysts, which lead to the formation of high volumes of sludge and secondary pollutants. To overcome these problems, an alternate option is the usage of heterogeneous catalyst. In this study, a heterogeneous catalyst was developed to provide an alternative solution for homogeneous Fenton oxidation. Iron Zeolite Socony Mobile-5 (Fe-ZSM-5) was synthesized using a new two-step process. Next, the catalyst was characterized by scanning electron microscopy, energy-dispersive X-ray spectroscopy, fourier transform infrared spectroscopy, and Brunauer-Emmett-Teller analysis and tested against a model wastewater containing the azo dye Acid Blue 113. Results showed that the loading of iron particles reduced the surface area of the catalyst from 293.59 to 243.93 m2/g; meanwhile, the average particle size of the loaded material was 12.29 nm. Furthermore, efficiency of the developed catalyst was evaluated by performing heterogeneous Fenton oxidation. Taguchi method was coupled with principal component analysis in order to assess and optimize mineralization efficiency. Experimental results showed that under optimized conditions, over 99.7% degradation and 77% mineralization was obtained, with a 90% reduction in the consumption of the developed catalyst. Furthermore, the developed catalyst was stable and reusable, with less than 2% leaching observed under optimized conditions. Thus, the present study proved that newly developed catalyst has enhanced the oxidation process and reduced the chemicals consumption.

The growth of small corrosion fatigue cracks in alloy 2024

NASA Technical Reports Server (NTRS)

Piascik, Robert S.; Willard, Scott A.

1993-01-01

The corrosion fatigue crack growth characteristics of small surface and corner cracks in aluminum alloy 2024 is established. The damaging effect of salt water on the early stages of small crack growth is characterized by crack initiation at constituent particle pits, intergranular microcracking for a less than 100 micrometers, and transgranular small crack growth for a micrometer. In aqueous 1 percent NaCl and at a constant anodic potential of -700 mV(sub SCE), small cracks exhibit a factor of three increase in fatigue crack growth rates compared to laboratory air. Small cracks exhibit accelerated corrosion fatigue crack growth rates at low levels of delta-K (less than 1 MPa square root of m) below long crack delta-K (sub th). When exposed to Paris regime levels of crack tip stress intensity, small corrosion fatigue cracks exhibit growth rates similar to that observed for long cracks. Results suggest that crack closure effects influence the corrosion fatigue crack growth rates of small cracks (a less than or equal to 100 micrometers). This is evidenced by similar small and long crack growth behavior at various levels of R. Contrary to the corrosion fatigue characteristics of small cracks in high strength steels, no pronounced chemical crack length effect is observed for Al by 2024 exposed to salt water.

Repair, Evaluation, Maintenance, and Rehabilitation Research Program: Evaluation of Civil Works Metal Structures

DTIC Science & Technology

1991-01-01

can be per- formed at any time, as a spot check, or periodically. Liauid Penetrant Inspection (PT) 19. Aplication . Liquid penetrant testing (PT) is a...increases the inspection \\MAGNE TIC PARTICLESiA - CRACK- Figure 6. Crack in bar magnet attracting magnetic particles 14 particle mobility and enables the...923-9800 or (312) 474-5860 Service: IA, IL, IN, MI, WI LOUISIANA O.S.I. Mobile Lab, Inc. X-Ray Inspection, Inc. P. 0. Box 395 P. 0. Box 51651 Harvey

Electrochemical Catalyst-Support Effects and Their Stabilizing Role for IrOx Nanoparticle Catalysts during the Oxygen Evolution Reaction.

PubMed

Oh, Hyung-Suk; Nong, Hong Nhan; Reier, Tobias; Bergmann, Arno; Gliech, Manuel; Ferreira de Araújo, Jorge; Willinger, Elena; Schlögl, Robert; Teschner, Detre; Strasser, Peter

2016-09-28

Redox-active support materials can help reduce the noble-metal loading of a solid chemical catalyst while offering electronic catalyst-support interactions beneficial for catalyst durability. This is well known in heterogeneous gas-phase catalysis but much less discussed for electrocatalysis at electrified liquid-solid interfaces. Here, we demonstrate experimental evidence for electronic catalyst-support interactions in electrochemical environments and study their role and contribution to the corrosion stability of catalyst/support couples. Electrochemically oxidized Ir oxide nanoparticles, supported on high surface area carbons and oxides, were selected as model catalyst/support systems for the electrocatalytic oxygen evolution reaction (OER). First, the electronic, chemical, and structural state of the catalyst/support couple was compared using XANES, EXAFS, TEM, and depth-resolved XPS. While carbon-supported oxidized Ir particle showed exclusively the redox state (+4), the Ir/IrOx/ATO system exhibited evidence of metal/metal-oxide support interactions (MMOSI) that stabilized the metal particles on antimony-doped tin oxide (ATO) in sustained lower Ir oxidation states (Ir(3.2+)). At the same time, the growth of higher valent Ir oxide layers that compromise catalyst stability was suppressed. Then the electrochemical stability and the charge-transfer kinetics of the electrocatalysts were evaluated under constant current and constant potential conditions, where the analysis of the metal dissolution confirmed that the ATO support mitigates Ir(z+) dissolution thanks to a stronger MMOSI effect. Our findings raise the possibility that MMOSI effects in electrochemistry-largely neglected in the past-may be more important for a detailed understanding of the durability of oxide-supported nanoparticle OER catalysts than previously thought.

Palladium-tin catalysts for the direct synthesis of H 2O 2 with high selectivity

DOE PAGES

Freakley, Simon J.; He, Qian; Harrhy, Jonathan H.; ...

2016-02-25

The direct synthesis of hydrogen peroxide (H 2O 2 ) from H 2 and O 2 represents a potentially atom-efficient alternative to the current industrial indirect process. We show that the addition of tin to palladium catalysts coupled with an appropriate heat treatment cycle switches off the sequential hydrogenation and decomposition reactions, enabling selectivities of >95% toward H 2O 2 . This effect arises from a tin oxide surface layer that encapsulates small Pd-rich particles while leaving larger Pd-Sn alloy particles exposed. In conclusion, we show that this effect is a general feature for oxide-supported Pd catalysts containing an appropriatemore » second metal oxide component, and we set out the design principles for producing high-selectivity Pd-based catalysts for direct H 2O 2 production that do not contain gold.« less

Population and hierarchy of active species in gold iron oxide catalysts for carbon monoxide oxidation.

PubMed

He, Qian; Freakley, Simon J; Edwards, Jennifer K; Carley, Albert F; Borisevich, Albina Y; Mineo, Yuki; Haruta, Masatake; Hutchings, Graham J; Kiely, Christopher J

2016-09-27

The identity of active species in supported gold catalysts for low temperature carbon monoxide oxidation remains an unsettled debate. With large amounts of experimental evidence supporting theories of either gold nanoparticles or sub-nm gold species being active, it was recently proposed that a size-dependent activity hierarchy should exist. Here we study the diverging catalytic behaviours after heat treatment of Au/FeO x materials prepared via co-precipitation and deposition precipitation methods. After ruling out any support effects, the gold particle size distributions in different catalysts are quantitatively studied using aberration corrected scanning transmission electron microscopy (STEM). A counting protocol is developed to reveal the true particle size distribution from HAADF-STEM images, which reliably includes all the gold species present. Correlation of the populations of the various gold species present with catalysis results demonstrate that a size-dependent activity hierarchy must exist in the Au/FeO x catalyst.

Sources of anthropogenic platinum-group elements (PGE): Automotive catalysts versus PGE-processing industries.

PubMed

Zereini, F; Dirksen, F; Skerstupp, B; Urban, H

1998-01-01

Soil samples from the area of Hanau (Hessen, Germany) were analyzed for anthropogenic platinum-group elements (PGE). The results confirm the existence of two different sources for anthropogenic PGE: 1. automotive catalysts, and 2. PGE-processing plants. Both sources emit qualitatively and quantitatively different PGE spectra and PGE interelemental ratios (especially the Pt/Rh ratio). Elevated PGE values which are due to automotive catalysts are restricted to a narrow-range along roadside soil, whereas those due to PGE-processing plants display a large-area dispersion. The emitted PGE-containing particles in the case of automotive catalysts are subject to transport by wind and water, whereas those from PGE-processing plants are preferably transported by wind. This points to a different aerodynamic particle size. Pt, Pd, and Rh concentrations along motorways are dependent on the amount of traffic and the driving characteristics.

Dye-sensitized MIL-101 metal organic frameworks loaded with Ni/NiO{sub x} nanoparticles for efficient visible-light-driven hydrogen generation

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

Liu, Xin-Ling; Wang, Rong; Yuan, Yu-Peng, E-mail: yupengyuan@ahu.edu.cn, E-mail: cxue@ntu.edu.sg

2015-10-01

The Ni/NiO{sub x} particles were in situ photodeposited on MIL-101 metal organic frameworks as catalysts for boosting H{sub 2} generation from Erythrosin B dye sensitization under visible-light irradiation. The highest H{sub 2} production rate of 125 μmol h{sup −1} was achieved from the system containing 5 wt. % Ni-loaded MIL-101 (20 mg) and 30 mg Erythrosin B dye. Moreover, the Ni/NiO{sub x} catalysts show excellent stability for long-term photocatalytic reaction. The enhancement on H{sub 2} generation is attributed to the efficient charge transfer from photoexcited dye to the Ni catalyst via MIL-101. Our results demonstrate that the economical Ni/NiO{sub x}more » particles are durable and active catalysts for photocatalytic H{sub 2} generation.« less

Self-healing coatings containing microcapsule

NASA Astrophysics Data System (ADS)

Zhao, Yang; Zhang, Wei; Liao, Le-ping; Wang, Si-jie; Li, Wu-jun

2012-01-01

Effectiveness of epoxy resin filled microcapsules was investigated for healing of cracks generated in coatings. Microcapsules were prepared by in situ polymerization of urea-formaldehyde resin to form shell over epoxy resin droplets. Characteristics of these capsules were studied by 3D measuring laser microscope, particle size analyzer, Fourier-transform infrared spectroscopy (FTIR) and differential scanning calorimeter (DSC) to investigate their surface morphology, size distribution, chemical structure and thermal stability, respectively. The results indicate that microcapsules containing epoxy resins can be synthesized successfully. The size is around 100 μm. The rough outer surface of microcapsule is composed of agglomerated urea-formaldehyde nanoparticles. The size and surface morphology of microcapsule can be controlled by selecting different processing parameters. The microcapsules basically exhibit good storage stability at room temperature, and they are chemically stable before the heating temperature is up to approximately 200 °C. The model system of self-healing coating consists of epoxy resin matrix, 10 wt% microencapsulated healing agent, 2 wt% catalyst solution. The self-healing function of this coating system is evaluated through self-healing testing of damaged and healed coated steel samples.

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.

Ziegler-Natta Catalyst Based on MgCl₂/Clay/ID/TiCl₄ for the Synthesis of Spherical Particles of Polypropylene Nanocomposites.

PubMed

Cardoso, Renata da Silva; Oliveira, Jaqueline da Silva; Ramis, Luciana Bortolin; Marques, Maria de Fátima V

2018-07-01

In the present work, we have designed MgCl2/clay/internal donor (ID)/TiCl4 based bisupported Ziegler-Natta catalysts containing varying amounts of organoclay (montmorillonite) in order to synthesize spherical particles of polypropylene/clay nanocomposites (PCN). The organoclay was introduced into the catalyst support formulation and PCN was obtained using the in situ polymerization technique. Decreasing the reaction time, it was possible to obtain nanocomposites with high concentrations of clay (masterbatches). Micrographs of SEM confirmed the spherical morphology of the catalysts. In addition, XRD patterns show that the active sites for polymerization were inserted in the clay galleries. The catalytic performance was evaluated in slurry propylene polymerization using triethylaluminium as cocatalyst and silane as external electron donor at 70 °C, 4 bar, and different reaction times. The PCNs obtained containing different clay amounts were characterized by X-ray diffraction, thermal analyses, transmission electronic microscopy, and extractables in heptane. The results revealed that the synthesized PP/clay particles were also spherical showing that the morphological control is possible even using catalysts containing high amounts of clay. The PCN presented high degradation temperature (459 °C). The XRD peak related to the clay interlamellar distance has shifted to lower angles, and TEM images confirmed the formation of exfoliated/intercalated clay on the PP matrix and absence of microparticles of clay.

Catalysts to reduce NO.sub.x in an exhaust gas stream and methods of preparation

DOEpatents

Castellano, Christopher R [Ringoes, NJ; Moini, Ahmad [Princeton, NJ; Koermer, Gerald S [Basking Ridge, NJ; Furbeck, Howard [Hamilton, NJ; Schmieg, Steven J [Troy, MI; Blint, Richard J [Shelby Township, MI

2011-05-17

Catalysts, systems and methods are described to reduce NO.sub.x emissions of an internal combustion engine. In one embodiment, an emissions treatment system for an exhaust stream is provided having a catalyst comprising silver and a platinum group metal on a particulate alumina support, the atomic fraction of the platinum group metal being less than or equal to about 0.25. Methods of manufacturing catalysts are described in which silver is impregnated on alumina particles.

Measurement of Fine Particles From Mobile and Stationary Sources, and Reducing the Air Conditioner Power Consumption in Hybrid Electric Vehicles

NASA Astrophysics Data System (ADS)

Brewer, Eli Henry

We study the PM2.5and ultrafine exhaust emissions from a new natural gas-fired turbine power facility to better understand air pollution in California. To characterize the emissions from new natural gas turbines, a series of tests were performed on a GE LMS100 gas turbine. These tests included PM2.5 and wet chemical tests for SO2/SO 3 and NH3, as well as ultrafine (less than 100 nm in diameter) particulate matter measurements. The turbine exhaust had an average particle number concentration that was 2.3x103 times higher than ambient air. The majority of these particles were nanoparticles; at the 100 nm size, stack particle concentrations were about 20 times higher than ambient, and increased to 3.9x104 times higher on average in the 2.5 - 3 nm particle size range. This study also found that ammonia emissions were higher than expected, but in compliance with permit conditions. This was possibly due to an ammonia imbalance entering the catalyst, some flue gas bypassing the catalyst, or not enough catalyst volume. SO3 accounted for an average of 23% of the total sulfur oxides emissions measured. Some of the SO3 is formed in the combustion process, it is likely that the majority formed as the SO2 in the combustion products passed across the oxidizing CO catalyst and SCR catalyst. The 100 MW turbine sampled in this study emitted particle loadings similar to those previously measured from turbines in the SCAQMD area, however, the turbine exhaust contained far more particles than ambient air. The power consumed by an air conditioner accounts for a significant fraction of the total power used by hybrid and electric vehicles especially during summer. This study examined the effect of recirculation of cabin air on power consumption of mobile air conditioners both in-lab and on-road. Real time power consumption and vehicle mileage were recorded by an On Board Diagnostic monitor and carbon balance method. Vehicle mileage improved with increased cabin air recirculation. The recirculation of cabin air also significantly reduced in-cabin particle concentrations. Recirculation of cabin air is an excellent and immediate solution to increase vehicle mileage and improve cabin air quality.

Hydrothermal alkali metal catalyst recovery process

DOEpatents

Eakman, James M.; Clavenna, LeRoy R.

1979-01-01

In a coal gasification operation or similar conversion process carried out in the presence of an alkali metal-containing catalyst wherein solid particles containing alkali metal residues are produced, alkali metal constituents are recovered from the particles primarily in the form of water soluble alkali metal formates by treating the particles with a calcium or magnesium-containing compound in the presence of water at a temperature between about 250.degree. F. and about 700.degree. F. and in the presence of added carbon monoxide. During the treating process the water insoluble alkali metal compounds comprising the insoluble alkali metal residues are converted into water soluble alkali metal formates. The resultant aqueous solution containing water soluble alkali metal formates is then separated from the treated particles and any insoluble materials formed during the treatment process, and recycled to the gasification process where the alkali metal formates serve as at least a portion of the alkali metal constituents which comprise the alkali metal-containing catalyst. This process permits increased recovery of alkali metal constituents, thereby decreasing the overall cost of the gasification process by reducing the amount of makeup alkali metal compounds necessary.

Lagrangian Approach to Jet Mixing and Optimization of the Reactor for Production of Carbon Nanotubes

NASA Technical Reports Server (NTRS)

Povitsky, Alex; Salas, Manuel D.

2001-01-01

This study was motivated by an attempt to optimize the High Pressure carbon oxide (HiPco) process for the production of carbon nanotubes from gaseous carbon oxide, The goal is to achieve rapid and uniform heating of catalyst particles by an optimal arrangement of jets. A mixed Eulerian and Lagrangian approach is implemented to track the temperature of catalyst particles along their trajectories as a function of time. The FLUENT CFD software with second-order upwind approximation of convective terms and an algebraic multigrid-based solver is used. The poor performance of the original reactor configuration is explained in terms of features of particle trajectories. The trajectories most exposed to the hot jets appear to be the most problematic for heating because they either bend towards the cold jet interior or rotate upwind of the mixing zone. To reduce undesirable slow and/or oscillatory heating of catalyst particles, a reactor configuration with three central jets is proposed and the optimal location of the central and peripheral nozzles is determined.

Synthesis and Stabilization of Supported Metal Catalysts by Atomic Layer Deposition

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

Lu, Junling; Elam, Jeffrey W.; Stair, Peter C.

2013-03-12

Supported metal nanoparticles are among the most important cata-lysts for many practical reactions, including petroleum refining, automobile exhaust treatment, and Fischer–Tropsch synthesis. The catalytic performance strongly depends on the size, composition, and structure of the metal nanoparticles, as well as the underlying support. Scientists have used conventional synthesis methods including impregnation, ion exchange, and deposition–precipitation to control and tune these factors, to establish structure–performance relationships, and to develop better catalysts. Meanwhile, chemists have improved the stability of metal nanoparticles against sintering by the application of protective layers, such as polymers and oxides that encapsulate the metal particle. This often leadsmore » to decreased catalytic activity due to a lack of precise control over the thickness of the protective layer. A promising method of catalyst synthesis is atomic layer deposition (ALD). ALD is a variation on chemical vapor deposition in which metals, oxides, and other materials are deposited on surfaces by a sequence of self-limiting reactions. The self-limiting character of these reactions makes it possible to achieve uniform deposits on high-surface-area porous solids. Therefore, design and synthesis of advanced catalysts on the nanoscale becomes possible through precise control over the structure and composition of the underlying support, the catalytic active sites, and the protective layer. In this Account, we describe our advances in the synthesis and stabilization of supported metal catalysts by ALD. After a short introduction to the technique of ALD, we show several strategies for metal catalyst synthesis by ALD that take advantage of its self-limiting feature. Monometallic and bimetallic catalysts with precise control over the metal particle size, composition, and structure were achieved by combining ALD sequences, surface treatments, and deposition temperature control. Next, we describe ALD oxide overcoats applied with atomically precise thickness control that stabilize metal catalysts while preserving their catalytic function. We also discuss strategies for generation and control over the porosity of the overcoats that allow the embedded metal particles to remain accessible by reactants, and the details for ALD alumina overcoats on metal catalysts. Moreover, using methanol decomposition and oxidative dehydrogenation of ethane as probe reactions, we demonstrate that selectively blocking low coordination metal sites by oxide overcoats can provide another strategy to enhance both the durability and selectivity of metal catalysts.« less

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

Effect of Particle Shape on Mechanical Behaviors of Rocks: A Numerical Study Using Clumped Particle Model

PubMed Central

Rong, Guan; Liu, Guang; Zhou, Chuang-bing

2013-01-01

Since rocks are aggregates of mineral particles, the effect of mineral microstructure on macroscopic mechanical behaviors of rocks is inneglectable. Rock samples of four different particle shapes are established in this study based on clumped particle model, and a sphericity index is used to quantify particle shape. Model parameters for simulation in PFC are obtained by triaxial compression test of quartz sandstone, and simulation of triaxial compression test is then conducted on four rock samples with different particle shapes. It is seen from the results that stress thresholds of rock samples such as crack initiation stress, crack damage stress, and peak stress decrease with the increasing of the sphericity index. The increase of sphericity leads to a drop of elastic modulus and a rise in Poisson ratio, while the decreasing sphericity usually results in the increase of cohesion and internal friction angle. Based on volume change of rock samples during simulation of triaxial compression test, variation of dilation angle with plastic strain is also studied. PMID:23997677

Effect of particle shape on mechanical behaviors of rocks: a numerical study using clumped particle model.

PubMed

Rong, Guan; Liu, Guang; Hou, Di; Zhou, Chuang-Bing

2013-01-01

Since rocks are aggregates of mineral particles, the effect of mineral microstructure on macroscopic mechanical behaviors of rocks is inneglectable. Rock samples of four different particle shapes are established in this study based on clumped particle model, and a sphericity index is used to quantify particle shape. Model parameters for simulation in PFC are obtained by triaxial compression test of quartz sandstone, and simulation of triaxial compression test is then conducted on four rock samples with different particle shapes. It is seen from the results that stress thresholds of rock samples such as crack initiation stress, crack damage stress, and peak stress decrease with the increasing of the sphericity index. The increase of sphericity leads to a drop of elastic modulus and a rise in Poisson ratio, while the decreasing sphericity usually results in the increase of cohesion and internal friction angle. Based on volume change of rock samples during simulation of triaxial compression test, variation of dilation angle with plastic strain is also studied.

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

Cherkaduvasala, V.; Murphy, D.W.; Ban, H.

Popcorn ash particles are fragments of sintered coal fly ash masses that resemble popcorn in low apparent density. They can travel with the flow in the furnace and settle on key places such as catalyst surfaces. Computational fluid dynamics (CFD) models are often used in the design process to prevent the carryover and settling of these particles on catalysts. Particle size, density, and drag coefficient are the most important aerodynamic parameters needed in CFD modeling of particle flow. The objective of this study was to experimentally determine particle size, shape, apparent density, and drag characteristics for popcorn ash particles frommore » a coal-fired power plant. Particle size and shape were characterized by digital photography in three orthogonal directions and by computer image analysis. Particle apparent density was determined by volume and mass measurements. Particle terminal velocities in three directions were measured in water and each particle was also weighed in air and in water. The experimental data were analyzed and models were developed for equivalent sphere and equivalent ellipsoid with apparent density and drag coefficient distributions. The method developed in this study can be used to characterize the aerodynamic properties of popcorn-like particles.« less

In-situ deformation studies of an aluminum metal-matrix composite in a scanning electron microscope

NASA Technical Reports Server (NTRS)

Manoharan, M.; Lewandowski, J. J.

1989-01-01

Tensile specimens made of a metal-matrix composite (cast and extruded aluminum alloy-based matrix reinforced with Al2O3 particulate) were tested in situ in a scanning electron microscope equipped with a deformation stage, to directly monitor the crack propagation phenomenon. The in situ SEM observations revealed the presence of microcracks both ahead of and near the crack-tip region. The microcracks were primarily associated with cracks in the alumina particles. The results suggest that a region of intense deformation exists ahead of the crack and corresponds to the region of microcracking. As the crack progresses, a region of plastically deformed material and associated microcracks remains in the wake of the crack.

Precursor-Based Synthesis of Porous Colloidal Particles towards Highly Efficient Catalysts.

PubMed

Zheng, Yun; Geng, Hongbo; Zhang, Yufei; Chen, Libao; Li, Cheng Chao

2018-04-02

In recent years, porous colloidal particles have found promising applications in catalytic fields, such as photocatalysis, electrocatalysis, industrial and automotive byproducts removal, as well as biomass upgrading. These applications are critical for alleviating the energy crisis and environmental pollution. Porous colloidal particles have remarkable specific areas and abundant reactive sites, which can significantly improve the mass/charge transport and reaction rate in catalysis. Precursor-based synthesis is among the most facile and widely-adopted methods to achieve monodisperse and homogeneous porous colloidal particles. In the current review, we briefly introduce the general catalytic applications of porous colloidal particles. The conventional precursor-based methods are reviewed to design state-of-the-art porous colloidal particles as highly efficient catalysts. The recent development of porous colloidal particles derived from metal-organic frameworks (MOFs), glycerates, carbonate precursors, and ion exchange methods are reviewed. In the end, the current concerns and future development of porous colloidal particles are outlined. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Direct Numerical Simulation of Fluid Flow and Mass Transfer in Particle Clusters

PubMed Central

2018-01-01

In this paper, an efficient ghost-cell based immersed boundary method is applied to perform direct numerical simulation (DNS) of mass transfer problems in particle clusters. To be specific, a nine-sphere cuboid cluster and a random-generated spherical cluster consisting of 100 spheres are studied. In both cases, the cluster is composed of active catalysts and inert particles, and the mutual influence of particles on their mass transfer performance is studied. To simulate active catalysts the Dirichlet boundary condition is imposed at the external surface of spheres, while the zero-flux Neumann boundary condition is applied for inert particles. Through our studies, clustering is found to have negative influence on the mass transfer performance, which can be then improved by dilution with inert particles and higher Reynolds numbers. The distribution of active/inert particles may lead to large variations of the cluster mass transfer performance, and individual particle deep inside the cluster may possess a high Sherwood number. PMID:29657359

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.

Crack Formation in Powder Metallurgy Carbon Nanotube (CNT)/Al Composites During Post Heat-Treatment

NASA Astrophysics Data System (ADS)

Chen, Biao; Imai, Hisashi; Li, Shufeng; Jia, Lei; Umeda, Junko; Kondoh, Katsuyoshi

2015-12-01

After the post heat-treatment (PHT) process of powder metallurgy carbon nanotubes (CNT)/Al composites, micro-cracks were observed in the composites, leading to greatly degraded mechanical properties. To understand and suppress the crack formation, an in situ observation of CNT/Al composites was performed at elevated temperatures. PHT was also applied to various bulk pure Al and CNT/Al composites fabricated under different processes. It was observed that the composites consolidated by hot-extrusion might form micro-cracks, but those consolidated by spark plasma sintering (SPS) showed no crack after PHT. A high-temperature SPS process before hot-extrusion was effective to prevent crack formation. The release of residual stress in severe plastic deformed (SPD) materials was responsible for the cracking phenomena during the PHT process. Furthermore, a good particle bonding was essential and effective to suppress cracks for SPD materials in the PHT process.

Friction Stir Welding of Al Alloy 2219-T8: Part II-Mechanical and Corrosion

NASA Astrophysics Data System (ADS)

Kang, Ju; Feng, Zhi-Cao; Li, Ji-Chao; Frankel, G. S.; Wang, Guo-Qing; Wu, Ai-Ping

2016-09-01

In Part I of this series, abnormal agglomerations of θ particles with size of about 100 to 1000 µm were observed in friction stir welded AA2219-T8 joints. In this work, the effects of these agglomerated θ particles on the mechanical and corrosion properties of the joints are studied. Tensile testing with in situ SEM imaging was utilized to monitor crack initiation and propagation in base metal and weld nugget zone (WNZ) samples. These tests showed that cracks initiated in the θ particles and at the θ/matrix interfaces, but not in the matrix. The WNZ samples containing abnormal agglomerated θ particles had a similar ultimate tensile stress but 3 pct less elongation than other WNZ samples with only normal θ particles. Measurements using the microcell technique indicated that the agglomerated θ particles acted as a cathode causing the dissolution of adjacent matrix. The abnormal θ particle agglomerations led to more severe localized attack due to the large cathode/anode ratio. Al preferential dissolution occurred in the abnormal θ particle agglomerations, which was different from the corrosion behavior of normal size θ particles.

Characterization of a catalyst-based conversion technique to measure total particulate nitrogen and organic carbon and comparison to a particle mass measurement instrument

NASA Astrophysics Data System (ADS)

Stockwell, Chelsea E.; Kupc, Agnieszka; Witkowski, Bartłomiej; Talukdar, Ranajit K.; Liu, Yong; Selimovic, Vanessa; Zarzana, Kyle J.; Sekimoto, Kanako; Warneke, Carsten; Washenfelder, Rebecca A.; Yokelson, Robert J.; Middlebrook, Ann M.; Roberts, James M.

2018-05-01

The chemical composition of aerosol particles is a key aspect in determining their impact on the environment. For example, nitrogen-containing particles impact atmospheric chemistry, air quality, and ecological N deposition. Instruments that measure total reactive nitrogen (Nr = all nitrogen compounds except for N2 and N2O) focus on gas-phase nitrogen and very few studies directly discuss the instrument capacity to measure the mass of Nr-containing particles. Here, we investigate the mass quantification of particle-bound nitrogen using a custom Nr system that involves total conversion to nitric oxide (NO) across platinum and molybdenum catalysts followed by NO-O3 chemiluminescence detection. We evaluate the particle conversion of the Nr instrument by comparing to mass-derived concentrations of size-selected and counted ammonium sulfate ((NH4)2SO4), ammonium nitrate (NH4NO3), ammonium chloride (NH4Cl), sodium nitrate (NaNO3), and ammonium oxalate ((NH4)2C2O4) particles determined using instruments that measure particle number and size. These measurements demonstrate Nr-particle conversion across the Nr catalysts that is independent of particle size with 98 ± 10 % efficiency for 100-600 nm particle diameters. We also show efficient conversion of particle-phase organic carbon species to CO2 across the instrument's platinum catalyst followed by a nondispersive infrared (NDIR) CO2 detector. However, the application of this method to the atmosphere presents a challenge due to the small signal above background at high ambient levels of common gas-phase carbon compounds (e.g., CO2). We show the Nr system is an accurate particle mass measurement method and demonstrate its ability to calibrate particle mass measurement instrumentation using single-component, laboratory-generated, Nr-containing particles below 2.5 µm in size. In addition we show agreement with mass measurements of an independently calibrated online particle-into-liquid sampler directly coupled to the electrospray ionization source of a quadrupole mass spectrometer (PILS-ESI/MS) sampling in the negative-ion mode. We obtain excellent correlations (R2 = 0.99) of particle mass measured as Nr with PILS-ESI/MS measurements converted to the corresponding particle anion mass (e.g., nitrate, sulfate, and chloride). The Nr and PILS-ESI/MS are shown to agree to within ˜ 6 % for particle mass loadings of up to 120 µg m-3. Consideration of all the sources of error in the PILS-ESI/MS technique yields an overall uncertainty of ±20 % for these single-component particle streams. These results demonstrate the Nr system is a reliable direct particle mass measurement technique that differs from other particle instrument calibration techniques that rely on knowledge of particle size, shape, density, and refractive index.

Bimetallic Pt-Au Nanocatalysts on ZnO/Al2O3/Monolith for Air Pollution Control.

PubMed

Kim, Ki-Joong; Ahn, Ho-Geun

2015-08-01

The catalytic activity of a monolithic catalyst with nanosized Pt and Au particles on ZnO/Al2O3 (Pt-Au/ZnO/Al2O3/M) prepared by a wash-coat method was examined, specifically for toluene oxidation. Scanning electron microscopy image showed clearly the formation of a ZnO/Al2O3 layer on the monolith. Nanosized Pt-Au particles on ZnO/Al2O3/M with different sizes could be found in the Pt-Au/ZnO/Al2O3/M catalyst. The conversion of toluene decreased with increasing toluene concentration and was also largely affected by the feed flow rate. The Pt-Au/ZnO/Al2O3/M catalysts prepared in this work have almost the same activity (molecules of toluene per second) compared with a powder Pt-Au/ZnO/Al2O3 catalyst with the same loadings of Pt and Au components; thus this catalyst could be used in controlling air pollution with very low concentrations and high flow rate.

CuO/CeO2 catalysts for glycerol selective conversion to lactic acid.

PubMed

Palacio, Ruben; Torres, Sebastian; Royer, Sébastien; Mamede, Anne Sophie; López, Diana; Hernández, Diana

2018-03-26

Ceria supported copper oxide catalysts were produced by a deposition-precipitation method, at a high copper loading (up to >25 wt%). These materials demonstrated excellent properties for glycerol selective conversion to lactic acid, with a conversion reaching up to 87% with a selectivity to lactic acid of 74% (8 h reaction, 220 °C, under N2 pressure). These catalysts also exhibited high stability upon 5 successive reaction cycles. The formation of a crystalline CuO phase was demonstrated in the nanocomposites at a high Cu loading, with elongated shaped particles formed on the cerium oxide surface. Such particles were however, not observed at low Cu loadings. XPS analysis revealed that Cu(ii) was the main Cu species on the fresh catalyst, and that this species was reduced to Cu(i) during the reaction. Complementary characterization over the spent catalyst clearly showed the morphological modifications of the CuO phase, however, did not impact significantly either glycerol conversion or selectivity to lactic acid upon recycling. For instance, apparently, the catalytic activity of CuO largely depends on the Cu(ii) species.

The research of breaking rock with liquid-solid two-phase jet flow

NASA Astrophysics Data System (ADS)

Cheng, X. Z.; Ren, F. S.; Fang, T. C.

2018-03-01

Abstracts. Particle impact drilling is an efficient way of breaking rock, which is mainly used in deep drilling and ultra-deep drilling. The differential equation was established based on the theory of Hertz and Newton’s second law, through the analysis of particle impact rock, the depth of particles into the rock was obtained. The mathematical model was established based on the effect of water impact crack. The research results show when water jet speed is more than 40 m/s, rock stability coefficient is more than 1.0, the rock fracture appear. Through the experimental research of particle impact drilling facilities, analysis of cuttings and the crack size which was analyzed through Scanning electron microscope consistent with the theoretical calculation, the validity of the model was verified.

Using precipitated Cr on the surface of Cu-Cr alloy powders as catalyst synthesizing CNTs/Cu composite powders by water-assisted CVD

NASA Astrophysics Data System (ADS)

Zhou, Honglei; Liu, Ping; Chen, Xiaohong; Bi, Liming; Zhang, Ke; Liu, Xinkuan; Li, Wei; Ma, Fengcang

2018-02-01

Given that the conventional catalyst is easily soluble in the matrix to result in the poor performance of the CNTs/Cu composite materials, the Cr nano-particles precipitated on the surface of Cu-Cr particles are first used as catalysts to prepare the CNTs/Cu composite powders by means of water-assisted chemical vapor deposition in situ synthesis. The results show that the morphological difference of the precipitated Cr nano-particle is obvious with the change of solution and aging treatment, and the morphology, length and diameter of the synthetic CNTs are also different. The catalyst of Cr nano-particle has the best morphology and the synthesized CNTs had a good wettability with Cu particles when the Cu-Cr composite powders was solution-treated at 1023 K for 60 min and then was aged at 723 K for 120 min. The length, diameter, yield and purity of the synthesized CNTs can be also affected by the moisture content in the reaction gas. It is the most suitable for the growth of CNTs when the moisture content is 0.4%, and the high purity and defect-free CNTs with the smooth pipe wall, a diameter of 20 ˜ 30 nm and a length of up to 1800 nm can be obtained. The yield of CNTs with the moisture content of 0.4% reached to 138%, which was increased by 119% to compare with that without moisture. In this paper, a feasible technology was offered for the preparation of high performance CNTs/Cu composites.

An evaluation of the cost effectiveness of D-cracking preventive measures : research implementation plan.

DOT National Transportation Integrated Search

2006-12-07

Laboratory studies have found that reducing the particle size of D-cracking susceptible coarse aggregates will greatly : improve the durability of concrete exposed to freeze-thaw conditions. A test road located on State Route 2 near : Vermilion, Ohio...

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.

Effect of the nanostructure and the surface composition of bimetallic Ni-Ru nanoparticles on the performance of CO methanation

NASA Astrophysics Data System (ADS)

Wang, Jing; Yuan, Changkun; Yao, Nan; Li, Xiaonian

2018-05-01

The Ni/SiO2 catalysts with trace Ru promoter were prepared by either polyethylene glycol (PEG)-assisted or PEG-free impregnation method and were used in CO methanation reaction. The presence of PEG molecules was beneficial to form bimetallic Ni-Ru particles with smaller size, better anti-sintering property and low-temperature reducibility on SiO2 support than the conventional PEG-free derived NiRu/SiO2 catalyst. Moreover, it was found that the low-temperature reduction at 573 K was favorable to form bimetallic Ni-Ru particles with more surface Ru atoms. This nanostructure not only allowed the electron transfer happening from Ru0 to Ni0 which led to its higher electron cloud density, but also could reduce the deposition of less reactive carbon on the catalyst. Therefore, the low-temperature reduction enhanced the reaction stability of NiRu/SiO2 catalyst. The increase of reduction temperature from 573 K to 693 K did not change the size of metallic particles, but decreased the amount of surface Ru atoms. It deactivated the catalyst due to the deposition of more less reactive carbon. Although the higher reduction temperature (e.g. 693 and 793 K) was unfavorable to the reaction stability, it created more surface defects. The amount of defects showed a volcano-shaped correlation with the reduction temperature which was consistent with the variation tendency of turnover frequency of CO conversion. Consequently, it evidenced that the amount of surface Ru atoms and defects on the bimetallic Ni-Ru particle played the critical roles on the stability and the intrinsic activity of methanation, respectively.

The control of Pt and Ru nanoparticle size on high surface area supports.

PubMed

Liu, Qiuli; Joshi, Upendra A; Über, Kevin; Regalbuto, John R

2014-12-28

Supported Ru and Pt nanoparticles are synthesized by the method of strong electrostatic adsorption and subsequently treated under different steaming-reduction conditions to achieve a series of catalysts with controlled particle sizes, ranging from 1 to 8 nm. While in the case of oxidation-reduction conditions, only Pt yielded particles ranging from 2.5 to 8 nm in size and a loss of Ru was observed. Both Ru and Pt sinter faster in air than in hydrogen. This methodology allows the control of particle size using a "production-scalable" catalyst synthesis method which can be applied to high surface area supports with common metal precursors.

Development of highly active and stable hybrid cathode catalyst for PEMFCs

NASA Astrophysics Data System (ADS)

Jung, Won Suk

Polymer electrolyte membrane fuel cells (PEMFCs) are attractive power sources of the future for a variety of applications including portable electronics, stationary power, and automobile application. However, sluggish cathode kinetics, high Pt cost, and durability issues inhibit the commercialization of PEMFCs. To overcome these drawbacks, research has been focused on alloying Pt with transition metals since alloy catalysts show significantly improved catalytic properties like high activity, selectivity, and durability. However, Pt-alloy catalysts synthesized using the conventional impregnation method exhibit uneven particle size and poor particle distribution resulting in poor performance and/or durability in PEMFCs. In this dissertation, a novel catalyst synthesis methodology is developed and compared with catalysts prepared using impregnation method and commercial catalysts. Two approaches are investigated for the catalyst development. The catalyst durability was studied under U. S. DRIVE Fuel Cell Tech Team suggested protocols. In the first approach, the carbon composite catalyst (CCC) having active sites for oxygen reduction reaction (ORR) is employed as a support for the synthesis of Pt/CCC catalyst. The structural and electrochemical properties of Pt/CCC catalyst are investigated using high-resolution transmission electron microscopy, X-ray diffraction, and X-ray photoelectron spectroscopy, while RDE and fuel cell testing are carried out to study the electrochemical properties. The synergistic effect of CCC and Pt is confirmed by the observed high activity towards ORR for the Pt/CCC catalyst. The second approach is the synthesis of Co-doped hybrid cathode catalysts (Co-doped Pt/CCC) by diffusing the Co metal present within the CCC support into the Pt nanoparticles during heat-treatment. The optimized Co-doped Pt/CCC catalyst performed better than the commercial catalysts and the catalyst prepared using the impregnation method in PEMFCs and showed high stability under 30,000 potential cycles between 0.6 and 1.0 V. To further increase the stability of the catalyst at high potential cycles (1.0-1.5 V), high temperature treatment is used to obtain graphitized carbon having optimum BET surface area. The novel catalyst synthesis procedure developed in this study was successfully applied for the synthesis of Co-doped Pt catalysts supported on the graphitized carbon which showed high activity and enhanced stability at high potentials.

Morphological investigation of nanostructured CoMo catalysts

NASA Astrophysics Data System (ADS)

Pawelec, B.; Castaño, P.; Zepeda, T. A.

2008-04-01

This work reports the morphological investigation of nanostructured sulfided CoMo catalysts by means of high-resolution transmission electron microscopy (HRTEM). The catalysts were supported on Ti-modified hexagonal mesoporous silica (HMS-Ti) and P-modified HMS-Ti (P/HMS-Ti) materials. The oxide precursors were characterized by specific surface area (S BET), temperature-programmed reduction (TPR), diffuse reflectance infrared Fourier transform spectroscopy in the OH region (DRIFTS-OH) and X-ray photoelectron spectroscopy (XPS) in order to elucidate the influence of the impregnation sequence (successive vs. simultaneous) and the effect of P-incorporation into HMS-Ti material on the morphology of calcined CoMo catalysts. Both TPR and XPS measurements indicate that the catalysts prepared by successive impregnation possess well-dispersed MoO 3 and CoO phases, whereas their counterparts prepared by simultaneous impregnation additionally possess the CoMoO 4 phase. For all sulfided catalysts, the presence of MoS 2 phase with particle size in the range 3.3-4.4 nm was confirmed by HRTEM. Catalytic activity was evaluated in the reaction of hydrodesulfurization (HDS) of dibenzothiophene (DBT) carried out in a flow reactor at 593 K and hydrogen pressure of 5.5 MPa. P-incorporation into the HMS-Ti material led to an overall increase in HDS activity and the hydrogenation ability of the sulfided catalysts. All catalysts proved to be stable during 10 h time-on-stream (TOS) operation. The activity of sulfide catalysts in the target reaction depends linearly on the surface exposure of Co species in the oxide precursors, as determined by XPS, and on the morphology of the sulfide form of catalysts (surface density of MoS 2 particles and their sizes) as determined by HRTEM.

Plasma-catalyst hybrid reactor with CeO2/γ-Al2O3 for benzene decomposition with synergetic effect and nano particle by-product reduction.

PubMed

Mao, Lingai; Chen, Zhizong; Wu, Xinyue; Tang, Xiujuan; Yao, Shuiliang; Zhang, Xuming; Jiang, Boqiong; Han, Jingyi; Wu, Zuliang; Lu, Hao; Nozaki, Tomohiro

2018-04-05

A dielectric barrier discharge (DBD) catalyst hybrid reactor with CeO 2 /γ-Al 2 O 3 catalyst balls was investigated for benzene decomposition at atmospheric pressure and 30 °C. At an energy density of 37-40 J/L, benzene decomposition was as high as 92.5% when using the hybrid reactor with 5.0wt%CeO 2 /γ-Al 2 O 3 ; while it was 10%-20% when using a normal DBD reactor without a catalyst. Benzene decomposition using the hybrid reactor was almost the same as that using an O 3 catalyst reactor with the same CeO 2 /γ-Al 2 O 3 catalyst, indicating that O 3 plays a key role in the benzene decomposition. Fourier transform infrared spectroscopy analysis showed that O 3 adsorption on CeO 2 /γ-Al 2 O 3 promotes the production of adsorbed O 2 - and O 2 2‒ , which contribute benzene decomposition over heterogeneous catalysts. Nano particles as by-products (phenol and 1,4-benzoquinone) from benzene decomposition can be significantly reduced using the CeO 2 /γ-Al 2 O 3 catalyst. H 2 O inhibits benzene decomposition; however, it improves CO 2 selectivity. The deactivated CeO 2 /γ-Al 2 O 3 catalyst can be regenerated by performing discharges at 100 °C and 192-204 J/L. The decomposition mechanism of benzene over CeO 2 /γ-Al 2 O 3 catalyst was proposed. Copyright © 2017 Elsevier B.V. All rights reserved.

Optimizing the deposition of hydrogen evolution sites on suspended semiconductor particles using on-line photocatalytic reforming of aqueous methanol solutions.

PubMed

Busser, G Wilma; Mei, Bastian; Muhler, Martin

2012-11-01

The deposition of hydrogen evolution sites on photocatalysts is a crucial step in the multistep process of synthesizing a catalyst that is active for overall photocatalytic water splitting. An alternative approach to conventional photodeposition was developed, applying the photocatalytic reforming of aqueous methanol solutions to deposit metal particles on semiconductor materials such as Ga₂O₃ and (Ga₀.₆ Zn₀.₄)(N₀.₆O₀.₄). The method allows optimizing the loading of the co-catalysts based on the stepwise addition of their precursors and the continuous online monitoring of the evolved hydrogen. Moreover, a synergetic effect between different co-catalysts can be directly established. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis and reactivity of ultra-fine coal liquefaction catalysts

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

Linehan, J.C.; Matson, D.W.; Fulton, J.L.

1992-10-01

The Pacific Northwest Laboratory is currently developing ultra-fine iron-based coal liquefaction catalysts using two new particle production technologies: (1) modified reverse micelles (MRM) and (2) rapid thermal decomposition of solutes (RTDS). These methodologies have been shown to allow control over both particle size (from 1 nm to 60 nm) and composition when used to produce ultra-fine iron-based materials. Powders produced using these methods are found to be selective catalysts for carbon-carbon bond scission using the naphthyl bibenzylmethane model compound, and to promote the production of THF soluble coal products during liquefaction studies. This report describes the materials produced by bothmore » MRM and the RTDS methods and summarizes the results of preliminary catalysis studies using these materials.« less

Initial growth of vertically aligned carbon nanofibers

NASA Astrophysics Data System (ADS)

Cui, Hongtao; Yang, Xiaojing; Simpson, Michael L.; Lowndes, Douglas H.; Varela, Maria

2004-05-01

Samples of vertically aligned carbon nanofibers (VACNFs) were viewed transverse to the growth direction and studied using both scanning and transmission electron microscopy. The VACNFs are composed of graphite layers nearly parallel to the substrate at their bottom end, gradually formed graphite "cups" in the main body, and a catalyst particle on the tip. The formation of such structure is due to the corresponding transformation of the shape of the catalyst particle during initial VACNF growth. A model for their initial growth is proposed.

Process for recycling components of a PEM fuel cell membrane electrode assembly

DOEpatents

Shore, Lawrence [Edison, NJ

2012-02-28

The membrane electrode assembly (MEA) of a PEM fuel cell can be recycled by contacting the MEA with a lower alkyl alcohol solvent which separates the membrane from the anode and cathode layers of the assembly. The resulting solution containing both the polymer membrane and supported noble metal catalysts can be heated under mild conditions to disperse the polymer membrane as particles and the supported noble metal catalysts and polymer membrane particles separated by known filtration means.

The fractography-modeling link in cleavage fracture

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

Thompson, A.W.

1997-12-31

Cleavage fracture has historically been modelled, out of necessity, in rather idealized terms. In real materials, however, there are a number of difficulties in linking such models with metallographic and fractographic observations. Some of the most vivid examples occur for {alpha}{sub 2} titanium aluminide alloys, in which, when the microstructure contains primary {alpha}{sub 2} particles, the primary particles crack first. When basketweave or Widmanstaetten structures of {alpha}{sub 2} laths comprise the microstructure, it appears that individual laths crack first. And in colony structures, cracking occurs first across the {alpha}{sub 2} lath colonies. Both detailed fractographic observations, and also a statisticalmore » model for brittle fracture by failure of weakest links, have been developed. The extent to which this can be interpreted in classical cleavage terms will be discussed.« less

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

Cracking evolution behaviors of lightweight materials based on in situ synchrotron X-ray tomography: A review

NASA Astrophysics Data System (ADS)

Luo, Y.; Wu, S. C.; Hu, Y. N.; Fu, Y. N.

2018-03-01

Damage accumulation and failure behaviors are crucial concerns during the design and service of a critical component, leading researchers and engineers to thoroughly identifying the crack evolution. Third-generation synchrotron radiation X-ray computed microtomography can be used to detect the inner damage evolution of a large-density material or component. This paper provides a brief review of studying the crack initiation and propagation inside lightweight materials with advanced synchrotron three-dimensional (3D) X-ray imaging, such as aluminum materials. Various damage modes under both static and dynamic loading are elucidated for pure aluminum, aluminum alloy matrix, aluminum alloy metal matrix composite, and aluminum alloy welded joint. For aluminum alloy matrix, metallurgical defects (porosity, void, inclusion, precipitate, etc.) or artificial defects (notch, scratch, pit, etc.) strongly affect the crack initiation and propagation. For aluminum alloy metal matrix composites, the fracture occurs either from the particle debonding or voids at the particle/matrix interface, and the void evolution is closely related with fatigued cycles. For the hybrid laser welded aluminum alloy, fatigue cracks usually initiate from gas pores located at the surface or sub-surface and gradually propagate to a quarter ellipse or a typical semi-ellipse profile.

Effects of TiB2 Particle and Short Fiber Sizes on the Microstructure and Properties of TiB2-Reinforced Composite Coatings

NASA Astrophysics Data System (ADS)

Lin, Yinghua; Yao, Jianhua; Wang, Liang; Zhang, Qunli; Li, Xueqiao; Lei, Yongping; Fu, Hanguang

2018-03-01

In this study, particle and short fiber-reinforced titanium matrix composite coatings are prepared via laser in situ technique using (0.5 and 50 μm) TiB2 and Ti powder as cladding materials. The microstructure and properties of the composite coatings are studied, and the changing mechanism of the microstructure is discussed. The results reveal that particle agglomeration is prone to appear with using fine TiB2 particles. Decomposition of the particles preferentially occurs with using coarse TiB2 particles. The cracks and pores on the surface of the coating are formed at a lower laser energy density. With the increase in the laser energy density, cracking on the surface of the coating diminishes, but the coating exhibits depression behavior. The depression extent of the coating using fine TiB2 particle as the reinforcement is much less than that of the coating using coarse TiB2 particle. Moreover, the size of the aggregate and the tendency of cracking can be reduced with the increase in Ti addition. Meanwhile, short TiB fiber bundles are formed by the diffusion mechanism of rod aggregate, and randomly oriented TiB short fibers are formed mainly by the dissolution-precipitation mechanism of fine TiB2 particles. Moreover, the growth of short TiB fibers can be in an alternating manner between B27 and Bf structures. The micro-hardness and wear resistance of the coatings are evidently higher than that of the titanium alloy substrate. The wear resistance of the large size TiB2 coating is higher than that of the small size TiB2 coating under the condition of low load.

Ten-gram-scale preparation of PTMS-based monodisperse ORMOSIL nano- and microparticles and conversion to silica particles

NASA Astrophysics Data System (ADS)

Kim, Jung Soo; Jung, Gyu Il; Kim, Soo Jung; Koo, Sang Man

2018-03-01

Monodisperse organically modified silica (ORMOSIL) particles, with an average diameter ranging from 550 nm to 4.2 μm, were prepared at low temperature at a scale of about 10 g/batch by a simple one-step self-emulsion process. The reaction mixture was composed only of water, phenyltrimethoxysilane (PTMS), and a base catalyst, without any surfactants. The size control of the particles and the monodispersity of resultant particles were achieved through the controlled supply of hydrolyzed PTMS monomer molecules, which was enabled by manipulating the reaction parameters, such as monomer concentration, type and amount of base catalyst, stirring rate, and reaction temperature. PTMS-based ORMOSIL particles were converted into silica particles by employing either a wet chemical reaction with an oleum-sulfuric acid mixture or thermal treatment above 650 °C. Complete removal of organic groups from the ORMOSIL particles was achieved by the thermal treatment while 74% removal was done by the chemical process used. [Figure not available: see fulltext.

An Exploration of Geometric and Electronic Effects in Metal Nanoparticle Catalysts

NASA Astrophysics Data System (ADS)

Childers, David

The goal of this thesis is to investigate the influence geometric and electronic effects on metal nanoparticle catalysis. There are three main methods which alter a catalyst's properties: changing support material, changing nanoparticle size and alloying a second metal. This work will focus on the latter two methods using Pt-group metals and alloys. Platinum and palladium were chosen as the active metals due to a large amount of industry significance and prior literature to draw upon. Neopentane conversion and propane dehydrogenation were the two probe reactions used to evaluate these catalysts mainly due to their relative simplicity and ease of operation on a laboratory scale. The effect of particle size was studied with Pt and Pd monometallic catalysts using neopentane hydrogenolysis/isomerization as the probe reaction. Particle size studies have been done previously using this reaction so there is literature data to compare this study's results. This data will also be used as comparison for the bimetallic studies conducted later so that particle size effects can be accounted for when attempting to determine the effect of alloying a second metal. Bimetallic catalysts have several different possible structures depending on a number of factors from the identity of the two metals to the synthesis procedure. Homogeneous, core-shell and intermetallic alloys are the three structures evaluated in this work. Determining the surface composition of a homogeneous alloy can be difficult especially if both metals adsorb CO. PtPd homogeneous alloys were used to evaluate the ability of EXAFS to give information about surface composition using CO adsorption. These catalysts were also tested using neopentane conversion to evaluate changes in catalytic performance. Core-shell catalysts can also exhibit unique properties although it is not clear whether the identity of the core metal is relevant or if surface changes are most important to changing catalytic behavior. PdAu catalysts were synthesized with varying Pd loadings to determine if the Au-rich core would continue to influence neopentane conversion performance with increasing Pd layers on the surface of the nanoparticle. Finally, intermetallic alloys have produced some very interesting literature results and can drastically alter catalyst surface structure. PdZn showed the potential to improve neopentane isomerization selectivity past that of Pt based on calculated electronic properties. Two PdZn catalysts with different loadings were synthesized to evaluate the electronic and geometric effects using both neopentane conversion and propane dehydrogenation.

High-temperature catalyst for catalytic combustion and decomposition

NASA Technical Reports Server (NTRS)

Mays, Jeffrey A. (Inventor); Lohner, Kevin A. (Inventor); Sevener, Kathleen M. (Inventor); Jensen, Jeff J. (Inventor)

2005-01-01

A robust, high temperature mixed metal oxide catalyst for propellant composition, including high concentration hydrogen peroxide, and catalytic combustion, including methane air mixtures. The uses include target, space, and on-orbit propulsion systems and low-emission terrestrial power and gas generation. The catalyst system requires no special preheat apparatus or special sequencing to meet start-up requirements, enabling a fast overall response time. Start-up transients of less than 1 second have been demonstrated with catalyst bed and propellant temperatures as low as 50 degrees Fahrenheit. The catalyst system has consistently demonstrated high decomposition effeciency, extremely low decomposition roughness, and long operating life on multiple test particles.

The synergistic effect in the Fe-Co bimetallic catalyst system for the growth of carbon nanotube forests

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

Hardeman, D.; Esconjauregui, S., E-mail: cse28@cam.ac.uk; Cartwright, R.

2015-01-28

We report the growth of multi-walled carbon nanotube forests employing an active-active bimetallic Fe-Co catalyst. Using this catalyst system, we observe a synergistic effect by which—in comparison to pure Fe or Co—the height of the forests increases significantly. The homogeneity in the as-grown nanotubes is also improved. By both energy dispersive spectroscopy and in-situ x-ray photoelectron spectroscopy, we show that the catalyst particles consist of Fe and Co, and this dramatically increases the growth rate of the tubes. Bimetallic catalysts are thus potentially useful for synthesising nanotube forests more efficiently.

Relating structure and composition with accessibility of a single catalyst particle using correlative 3-dimensional micro-spectroscopy

DOE PAGES

Liu, Yijin; Meirer, Florian; Krest, Courtney M.; ...

2016-08-30

To understand how hierarchically structured functional materials operate, analytical tools are needed that can reveal small structural and chemical details in large sample volumes. Often, a single method alone is not sufficient to get a complete picture of processes happening at multiple length scales. Here we present a correlative approach combining three-dimensional X-ray imaging techniques at different length scales for the analysis of metal poisoning of an individual catalyst particle. The correlative nature of the data allowed establishing a macro-pore network model that interprets metal accumulations as a resistance to mass transport and can, by tuning the effect of metalmore » deposition, simulate the response of the network to a virtual ageing of the catalyst particle. In conclusion, the developed approach is generally applicable and provides an unprecedented view on dynamic changes in a material’s pore space, which is an essential factor in the rational design of functional porous materials.« less

n-Hexane conversion over supported Pt catalysts: Reply to Zoltan Paal

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

Sharma, S.B.; Dumesic, J.A.

In the accompanying letter to the Journal of Catalysis, Paal has questioned the findings and conclusions of the author`s recently published paper. It is important to stress that many of these conclusions are based on the combined interpretation of the data from the author`s recently published paper with results form spectroscopic and microcalorimetric studies of various supported platinum catalysts. In short, the authors have shown that highly dispersed, cluster-sized platinum particles supported in L-zeolite have the same heats of H{sub 2} and CO adsorption as larger platinum particles supported on silica; however, Pt/L-zeolite catalysts are more resistant to self-poisoning reactions,more » exhibit higher turnover frequencies, and show enhanced formation of benzene and methylcyclopentane (MCP) compared to larger particles of Pt supported on silica during n-hexane conversion at total pressures of 3 atm and hydrogen pressures near 276 kPa. 13 refs., 1 tab.« less

Numerical Investigation of the Ability of Salt Tracers to Represent the Residence Time Distribution of Fluidized Catalytic Cracking Particles

DOE PAGES

Lu, Liqiang; Gao, Xi; Li, Tingwen; ...

2017-11-02

For a long time, salt tracers have been used to measure the residence time distribution (RTD) of fluidized catalytic cracking (FCC) particles. However, due to limitations in experimental measurements and simulation methods, the ability of salt tracers to faithfully represent RTDs has never been directly investigated. Our current simulation results using coarse-grained computational fluid dynamic coupled with discrete element method (CFD-DEM) with filtered drag models show that the residence time of salt tracers with the same terminal velocity as FCC particles is slightly larger than that of FCC particles. This research also demonstrates the ability of filtered drag models tomore » predict the correct RTD curve for FCC particles while the homogeneous drag model may only be used in the dilute riser flow of Geldart type B particles. The RTD of large-scale reactors can then be efficiently investigated with our proposed numerical method as well as by using the old-fashioned salt tracer technology.« less

Surface treated carbon catalysts produced from waste tires for fatty acids to biofuel conversion

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

Hood, Zachary D.; Adhikari, Shiba P.; Wright, Marcus W.

A method of making solid acid catalysts includes the step of sulfonating waste tire pieces in a first sulfonation step. The sulfonated waste tire pieces are pyrolyzed to produce carbon composite pieces having a pore size less than 10 nm. The carbon composite pieces are then ground to produce carbon composite powders having a size less than 50 .mu.m. The carbon composite particles are sulfonated in a second sulfonation step to produce sulfonated solid acid catalysts. A method of making biofuels and solid acid catalysts are also disclosed.

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.

Oxidation of CO and Methanol on Pd-Ni Catalysts Supported on Different Chemically-Treated Carbon Nanofibers

PubMed Central

Calderón, Juan Carlos; Rios Ráfales, Miguel; Nieto-Monge, María Jesús; Pardo, Juan Ignacio; Moliner, Rafael; Lázaro, María Jesús

2016-01-01

In this work, palladium-nickel nanoparticles supported on carbon nanofibers were synthesized, with metal contents close to 25 wt % and Pd:Ni atomic ratios near to 1:2. These catalysts were previously studied in order to determine their activity toward the oxygen reduction reaction. Before the deposition of metals, the carbon nanofibers were chemically treated in order to generate oxygen and nitrogen groups on their surface. Transmission electron microscopy analysis (TEM) images revealed particle diameters between 3 and 4 nm, overcoming the sizes observed for the nanoparticles supported on carbon black (catalyst Pd-Ni CB 1:2). From the CO oxidation at different temperatures, the activation energy Eact for this reaction was determined. These values indicated a high tolerance of the catalysts toward the CO poisoning, especially in the case of the catalysts supported on the non-chemically treated carbon nanofibers. On the other hand, apparent activation energy Eap for the methanol oxidation was also determined finding—as a rate determining step—the COads diffusion to the OHads for the catalysts supported on carbon nanofibers. The results here presented showed that the surface functional groups only play a role in the obtaining of lower particle sizes, which is an important factor in the obtaining of low CO oxidation activation energies. PMID:28335315

Corrosion and Corrosion-Fatigue Behavior of 7075 Aluminum Alloys Studied by In Situ X-Ray Tomography

NASA Astrophysics Data System (ADS)

Stannard, Tyler

7XXX Aluminum alloys have high strength to weight ratio and low cost. They are used in many critical structural applications including automotive and aerospace components. These applications frequently subject the alloys to static and cyclic loading in service. Additionally, the alloys are often subjected to aggressive corrosive environments such as saltwater spray. These chemical and mechanical exposures have been known to cause premature failure in critical applications. Hence, the microstructural behavior of the alloys under combined chemical attack and mechanical loading must be characterized further. Most studies to date have analyzed the microstructure of the 7XXX alloys using two dimensional (2D) techniques. While 2D studies yield valuable insights about the properties of the alloys, they do not provide sufficiently accurate results because the microstructure is three dimensional and hence its response to external stimuli is also three dimensional (3D). Relevant features of the alloys include the grains, subgrains, intermetallic inclusion particles, and intermetallic precipitate particles. The effects of microstructural features on corrosion pitting and corrosion fatigue of aluminum alloys has primarily been studied using 2D techniques such as scanning electron microscopy (SEM) surface analysis along with post-mortem SEM fracture surface analysis to estimate the corrosion pit size and fatigue crack initiation site. These studies often limited the corrosion-fatigue testing to samples in air or specialized solutions, because samples tested in NaCl solution typically have fracture surfaces covered in corrosion product. Recent technological advancements allow observation of the microstructure, corrosion and crack behavior of aluminum alloys in solution in three dimensions over time (4D). In situ synchrotron X-Ray microtomography was used to analyze the corrosion and cracking behavior of the alloy in four dimensions to elucidate crack initiation at corrosion pits for samples of multiple aging conditions and impurity concentrations. Additionally, chemical reactions between the 3.5 wt% NaCl solution and the crack surfaces were quantified by observing the evolution of hydrogen bubbles from the crack. The effects of the impurity particles and age-hardening particles on the corrosion and fatigue properties were examined in 4D.

An XAS experimental approach to study low Pt content electrocatalysts operating in PEM fuel cells.

PubMed

Principi, Emiliano; Witkowska, Agnieszka; Dsoke, Sonia; Marassi, Roberto; Di Cicco, Andrea

2009-11-21

We present an X-ray absorption spectroscopy (XAS) study of a low Pt content catalyst layer (Pt loading 0.1 mg cm(-2)) operating at the cathode of a proton exchange membrane fuel cell (PEMFC). This catalyst is based on the use of a mesoporous inorganic matrix as a support for the catalyst Pt nanoparticles. Due to the high Pt dilution, in situ measurements of its structural properties by XAS are challenging and suitable experimental strategies must be devised for this purpose. In particular, we show that accurate XAS in situ fluorescence measurements can be obtained using an optimized fuel cell, suitable protocols for alignment of a focused X-ray beam and an appropriate filter for the background signal of the other atomic species contained in the electrodes. Details, advantages and limitations of the XAS technique for in situ measurements are discussed. Analysis of the near-edge XAS and EXAFS (extended X-ray absorption fine structure) data, corroborated by a HRTEM (high-resolution transmission electron microscopy) study, shows that the Pt particles have a local structure compatible with that of bulk Pt (fcc) and coordination numbers match those expected for particles with typical sizes in the 1.5-2.0 nm range. Substantial changes in the oxidation state and in local atomic arrangement of the Pt particles are found for different applied potentials. The catalyst support, containing W atoms, exhibits a partial reduction upon PEMFC activation, thus mimicking the catalyst behavior. This indicates a possible role of the mesoporous matrix in favouring the oxygen reduction reaction (ORR) and stimulates further research on active catalyst supports.

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.

Small-sized and contacting Pt-WC nanostructures on graphene as highly efficient anode catalysts for direct methanol fuel cells.

PubMed

Wang, Ruihong; Xie, Ying; Shi, Keying; Wang, Jianqiang; Tian, Chungui; Shen, Peikang; Fu, Honggang

2012-06-11

The synergistic effect between Pt and WC is beneficial for methanol electro-oxidation, and makes Pt-WC catalyst a promising anode candidate for the direct methanol fuel cell. This paper reports on the design and synthesis of small-sized and contacting Pt-WC nanostructures on graphene that bring the synergistic effect into full play. Firstly, DFT calculations show the existence of a strong covalent interaction between WC and graphene, which suggests great potential for anchoring WC on graphene with formation of small-sized, well-dispersed WC particles. The calculations also reveal that, when Pt attaches to the pre-existing WC/graphene hybrid, Pt particles preferentially grow on WC rather than graphene. Our experiments confirmed that highly disperse WC nanoparticles (ca. 5 nm) can indeed be anchored on graphene. Also, Pt particles 2-3 nm in size are well dispersed on WC/graphene hybrid and preferentially grow on WC grains, forming contacting Pt-WC nanostructures. These results are consistent with the theoretical findings. X-ray absorption fine structure spectroscopy further confirms the intimate contact between Pt and WC, and demonstrates that the presence of WC can facilitate the crystallinity of Pt particles. This new Pt-WC/graphene catalyst exhibits a high catalytic efficiency toward methanol oxidation, with a mass activity 1.98 and 4.52 times those of commercial PtRu/C and Pt/C catalysts, respectively. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Fatigue Analyses Under Constant- and Variable-Amplitude Loading Using Small-Crack Theory

NASA Technical Reports Server (NTRS)

Newman, J. C., Jr.; Phillips, E. P.; Everett, R. A., Jr.

1999-01-01

Studies on the growth of small cracks have led to the observation that fatigue life of many engineering materials is primarily "crack growth" from micro-structural features, such as inclusion particles, voids, slip-bands or from manufacturing defects. This paper reviews the capabilities of a plasticity-induced crack-closure model to predict fatigue lives of metallic materials using "small-crack theory" under various loading conditions. Constraint factors, to account for three-dimensional effects, were selected to correlate large-crack growth rate data as a function of the effective stress-intensity factor range (delta-Keff) under constant-amplitude loading. Modifications to the delta-Keff-rate relations in the near-threshold regime were needed to fit measured small-crack growth rate behavior. The model was then used to calculate small-and large-crack growth rates, and to predict total fatigue lives, for notched and un-notched specimens under constant-amplitude and spectrum loading. Fatigue lives were predicted using crack-growth relations and micro-structural features like those that initiated cracks in the fatigue specimens for most of the materials analyzed. Results from the tests and analyses agreed well.

The catalytic behavior of precisely synthesized Pt–Pd bimetallic catalysts for use as diesel oxidation catalysts

DOE PAGES

Wong, Andrew P.; Kyriakidou, Eleni A.; Toops, Todd J.; ...

2016-04-17

The demands of stricter diesel engine emission regulations have created challenges for current exhaust systems. With advances in low-temperature internal combustion engines and their operations, advances must also be made in vehicle exhaust catalysts. Most current diesel oxidation catalysts use heavy amounts of precious group metals (PGMs) for hydrocarbon (HC), CO, and NO oxidation. These catalysts are expensive and are most often synthesized with poor bimetallic interaction and dispersion. In this paper, the goal was to study the effect of aging on diesel emission abatement of Pt–Pd bimetallic nanoparticles precisely prepared with different morphologies: well dispersed core–shell vs. well dispersedmore » homogeneously alloyed vs. poorly dispersed, poorly alloyed particles. Alumina and silica supports were studied. Particle morphology and dispersion were analyzed before and after hydrothermal treatments by XRD, EDX, and STEM. Reactivity as a function of aging was measured in simulated diesel engine exhaust. While carefully controlled bimetallic catalyst nanoparticle structure has a profound influence on initial or low temperature catalytic activity, the differences in behavior disappear with higher temperature aging as thermodynamic equilibrium is achieved. The metallic character of Pt-rich alumina-supported catalysts is such that behavior rather closely follows the Pt–Pd metal phase diagram. Nanoparticles disparately composed as well-dispersed core–shell (via seq-SEA), well-dispersed homogeneously alloyed (via co-SEA), and poorly dispersed, poorly alloyed (via co-DI) end up as well alloyed, large particles of almost the same size and activity. With Pd-rich systems, the oxidation of Pd also figures into the equilibrium, such that Pd-rich oxide phases appear in the high temperature forms along with alloyed metal cores. Finally, the small differences in activity after high temperature aging can be attributed to the synthesis methods, sequential SEA and co-DI which give rise, after aging, to a bimetallic surface enriched in Pd.« less

Direct Simulations of Coupled Transport and Reaction on Nano-Scale X-Ray Computed Tomography Images of Platinum Group Metal-Free Catalyst Cathodes

DOE PAGES

Ogawa, S.; Komini Babu, S.; Chung, H. T.; ...

2016-08-22

The nano/micro-scale geometry of polymer electrolyte fuel cell (PEFC) catalyst layers critically affects cell performance. The small length scales and complex structure of these composite layers make it challenging to analyze cell performance and physics at the particle scale by experiment. We present a computational method to simulate transport and chemical reaction phenomena at the pore/particle-scale and apply it to a PEFC cathode with platinum group metal free (PGM-free) catalyst. Here, we numerically solve the governing equations for the physics with heterogeneous oxygen diffusion coefficient and proton conductivity evaluated using the actual electrode structure and ionomer distribution obtained using nano-scalemore » resolution X-ray computed tomography (nano-CT). Using this approach, the oxygen concentration and electrolyte potential distributions imposed by the oxygen reduction reaction are solved and the impact of the catalyst layer structure on performance is evaluated.« less

Population and hierarchy of active species in gold iron oxide catalysts for carbon monoxide oxidation

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

He, Qian; Freakley, Simon J.; Edwards, Jennifer K.

The identity of active species in supported gold catalysts for low temperature carbon monoxide oxidation remains an unsettled debate. With large amounts of experimental evidence supporting theories of either gold nanoparticles or sub-nm gold species being active, it was recently proposed that a size-dependent activity hierarchy should exist. Here we study the diverging catalytic behaviors after heat treatment of Au/FeO x materials prepared via co-precipitation and deposition precipitation methods. After ruling out any support effects, the gold particle size distributions in different catalysts are quantitatively studied using aberration corrected scanning transmission electron microscopy (STEM). A counting protocol is developed tomore » reveal the true particle size distribution from HAADF-STEM images, which reliably includes all the gold species present. As a result, correlation of the populations of the various gold species present with catalysis results demonstrate that a size-dependent activity hierarchy must exist in the Au/FeO x catalyst.« less

Population and hierarchy of active species in gold iron oxide catalysts for carbon monoxide oxidation

DOE PAGES

He, Qian; Freakley, Simon J.; Edwards, Jennifer K.; ...

2016-09-27

The identity of active species in supported gold catalysts for low temperature carbon monoxide oxidation remains an unsettled debate. With large amounts of experimental evidence supporting theories of either gold nanoparticles or sub-nm gold species being active, it was recently proposed that a size-dependent activity hierarchy should exist. Here we study the diverging catalytic behaviors after heat treatment of Au/FeO x materials prepared via co-precipitation and deposition precipitation methods. After ruling out any support effects, the gold particle size distributions in different catalysts are quantitatively studied using aberration corrected scanning transmission electron microscopy (STEM). A counting protocol is developed tomore » reveal the true particle size distribution from HAADF-STEM images, which reliably includes all the gold species present. As a result, correlation of the populations of the various gold species present with catalysis results demonstrate that a size-dependent activity hierarchy must exist in the Au/FeO x catalyst.« less

Direct Simulations of Coupled Transport and Reaction on Nano-Scale X-Ray Computed Tomography Images of Platinum Group Metal-Free Catalyst Cathodes

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

Ogawa, S.; Komini Babu, S.; Chung, H. T.

The nano/micro-scale geometry of polymer electrolyte fuel cell (PEFC) catalyst layers critically affects cell performance. The small length scales and complex structure of these composite layers make it challenging to analyze cell performance and physics at the particle scale by experiment. We present a computational method to simulate transport and chemical reaction phenomena at the pore/particle-scale and apply it to a PEFC cathode with platinum group metal free (PGM-free) catalyst. Here, we numerically solve the governing equations for the physics with heterogeneous oxygen diffusion coefficient and proton conductivity evaluated using the actual electrode structure and ionomer distribution obtained using nano-scalemore » resolution X-ray computed tomography (nano-CT). Using this approach, the oxygen concentration and electrolyte potential distributions imposed by the oxygen reduction reaction are solved and the impact of the catalyst layer structure on performance is evaluated.« less

Efficient hydrogen evolution by ternary molybdenum sulfoselenide particles on self-standing porous nickel diselenide foam

DOE PAGES

Zhou, Haiqing; Yu, Fang; Huang, Yufeng; ...

2016-09-16

With the massive consumption of fossil fuels and its detrimental impact on the environment, methods of generating clean power are urgent. Hydrogen is an ideal carrier for renewable energy; however, hydrogen generation is inefficient because of the lack of robust catalysts that are substantially cheaper than platinum. Therefore, robust and durable earth-abundant and cost-effective catalysts are desirable for hydrogen generation from water splitting via hydrogen evolution reaction. In this paper, we report an active and durable earth-abundant transition metal dichalcogenide-based hybrid catalyst that exhibits high hydrogen evolution activity approaching the state-of-the-art platinum catalysts, and superior to those of most transitionmore » metal dichalcogenides (molybdenum sulfide, cobalt diselenide and so on). Our material is fabricated by growing ternary molybdenum sulfoselenide particles on self-standing porous nickel diselenide foam. This advance provides a different pathway to design cheap, efficient and sizable hydrogen-evolving electrode by simultaneously tuning the number of catalytic edge sites, porosity, heteroatom doping and electrical conductivity.« less

Efficient hydrogen evolution by ternary molybdenum sulfoselenide particles on self-standing porous nickel diselenide foam

NASA Astrophysics Data System (ADS)

Zhou, Haiqing; Yu, Fang; Huang, Yufeng; Sun, Jingying; Zhu, Zhuan; Nielsen, Robert J.; He, Ran; Bao, Jiming; Goddard, William A., III; Chen, Shuo; Ren, Zhifeng

2016-09-01

With the massive consumption of fossil fuels and its detrimental impact on the environment, methods of generating clean power are urgent. Hydrogen is an ideal carrier for renewable energy; however, hydrogen generation is inefficient because of the lack of robust catalysts that are substantially cheaper than platinum. Therefore, robust and durable earth-abundant and cost-effective catalysts are desirable for hydrogen generation from water splitting via hydrogen evolution reaction. Here we report an active and durable earth-abundant transition metal dichalcogenide-based hybrid catalyst that exhibits high hydrogen evolution activity approaching the state-of-the-art platinum catalysts, and superior to those of most transition metal dichalcogenides (molybdenum sulfide, cobalt diselenide and so on). Our material is fabricated by growing ternary molybdenum sulfoselenide particles on self-standing porous nickel diselenide foam. This advance provides a different pathway to design cheap, efficient and sizable hydrogen-evolving electrode by simultaneously tuning the number of catalytic edge sites, porosity, heteroatom doping and electrical conductivity.

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

In-Situ X-ray Tomography Observation of Structure Evolution in 1,3,5-Triamino-2,4,6-Trinitrobenzene Based Polymer Bonded Explosive (TATB-PBX) under Thermo-Mechanical Loading.

PubMed

Yuan, Zeng-Nian; Chen, Hua; Li, Jing-Ming; Dai, Bin; Zhang, Wei-Bin

2018-05-04

In order to study the fracture behavior and structure evolution of 1,3,5-Triamino-2,4,6-Trinitrobenzene (TATB)-based polymer bonded explosive in thermal-mechanical loading, in-situ studies were performed on X-ray computed tomography system using quasi-static Brazilian test. The experiment temperature was set from −20 °C to 70 °C. Three-dimensional morphology of cracks at different temperatures was obtained through digital image process. The various fracture modes were compared by scanning electron microscopy. Fracture degree and complexity were defined to quantitatively characterize the different types of fractures. Fractal dimension was used to characterize the roughness of the crack surface. The displacement field of particles in polymer bonded explosive (PBX) was used to analyze the interior structure evolution during the process of thermal-mechanical loading. It was found that the brittleness of PBX reduced, the fracture got more tortuous, and the crack surface got smoother as the temperature rose. At lower temperatures, especially lower than glass transition temperature of binders, there were slipping and shear among particles, and particles tended to displace and disperse; while at higher temperatures, especially above the glass transition temperature of binders, there was reorganization of particles and particles tended to merge, disperse, and reduce sizes, rather than displacing.

Validation Testing of a Peridynamic Impact Damage Model Using NASA's Micro-Particle Gun

NASA Technical Reports Server (NTRS)

Baber, Forrest E.; Zelinski, Brian J.; Guven, Ibrahim; Gray, Perry

2017-01-01

Through a collaborative effort between the Virginia Commonwealth University and Raytheon, a peridynamic model for sand impact damage has been developed1-3. Model development has focused on simulating impacts of sand particles on ZnS traveling at velocities consistent with aircraft take-off and landing speeds. The model reproduces common features of impact damage including pit and radial cracks, and, under some conditions, lateral cracks. This study focuses on a preliminary validation exercise in which simulation results from the peridynamic model are compared to a limited experimental data set generated by NASA's recently developed micro-particle gun (MPG). The MPG facility measures the dimensions and incoming and rebound velocities of the impact particles. It also links each particle to a specific impact site and its associated damage. In this validation exercise parameters of the peridynamic model are adjusted to fit the experimentally observed pit diameter, average length of radial cracks and rebound velocities for 4 impacts of 300 µm glass beads on ZnS. Results indicate that a reasonable fit of these impact characteristics can be obtained by suitable adjustment of the peridynamic input parameters, demonstrating that the MPG can be used effectively as a validation tool for impact modeling and that the peridynamic sand impact model described herein possesses not only a qualitative but also a quantitative ability to simulate sand impact events.

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.

The effects of the catalytic converter and fuel sulfur level on motor vehicle particulate matter emissions: gasoline vehicles.

PubMed

Maricq, M Matti; Chase, Richard E; Xu, Ning; Podsiadlik, Diane H

2002-01-15

Scanning mobility and electrical low-pressure impactor particle size measurements conducted during chassis dynamometer testing reveal that neither the catalytic converter nor the fuel sulfur content has a significant effect on gasoline vehicle tailpipe particulate matter (PM) emissions. For current technology, port fuel injection, gasoline engines, particle number emissions are < or = 2 times higher from vehicles equipped with blank monoliths as compared to active catalysts, insignificant in contrast to the 90+% removal of hydrocarbons. PM mass emission rates derived from the size distributions are equal within the experimental uncertainty of 50-100%. Gravimetric measurements exhibit a 3-10-fold PM mass increase when the active catalyst is omitted, which is attributed to gaseous hydrocarbons adsorbing onto the filter medium. Both particle number and gravimetric measurements show that gasoline vehicle tailpipe PM emissions are independent (within 2 mg/mi) of fuel sulfur content over the 30-990 ppm concentration range. Nuclei mode sulfate aerosol is not observed in either test cell measurements or during wind tunnel testing. For three-way catalyst equipped vehicles, the principal sulfur emission is SO2; however a sulfur balance is not obtained over the drive cycle. Instead, sulfur is stored on the catalyst during moderate driving and then partially removed during high speed/load operation.

Synthesis of platinum nanoparticle electrocatalysts by atomic layer deposition

NASA Astrophysics Data System (ADS)

Lubers, Alia Marie

Demand for energy continues to increase, and without alternatives to fossil fuel combustion the effects on our environment will become increasingly severe. Fuel cells offer a promising improvement on current methods of energy generation; they are able to convert hydrogen fuel into electricity with a theoretical efficiency of up to 83% and interface smoothly with renewable hydrogen production. Fuel cells can replace internal combustion engines in vehicles and are used in stationary applications to power homes and businesses. The efficiency of a fuel cell is maximized by its catalyst, which is often composed of platinum nanoparticles supported on carbon. Economical production of fuel cell catalysts will promote adoption of this technology. Atomic layer deposition (ALD) is a possible method for producing catalysts at a large scale when employed in a fluidized bed. ALD relies on sequential dosing of gas-phase precursors to grow a material layer by layer. We have synthesized platinum nanoparticles on a carbon particle support (Pt/C) by ALD for use in proton exchange membrane fuel cells (PEMFCs) and electrochemical hydrogen pumps. Platinum nanoparticles with different characteristics were deposited by changing two chemistries: the carbon substrate through functionalization; and the deposition process by use of either oxygen or hydrogen as ligand removing reactants. The metal depositing reactant was trimethyl(methylcyclopentadienyl)platinum(IV). Functionalizing the carbon substrate increased nucleation during deposition resulting in smaller and more dispersed nanoparticles. Use of hydrogen produced smaller nanoparticles than oxygen, due to a gentler hydrogenation reaction compared to using oxygen's destructive combustion reaction. Synthesized Pt/C materials were used as catalysts in an electrochemical hydrogen pump, a device used to separate hydrogen fuel from contaminants. Catalysts deposited by ALD on functionalized carbon using a hydrogen chemistry were the most successful hydrogen pumping catalysts, comparable to a commercial Pt/C catalyst. Synthesized Pt/C materials were also used as PEMFC catalysts. We found the ALD catalysts with lower platinum loading to be competitive with a commercial fuel cell catalyst, especially when exhibiting similar platinum particle characteristics. The functionalized carbon helped produce smaller and more dispersed platinum particles; however, it encouraged carbon corrosion within an electrode, severing electrical connections and lowering energy production. The most suitable chemistry for competitive Pt/C catalysts was produced by platinum ALD on unmodified carbon using hydrogen as a reactant. ALD is a promising method for fabricating electrocatalysts, which could help fuel cells become an economically viable alternative to fossil fuels.

Effect of raw soya bean particle size on productive performance and digestion of dairy cows.

PubMed

Naves, A B; Freitas Júnior, J E; Barletta, R V; Gandra, J R; Calomeni, G D; Gardinal, R; Takiya, C S; Vendramini, T H A; Mingoti, R D; Rennó, F P

2016-08-01

Differing soya bean particle sizes may affect productive performance and ruminal fermentation due to the level of fatty acid (FA) exposure of the cotyledon in soya bean grain and because the protein in small particles is more rapidly degraded than the protein in large particles, which influence ruminal fibre digestion and the amounts of ruminally undegradable nutrients. The objective of this experiment was to investigate the effects of raw soya bean particle size on productive performance, digestion and milk FA profile of dairy cows. Twelve Holstein cows were assigned to three 4 × 4 Latin squares with 21-day periods. At the start of the experiment, cows were 121 days in milk (DIM) and yielded 30.2 kg/day of milk. Cows were fed 4 diets: (i) control diet (CO), without raw soya bean; (ii) whole raw soya bean (WRS); (iii) cracked raw soya bean in Wiley mill 4-mm screen (CS4); and (iv) cracked raw soya bean in Wiley mill 2-mm screen (CS2). The inclusion of soya beans (whole or cracked) was 200 g/kg on dry matter (DM) basis and partially replaced ground corn and soya bean meal. Uncorrected milk yield and composition were not influenced by experimental diets; however, fat-corrected milk (FCM) decreased when cows were fed soya bean treatments. Soya bean diets increased the intake of ether extract (EE) and net energy of lactation (NEL ), and decreased the intake of DM and non-fibre carbohydrate (NFC). Ruminal propionate concentration was lower in cows fed WRS than cows fed CS2 or CS4. Cows fed cracked raw soya bean presented lower nitrogen in faeces than cows fed WRS. The milk of cows fed WRS, CS2 and CS4 presented higher unsaturated FA than cows fed CO. The addition of raw soya bean in cow diets, regardless of the particle size, did not impair uncorrected milk yield and nutrient digestion, and increased the concentration of unsaturated FA in milk. Cows fed cracked raw soya bean presented similar productive performance to cows fed whole raw soya bean. Journal of Animal Physiology and Animal Nutrition © 2015 Blackwell Verlag GmbH.

Thermal and photo-thermal PROX reaction over Ag/SiO2 catalysts

NASA Astrophysics Data System (ADS)

Sabinas-Hernández, S. A.; Romero-Núñez, A.; Díaz, G.

2018-02-01

The effect of plasmonic excitation of Ag/SiO2 catalysts was studied in the preferential CO oxidation in presence of H2 (PROX) at low temperature. Catalysts with 5 wt% silver loading were prepared by wet impregnation in aqueous and basic media. TEM analysis indicates the presence of Ag nanoparticles with a broad particle size distribution which can achieve both, good PROX activity at low temperature and plasmonic interaction with visible light. Photo-assisted reaction at 35 °C enhance CO and O2 conversions; however, the greater improvement was found for O2 conversion. The selectivity towards CO2 decrease when reaction took place under photo-thermal conditions. Occurrence of different silver species and particle size changed after reaction as evidenced by DRS-UV-vis and TEM.

Use of manganese oxide and activated carbon fibers for removing a particle, volatile organic compound or ozone from a gas

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

Sidheswaran, Meera A.; Destaillats, Hugo; Fisk, William J.

The present invention provides for a device for reducing a volatile organic compound (VOC) content of a gas comprising a manganese oxide (MnO.sub.x) catalyst. The manganese oxide (MnO.sub.x) catalyst is capable of catalyzing formaldehyde at room temperature, with complete conversion, to CO.sub.2 and water vapor. The manganese oxide (MnO.sub.x) catalyst itself is not consumed by the reaction of formaldehyde into CO.sub.2 and water vapor. The present invention also provides for a device for reducing or removing a particle, a VOC and/or ozone from a gas comprising an activated carbon filter (ACF) on a media that is capable of being periodicallymore » regenerated.« less

Predictions and Experimental Microstructural Characterization of High Strain Rate Failure Modes in Layered Aluminum Composites

NASA Astrophysics Data System (ADS)

Khanikar, Prasenjit

Different aluminum alloys can be combined, as composites, for tailored dynamic applications. Most investigations pertaining to metallic alloy layered composites, however, have been based on quasi-static approaches. The dynamic failure of layered metallic composites, therefore, needs to be characterized in terms of strength, toughness, and fracture response. A dislocation-density based crystalline plasticity formulation, finite-element techniques, rational crystallographic orientation relations and a new fracture methodology were used to predict the failure modes associated with the high strain rate behavior of aluminum layered composites. Two alloy layers, a high strength alloy, aluminum 2195, and an aluminum alloy 2139, with high toughness, were modeled with representative microstructures that included precipitates, dispersed particles, and different grain boundary (GB) distributions. The new fracture methodology, based on an overlap method and phantom nodes, is used with a fracture criteria specialized for fracture on different cleavage planes. One of the objectives of this investigation, therefore, was to determine the optimal arrangements of the 2139 and 2195 aluminum alloys for a metallic layered composite that would combine strength, toughness and fracture resistance for high strain-rate applications. Different layer arrangements were investigated for high strain-rate applications, and the optimal arrangement was with the high toughness 2139 layer on the bottom, which provided extensive shear strain localization, and the high strength 2195 layer on the top for high strength resistance. The layer thickness of the bottom high toughness layer also affected the bending behavior of the roll-boned interface and the potential delamination of the layers. Shear strain localization, dynamic cracking and delamination were the mutually competing failure mechanisms for the layered metallic composite, and control of these failure modes can be optimized for high strain-rate applications. The second major objective of this investigation was the use of recently developed dynamic fracture formulations to model and analyze the crack nucleation and propagation of aluminum layered composites subjected to high strain rate loading conditions and how microstructural effects, such as precipitates, dispersed particles, and GB orientations affect failure evolution. This dynamic fracture approach is used to investigate crack nucleation and crack growth as a function of the different microstructural characteristics of each alloy in layered composites with and without pre-existing cracks. The zigzag nature of the crack paths were mainly due to the microstructural features, such as precipitates and dispersed particles distributions and orientations ahead of the crack front, and it underscored the capabilities of the fracture methodology. The evolution of dislocation density and the formation of localized shear slip contributed to the blunting of the propagating crack. Extensive geometrical and thermal softening due to the localized plastic slip also affected crack path orientations and directions. These softening mechanisms resulted in the switching of cleavage planes, which affected crack path orientations. Interface delamination can also have an important role in the failure and toughening of the layered composites. Different scenarios of delamination were investigated, such as planar crack growth and crack penetration into the layers. The presence of brittle surface oxide platelets in the interface region also significantly influenced the interface delamination process. Transmission Electron Microscopy (TEM), Scanning Electron Microscopy (SEM) and Optical Microscopy (OM) characterization provided further physical insights and validation of the predictive capabilities. The inherent microstructural features of each alloy play a significant role in the dynamic fracture, shear strain localization, and interface delamination of the layered metallic composite. These microstructural features, such as precipitates, dispersed particles, and GB orientations and distributions can be optimized for desired behavior of metallic composites.

Investigating the Catalytic Growth of Carbon Nanotubes with In Situ Raman Monitoring

DTIC Science & Technology

2015-06-01

single-walled carbon nanotube growth using cobalt deposited on Si/SiO2 as a model system. In situ Raman studies revealed that thin catalyst layers... cobalt thickness were studied. Surface analyses showed that during the catalyst preparation, catalyst atoms at the interface with silica form small...nanostructures. However, highly-reducing conditions are required to reduce the small silicate domains into small cobalt particles able to grow single-walled

Investigation of the plastic fracture of high-strength aluminum alloys

NASA Technical Reports Server (NTRS)

Van Stone, R. H.; Merchant, R. H.; Low, J. R., Jr.

1974-01-01

In a study of plastic fracture in five high-strength aluminum alloys (2014, 2024, 2124, 7075, and 7079), it has been shown that fracture toughness is affected primarily by the size and volume fraction of the larger (2 to 10 microms) second-phase particles. Certain of these particles crack at small plastic strains, nucleating voids which, with further plastic strain, coalesce to cause fracture. Not all second-phase particles crack at small plastic strains, and qualitative analysis of those which are primarily responsible for void nucleation shows that they contain iron or silicon or both. This result suggests that a reduction in the iron and silicon impurity content of the alloys should improve fracture toughness without loss of strength.

76 FR 18865 - Airworthiness Directives; Bell Helicopter Textron, Inc. Model 212 Helicopters

Federal Register 2010, 2011, 2012, 2013, 2014

2011-04-06

... also requires performing a magnetic particle inspection (MPI) on fittings with certain serial numbers... expanding the applicability to require performing a magnetic particle inspection (MPI) for a crack on the...

Particle size of wheat, maize, and oat test meals: effects on plasma glucose and insulin responses and on the rate of starch digestion in vitro.

PubMed

Heaton, K W; Marcus, S N; Emmett, P M; Bolton, C H

1988-04-01

When normal volunteers ate isocaloric wheat-based meals, their plasma insulin responses (peak concentration and area under curve) increased stepwise: whole grains less than cracked grains less than coarse flour less than fine flour. Insulin responses were also greater with fine maizemeal than with whole or cracked maize grains but were similar with whole groats, rolled oats, and fine oatmeal. The peak-to-nadir swing of plasma glucose was greater with wheat flour than with cracked or whole grains. In vitro starch hydrolysis by pancreatic amylase was faster with decreasing particle size with all three cereals. Correlation with the in vivo data was imperfect. Oat-based meals evoked smaller glucose and insulin responses than wheat- or maize-based meals. Particle size influences the digestion rate and consequent metabolic effects of wheat and maize but not oats. The increased insulin response to finely ground flour may be relevant to the etiology of diseases associated with hyperinsulinemia and to the management of diabetes.

Selective hydrodeoxygenation of cyclic vicinal diols to cyclic alcohols over tungsten oxide-palladium catalysts.

PubMed

Amada, Yasushi; Ota, Nobuhiko; Tamura, Masazumi; Nakagawa, Yoshinao; Tomishige, Keiichi

2014-08-01

Hydrodeoxygenation of cyclic vicinal diols such as 1,4-anhydroerythritol was conducted over catalysts containing both a noble metal and a group 5-7 transition-metal oxide. The combination of Pd and WOx allowed the removal of one of the two OH groups selectively. 3-Hydroxytetrahydrofuran was obtained from 1,4-anhydroerythritol in 72 and 74% yield over WOx -Pd/C and WOx -Pd/ZrO2 , respectively. The WOx -Pd/ZrO2 catalyst was reusable without significant loss of activity if the catalyst was calcined as a method of regeneration. Characterization of WOx -Pd/C with temperature-programmed reduction, X-ray diffraction, and transmission electron microscopy/energy-dispersive X-ray spectroscopy suggested that Pd metal particles approximately 9 nm in size were formed on amorphous tungsten oxide particles. A reaction mechanism was proposed on the basis of kinetics, reaction results with tungsten oxides under an atmosphere of Ar, and density functional theory calculations. A tetravalent tungsten center (W(IV) ) was formed by reduction of WO3 with the Pd catalyst and H2 , and this center served as the reductant for partial hydrodeoxygenation. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Characteristics of back corona discharge in a honeycomb catalyst and its application for treatment of volatile organic compounds.

PubMed

Feng, Fada; Zheng, Yanyan; Shen, Xinjun; Zheng, Qinzhen; Dai, Shaolong; Zhang, Xuming; Huang, Yifan; Liu, Zhen; Yan, Keping

2015-06-02

The main technical challenges for the treatment of volatile organic compounds (VOCs) with plasma-assisted catalysis in industrial applications are large volume plasma generation under atmospheric pressure, byproduct control, and aerosol collection. To solve these problems, a back corona discharge (BCD) configuration has been designed to evenly generate nonthermal plasma in a honeycomb catalyst. Voltage-current curves, discharge images, and emission spectra have been used to characterize the plasma. Grade particle collection results and flow field visualization in the discharge zones show not only that the particles can be collected efficiently, but also that the pressure drop of the catalyst layer is relatively low. A three-stage plasma-assisted catalysis system, comprising a dielectric barrier discharge (DBD) stage, BCD stage, and catalyst stage, was built to evaluate toluene treatment performance by BCD. The ozone analysis results indicate that BCD enhances the ozone decomposition by collecting aerosols and protecting the Ag-Mn-O catalyst downstream from aerosol contamination. The GC and FTIR results show that BCD contributes to toluene removal, especially when the specific energy input is low, and the total removal efficiency reaches almost 100%. Furthermore, this removal results in the emission of fewer byproducts.

Hydrogen production from steam reforming of ethylene glycol over iron loaded on MgO

NASA Astrophysics Data System (ADS)

Chen, Mingqiang; Wang, Yishuang; Liang, Tian; Yang, Jie; Yang, Zhonglian

2017-01-01

In this study, a series of Fe-based catalysts loaded on MgO were prepared by a precipitation technique. And they were tested in hydrogen production from steam reforming of ethylene glycol (SRE), which was a representative model compound of fast bio-oil. The catalysts were characterized by XRD, SEM and H2-TPR analysis. The results showed that the crystalline phases of catalysts contained Fe2O3 (Hematite), Fe3O4 (Magnetite), Fe2MgO4 (iron magnesium oxide) and MgO, and morphology of MgO was changed from the rugby-ball like particles to spherical particles with the addition of Fe. In addition, the catalytic test results indicated that the 18%Fe/MgO catalyst exhibited the highest ethylene glycol conversion (˜99.8%) and H2 molar percent (˜77%) during at the following conditions: H2O/C molar ratio is 5˜7, the feeding rate is 14 mL/h and the reaction temperature at 600˜650°C. Furthermore, the 18%Fe/MgO catalyst can keep outstanding stability during SRE for 12 h.

Comparison of non-catalytic and catalytic fast pyrolysis of corncob in a fluidized bed reactor.

PubMed

Zhang, Huiyan; Xiao, Rui; Huang, He; Xiao, Gang

2009-02-01

Fast pyrolysis of corncob with and without catalyst was investigated in a fluidized bed to determine the effects of pyrolysis parameters (temperature, gas flow rate, static bed height and particle size) and a HZSM-5 zeolite catalyst on the product yields and the qualities of the liquid products. The result showed that the optimal conditions for liquid yield (56.8%) were a pyrolysis temperature of 550 degrees C, gas flow rate of 3.4 L/min, static bed height of 10 cm and particle size of 1.0-2.0mm. The presence of the catalyst increased the yields of non-condensable gas, water and coke, while decreased the liquid and char yields. The elemental analysis showed that more than 25% decrease in oxygen content of the collected liquid in the second condenser with HZSM-5 was observed compared with that without catalyst. The H/C, O/C molar ratios and the higher heating value of the oil fraction in the collected liquid with the catalyst were 1.511, 0.149 and 34.6 MJ/kg, respectively. It was indicated that the collected liquid in the second condenser had high qualities and might be used as transport oil.

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

A statistical model of brittle fracture by transgranular cleavage

NASA Astrophysics Data System (ADS)

Lin, Tsann; Evans, A. G.; Ritchie, R. O.

A MODEL for brittle fracture by transgranular cleavage cracking is presented based on the application of weakest link statistics to the critical microstructural fracture mechanisms. The model permits prediction of the macroscopic fracture toughness, KI c, in single phase microstructures containing a known distribution of particles, and defines the critical distance from the crack tip at which the initial cracking event is most probable. The model is developed for unstable fracture ahead of a sharp crack considering both linear elastic and nonlinear elastic ("elastic/plastic") crack tip stress fields. Predictions are evaluated by comparison with experimental results on the low temperature flow and fracture behavior of a low carbon mild steel with a simple ferrite/grain boundary carbide microstructure.

Vapor phase hydrogenation of furfural over nickel mixed metal oxide catalysts derived from layered double hydroxides

DOE PAGES

Sulmonetti, Taylor P.; Pang, Simon H.; Claure, Micaela Taborga; ...

2016-03-09

The hydrogenation of furfural is investigated over various reduced nickel mixed metal oxides derived from layered double hydroxides (LDHs) containing Ni-Mg-Al and Ni-Co-Al. Upon reduction, relatively large Ni(0) domains develop in the Ni-Mg-Al catalysts, whereas in the Ni-Co-Al catalysts smaller metal particles of Ni(0) and Co(0), potentially as alloys, are formed, as evidenced by XAS, XPS, STEM and EELS. All the reduced Ni catalysts display similar selectivities towards major hydrogenation products (furfuryl alcohol and tetrahydrofurfuryl alcohol), though the side products varied with the catalyst composition. The 1.1Ni-0.8Co-Al catalyst showed the greatest activity per titrated site when compared to the othermore » catalysts, with promising activity compared to related catalysts in the literature. In conclusion, the use of base metal catalysts for hydrogenation of furanic compounds may be a promising alternative to the well-studied precious metal catalysts for making biomass-derived chemicals if catalyst selectivity can be improved in future work by alloying or tuning metal-oxide support interactions.« less

Vapor phase hydrogenation of furfural over nickel mixed metal oxide catalysts derived from layered double hydroxides

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

Sulmonetti, Taylor P.; Pang, Simon H.; Claure, Micaela Taborga

2016-05-01

The hydrogenation of furfural is investigated over various reduced nickel mixed metal oxides derived from layered double hydroxides (LDHs) containing Ni-Mg-Al and Ni-Co-Al. Upon reduction, relatively large Ni(0) domains develop in the Ni-Mg-Al catalysts, whereas in the Ni-Co-Al catalysts smaller metal particles of Ni(0) and Co(0), potentially as alloys, are formed, as evidenced by XAS, XPS, STEM and EELS. All the reduced Ni catalysts display similar selectivities towards major hydrogenation products (furfuryl alcohol and tetrahydrofurfuryl alcohol), though the side products varied with the catalyst composition. The 1.1Ni-0.8Co-Al catalyst showed the greatest activity per titrated site when compared to the othermore » catalysts, with promising activity compared to related catalysts in the literature. The use of base metal catalysts for hydrogenation of furanic compounds may be a promising alternative to the well-studied precious metal catalysts for making biomass-derived chemicals if catalyst selectivity can be improved in future work by alloying or tuning metal-oxide support interactions.« less

Effect of advanced aftertreatment for PM and NOx reduction on heavy-duty diesel engine ultrafine particle emissions.

PubMed

Herner, Jorn Dinh; Hu, Shaohua; Robertson, William H; Huai, Tao; Chang, M-C Oliver; Rieger, Paul; Ayala, Alberto

2011-03-15

Four heavy-duty and medium-duty diesel vehicles were tested in six different aftertreament configurations using a chassis dynamometer to characterize the occurrence of nucleation (the conversion of exhaust gases to particles upon dilution). The aftertreatment included four different diesel particulate filters and two selective catalytic reduction (SCR) devices. All DPFs reduced the emissions of solid particles by several orders of magnitude, but in certain cases the occurrence of a volatile nucleation mode could increase total particle number emissions. The occurrence of a nucleation mode could be predicted based on the level of catalyst in the aftertreatment, the prevailing temperature in the aftertreatment, and the age of the aftertreatment. The particles measured during nucleation had a high fraction of sulfate, up to 62% of reconstructed mass. Additionally the catalyst reduced the toxicity measured in chemical and cellular assays suggesting a pathway for an inverse correlation between particle number and toxicity. The results have implications for exposure to and toxicity of diesel PM.

Tracking the shape-dependent sintering of platinum-rhodium model catalysts under operando conditions

NASA Astrophysics Data System (ADS)

Hejral, Uta; Müller, Patrick; Balmes, Olivier; Pontoni, Diego; Stierle, Andreas

2016-03-01

Nanoparticle sintering during catalytic reactions is a major cause for catalyst deactivation. Understanding its atomic-scale processes and finding strategies to reduce it is of paramount scientific and economic interest. Here, we report on the composition-dependent three-dimensional restructuring of epitaxial platinum-rhodium alloy nanoparticles on alumina during carbon monoxide oxidation at 550 K and near-atmospheric pressures employing in situ high-energy grazing incidence x-ray diffraction, online mass spectrometry and a combinatorial sample design. For platinum-rich particles our results disclose a dramatic reaction-induced height increase, accompanied by a corresponding reduction of the total particle surface coverage. We find this restructuring to be progressively reduced for particles with increasing rhodium composition. We explain our observations by a carbon monoxide oxidation promoted non-classical Ostwald ripening process during which smaller particles are destabilized by the heat of reaction. Its driving force lies in the initial particle shape which features for platinum-rich particles a kinetically stabilized, low aspect ratio.

Ultrasound-assisted Micro-emulsion Synthesis of a Highly Active Nano-particle Catalyst

DTIC Science & Technology

2010-03-01

saturated calomel electrode [SCE]). 15. SUBJECT TERMS Microemulsion synthesis, Nano particles, Catalysts, Ultrasound, Oxygen reduction, Rotating disk...30 40 50 60 ω1/2 (rpm 1/2) i ( m A .c m -2 ) Ultrasound Assisted Microemulsion Microemulsion non- Microemulsion O2 4e Redc by Diff. Figure 17. Levich...2.0 2.4 0 0.02 0.04 0.06 0.08 0.1 0.12 ω-1/2(rpm-1/2) i-1 (m A -1 cm 2 ) non- Microemulsion Microemulsion Ultrasound Assisted Microemulsion O2 4-e Redc

Hydrodeoxygenation of phenol over zirconia supported Pd bimetallic catalysts. The effect of second metal on catalyst performance

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

Resende, Karen A.; Teles, Camila A.; Jacobs, Gary

Here, this work investigated the effect of the addition of a second metal (Cu, Ag, Zn, Sn) on the performance of Pd/ZrO 2 catalyst for HDO of phenol at 573 K in the gas phase. The incorporation of dopants resulted in the formation of Pd–X (Cu, Ag, Zn) alloys, which reduced the reaction rate for HDO and increased the selectivity to hydrogenation products (cyclohexanone and cyclohexanol). The lower activity of the bimetallic catalysts was due to the segregation of the second metal on the surface of the Pd particle. For PdSn/ZrO 2, alloying was also observed but tin oxide wasmore » still present on the surface after reduction at 773 K. For Pd and PdSn/ZrO 2, the oxophilic sites represented by Zr and Sn cations promotes the hydrogenation of the carbonyl group of the keto-tautomer intermediate formed, producing benzene as the main product. All catalysts significantly deactivated during the reaction but the deactivation degree depended on the type of the metal. Pd/ZrO 2 and PdZn/ZrO 2 and PdAg/ZrO 2 exhibited approximately the same deactivation degree. However, the loss of activity was less pronounced for PdSn/ZrO2 catalyst. Finally, Pd dispersion significantly decreased during the reaction, indicating that the sintering of Pd particles is one of the causes for catalyst deactivation.« less

Impact of initial catalyst form on the 3D structure and performance of ball-milled Ni-catalyzed MgH 2 for hydrogen storage

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

House, Stephen D.; Vajo, John J.; Ren, Chai

Although it has been shown that the hydrogen storage kinetics of metal hydrides can be significantly improved by the addition of transition metal-based catalysts, relatively little attention has been paid to the impact that the form in which these catalysts are introduced during synthesis has on the resulting structure and how this alters performance. Two mixtures of MgH 2 doped with Ni were prepared via high-energy ball-milling under identical conditions, one using a pure Ni nanopowder catalyst and the other using anhydrous NiCl 2. The resulting Ni catalyst particles of the NiCl 2-doped material were 10-100 times smaller, as wellmore » as more uniform in size and shape. Electron tomography revealed that the additive form also altered its incorporation and 3D spatial distribution, with Ni particles limited to the outer surface in the NiCl 2-doped case. The significantly lower desorption performance measured in the NiCl 2-doped material is attributed to regions of MgCl 2 acting as barriers between the MgH 2 and Ni, hindering the ability of the latter to effectively catalyze the reactions. Finally, this work demonstrates the hazards in assuming different catalyst forms produce similar final structures and highlights the potential of catalyst form as a synthesis tool for optimizing the material structure and performance.« less

Hydrodeoxygenation of phenol over zirconia supported Pd bimetallic catalysts. The effect of second metal on catalyst performance

DOE PAGES

Resende, Karen A.; Teles, Camila A.; Jacobs, Gary; ...

2018-03-21

Here, this work investigated the effect of the addition of a second metal (Cu, Ag, Zn, Sn) on the performance of Pd/ZrO 2 catalyst for HDO of phenol at 573 K in the gas phase. The incorporation of dopants resulted in the formation of Pd–X (Cu, Ag, Zn) alloys, which reduced the reaction rate for HDO and increased the selectivity to hydrogenation products (cyclohexanone and cyclohexanol). The lower activity of the bimetallic catalysts was due to the segregation of the second metal on the surface of the Pd particle. For PdSn/ZrO 2, alloying was also observed but tin oxide wasmore » still present on the surface after reduction at 773 K. For Pd and PdSn/ZrO 2, the oxophilic sites represented by Zr and Sn cations promotes the hydrogenation of the carbonyl group of the keto-tautomer intermediate formed, producing benzene as the main product. All catalysts significantly deactivated during the reaction but the deactivation degree depended on the type of the metal. Pd/ZrO 2 and PdZn/ZrO 2 and PdAg/ZrO 2 exhibited approximately the same deactivation degree. However, the loss of activity was less pronounced for PdSn/ZrO2 catalyst. Finally, Pd dispersion significantly decreased during the reaction, indicating that the sintering of Pd particles is one of the causes for catalyst deactivation.« less

Impact of initial catalyst form on the 3D structure and performance of ball-milled Ni-catalyzed MgH 2 for hydrogen storage

DOE PAGES

House, Stephen D.; Vajo, John J.; Ren, Chai; ...

2017-02-24

Although it has been shown that the hydrogen storage kinetics of metal hydrides can be significantly improved by the addition of transition metal-based catalysts, relatively little attention has been paid to the impact that the form in which these catalysts are introduced during synthesis has on the resulting structure and how this alters performance. Two mixtures of MgH 2 doped with Ni were prepared via high-energy ball-milling under identical conditions, one using a pure Ni nanopowder catalyst and the other using anhydrous NiCl 2. The resulting Ni catalyst particles of the NiCl 2-doped material were 10-100 times smaller, as wellmore » as more uniform in size and shape. Electron tomography revealed that the additive form also altered its incorporation and 3D spatial distribution, with Ni particles limited to the outer surface in the NiCl 2-doped case. The significantly lower desorption performance measured in the NiCl 2-doped material is attributed to regions of MgCl 2 acting as barriers between the MgH 2 and Ni, hindering the ability of the latter to effectively catalyze the reactions. Finally, this work demonstrates the hazards in assuming different catalyst forms produce similar final structures and highlights the potential of catalyst form as a synthesis tool for optimizing the material structure and performance.« less

Co-Pt core-shell nanostructured catalyst prepared by selective chemical vapor pulse deposition of Pt on Co as a cathode in polymer electrolyte fuel cells

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

Seo, Sang-Joon; Chung, Ho-Kyoon; Yoo, Ji-Beom

2014-01-15

A new type of PtCo/C catalyst for use as a cathode in polymer electrolyte fuel cells was prepared by selective chemical vapor pulse deposition (CVPD) of Pt on the surface of Co. The activity of the prepared catalyst for oxygen reduction was higher than that of a catalyst prepared by sequential impregnation (IMP) with the two metallic components. This catalytic activity difference occurs because the former catalyst has smaller Pt crystallites that produce stronger Pt-Co interactions and have a larger Pt surface area. Consequently, the CVPD catalyst has a great number of Co particles that are in close contact withmore » the added Pt. The Pt surface was also electronically modified by interactions with Co, which were stronger in the CVPD catalyst than in the IMP catalyst, as indicated by X-ray diffraction, X-ray photoemission spectroscopy, and cyclic voltammetry measurements of the catalysts.« less

Titanium Dioxide as a Catalyst Support in Heterogeneous Catalysis

PubMed Central

Bagheri, Samira; Muhd Julkapli, Nurhidayatullaili; Bee Abd Hamid, Sharifah

2014-01-01

The lack of stability is a challenge for most heterogeneous catalysts. During operations, the agglomeration of particles may block the active sites of the catalyst, which is believed to contribute to its instability. Recently, titanium oxide (TiO2) was introduced as an alternative support material for heterogeneous catalyst due to the effect of its high surface area stabilizing the catalysts in its mesoporous structure. TiO2 supported metal catalysts have attracted interest due to TiO2 nanoparticles high activity for various reduction and oxidation reactions at low pressures and temperatures. Furthermore, TiO2 was found to be a good metal oxide catalyst support due to the strong metal support interaction, chemical stability, and acid-base property. The aforementioned properties make heterogeneous TiO2 supported catalysts show a high potential in photocatalyst-related applications, electrodes for wet solar cells, synthesis of fine chemicals, and others. This review focuses on TiO2 as a support material for heterogeneous catalysts and its potential applications. PMID:25383380

Oxygen Release Induced Chemomechanical Breakdown of Layered Cathode Materials

DOE PAGES

Mu, Linqin; Lin, Ruoqian; Xu, Rong; ...

2018-04-18

Chemical and mechanical properties interplay on the nanometric scale and collectively govern the functionalities of battery materials. Understanding the relationship between the two can inform the design of battery materials with optimal chemomechanical properties for long-life lithium batteries. Herein, we report a mechanism of nanoscale mechanical breakdown in layered oxide cathode materials, originating from oxygen release at high states of charge under thermal abuse conditions. Here, we observe that the mechanical breakdown of charged Li 1-xNi 0.4Mn 0.4Co 0.2O 2 materials proceeds via a two-step pathway involving intergranular and intragranular crack formation. Owing to the oxygen release, sporadic phase transformationsmore » from the layered structure to the spinel and/or rocksalt structures introduce local stress, which initiates microcracks along grain boundaries and ultimately leads to the detachment of primary particles; i.e., intergranular crack formation. Furthermore, intragranular cracks (pores and exfoliations) form, likely due to the accumulation of oxygen vacancies and continuous phase transformations at the surfaces of primary particles. Finally, finite element modeling confirms our experimental observation that the crack formation is attributable to formation of oxygen vacancies, oxygen release, and phase transformations. This study is designed to directly observe the chemomechanical behavior of layered oxide cathode materials and provides a chemical basis for strengthening primary and secondary particles by stabilizing the oxygen anions in the lattice.« less

Oxygen Release Induced Chemomechanical Breakdown of Layered Cathode Materials

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

Mu, Linqin; Lin, Ruoqian; Xu, Rong

Chemical and mechanical properties interplay on the nanometric scale and collectively govern the functionalities of battery materials. Understanding the relationship between the two can inform the design of battery materials with optimal chemomechanical properties for long-life lithium batteries. Herein, we report a mechanism of nanoscale mechanical breakdown in layered oxide cathode materials, originating from oxygen release at high states of charge under thermal abuse conditions. Here, we observe that the mechanical breakdown of charged Li 1-xNi 0.4Mn 0.4Co 0.2O 2 materials proceeds via a two-step pathway involving intergranular and intragranular crack formation. Owing to the oxygen release, sporadic phase transformationsmore » from the layered structure to the spinel and/or rocksalt structures introduce local stress, which initiates microcracks along grain boundaries and ultimately leads to the detachment of primary particles; i.e., intergranular crack formation. Furthermore, intragranular cracks (pores and exfoliations) form, likely due to the accumulation of oxygen vacancies and continuous phase transformations at the surfaces of primary particles. Finally, finite element modeling confirms our experimental observation that the crack formation is attributable to formation of oxygen vacancies, oxygen release, and phase transformations. This study is designed to directly observe the chemomechanical behavior of layered oxide cathode materials and provides a chemical basis for strengthening primary and secondary particles by stabilizing the oxygen anions in the lattice.« less

Controlled boiling on Enceladus. 1. Model of the vapor-driven jets

NASA Astrophysics Data System (ADS)

Nakajima, Miki; Ingersoll, Andrew P.

2016-07-01

Plumes of water vapor and ice particles have been observed from the so-called tiger stripes at the south polar terrain (SPT) of Saturn's satellite, Enceladus. The observed high salinity (∼0.5-2%) of the ice particles in the plumes may indicate that the plumes originate from a subsurface liquid ocean. Additionally, the SPT is the source of strong infrared radiation (∼4.2 GW), which is especially intense near (within tens of meters) the tiger stripes. This could indicate that the radiation is associated with plume activity, but the connection remains unclear. Here we investigate the constraints that plume observations place on the widths of the cracks, the depth to the liquid-vapor interface, and the mechanisms controlling plume variability. We solve the fluid dynamics of the flow in the crack and the interaction between the flow and ice walls assuming that the flows of water vapor and ice particles originate from a few kilometers deep liquid ocean. For a crack with a uniform width, we find that our model could explain the observed vapor mass flow rate of the plumes when the crack width is 0.05-0.075 m. A wider crack is not favorable because it would produce a higher vapor mass flow rate than the observed value, but it may be allowed if there are some flows that do not reach the surface of Enceladus either due to condensation on the icy walls or the tortuosity of the crack. The observed heat flow can be explained if the total crack length is approximately 1.7 × 500 km. A tapering crack (a crack which is ∼1 m wide at the bottom of the flow and sharply becomes 0.05-0.075 m at shallower depths) can also explain the observed vapor mass flow rate and heat flow. Widths of 1 m or more are necessary to avoid freezing at the liquid-vapor interface, as shown in our paired paper (Ingersoll and Nakajima [2016] Icarus). The observed intense heat flow along the tiger stripes can be explained by the latent heat release due to vapor condensation onto the ice walls near the surface. The resulting buildup of ice causes the vents to seal themselves on time scales less than a year. We also find that the ice to vapor ratio of the plumes is sensitive to the ice mass fraction at the bottom of the flow (liquid-vapor interface). We find that the total mass flow rate of the plumes becomes larger when the crack width is larger, which is consistent with the observation that the flow rate increases near the orbital apocenter, where the crack is expected to be widest.

Synthesis and Characterization of Platinum-Ruthenium-Tin Catalysts

NASA Astrophysics Data System (ADS)

Uffalussy, Karen

Magnesia-supported trimetallic Pt-Ru-Sn catalysts prepared through a cluster and a conventional synthetic route have been investigated in terms of their structural properties and their catalytic activity for the hydrogenation of citral and crotonaldehyde. FTIR results indicate that the majority of the stabilizing ligands remain attached to the PtRu5(μ-SnPh 2)(C)(CO)15 cluster used following impregnation onto the MgO support. Under H2 reduction conditions, partial and full ligand removal are both observed at 473 and 573 K, respectively. HRSTEM analysis shows that cluster-derived samples exhibit significantly smaller average metal particle sizes, as well as narrower particle size distributions than the corresponding conventionally prepared ones. EDX measurements show that in the cluster-derived catalysts, the majority of the metal particles present are trimetallic in nature, with metal compositions similar to those of the original cluster. In contrast, the conventionally prepared materials contain mostly bimetallic and monometallic particles with variable compositions. XPS was used to determine how the variation in method of Sn addition to bimetallic Pt-Ru affects the electronic state for the trimetallic Pt-Ru-Sn/MgO system prepared by impregnation using multimetallic clusters, metal-salts, and the combination of both precursor types. Results show that the PtRu5Sn/MgO material has a significantly higher percentage of Sn0 in comparison to Pt-Ru-Sn/MgO and PtRu5-Sn/MgO, and a corresponding shift in both Pt and Ru peaks can be correlated to this relative change in Sn oxidation state. The formation of smaller metal particles and electronic modification of Pt and Ru by Sn in the cluster-derived catalysts and the presence of the three metals in these particles in close proximity result in higher activity and selectivity to the unsaturated alcohols for the hydrogenation of both citral and crotonaldehyde.

New Pt/Alumina model catalysts for STM and in situ XPS studies

NASA Astrophysics Data System (ADS)

Nartova, Anna V.; Gharachorlou, Amir; Bukhtiyarov, Andrey V.; Kvon, Ren I.; Bukhtiyarov, Valerii I.

2017-04-01

The new Pt/alumina model catalysts for STM and in situ XPS studies based on thin alumina film formed over the conductive substrate are proposed. Procedure of platinum deposition developed for porous alumina was adapted for the model alumina support. The set of Pt/AlOx-film samples with the different mean platinum particle size was prepared. Capabilities of in situ XPS investigations of the proposed catalysts were demonstrated in study of NO decomposition on platinum nanoparticles. It is shown that proposed model catalysts behave similarly to Pt/γ-Al2O3 and provide the new opportunities for the instrumental studies of platinum catalysts due to resolving several issues (charging, heating, screening) that are typical for the investigation of the porous oxide supported catalysts.

Single Atomic Iron Catalysts for Oxygen Reduction in Acidic Media: Particle Size Control and Thermal Activation

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

Zhang, Hanguang; Hwang, Sooyeon; Wang, Maoyu

It remains a grand challenge to replace platinum group metal (PGM) catalysts with earth-abundant materials for the oxygen reduction reaction (ORR) in acidic media, which is crucial for large-scale deployment of proton exchange membrane fuel cells (PEMFCs). Here, we report a high-performance atomic Fe catalyst derived from chemically Fe-doped zeolitic imidazolate frameworks (ZIFs) by directly bonding Fe ions to imidazolate ligands within 3D frameworks. Although the ZIF was identified as a promising precursor, the new synthetic chemistry enables the creation of well-dispersed atomic Fe sites embedded into porous carbon without the formation of aggregates. The size of catalyst particles ismore » tunable through synthesizing Fe-doped ZIF nanocrystal precursors in a wide range from 20 to 1000 nm followed by one-step thermal activation. Similar to Pt nanoparticles, the unique size control without altering chemical properties afforded by this approach is able to increase the number of PGM-free active sites. The best ORR activity is measured with the catalyst at a size of 50 nm. Further size reduction to 20 nm leads to significant particle agglomeration, thus decreasing the activity. Using the homogeneous atomic Fe model catalysts, we elucidated the active site formation process through correlating measured ORR activity with the change of chemical bonds in precursors during thermal activation up to 1100 °C. The critical temperature to form active sites is 800 °C, which is associated with a new Fe species with a reduced oxidation number (from Fe3+ to Fe2+) likely bonded with pyridinic N (FeN4) embedded into the carbon planes. Further increasing the temperature leads to continuously enhanced activity, linked to the rise of graphitic N and Fe–N species. The new atomic Fe catalyst has achieved respectable ORR activity in challenging acidic media (0.5 M H2SO4), showing a half-wave potential of 0.85 V vs RHE and leaving only a 30 mV gap with Pt/C (60 μgPt/cm2). Enhanced stability is attained with the same catalyst, which loses only 20 mV after 10 000 potential cycles (0.6–1.0 V) in O2 saturated acid. The high-performance atomic Fe PGM-free catalyst holds great promise as a replacement for Pt in future PEMFCs.« less

Single Atomic Iron Catalysts for Oxygen Reduction in Acidic Media: Particle Size Control and Thermal Activation

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

Zhang, Hanguang; Hwang, Sooyeon; Wang, Maoyu

It remains a grand challenge to replace platinum group metal (PGM) catalysts with earth-abundant materials for the oxygen reduction reaction (ORR) in acidic media, which is crucial for large-scale deployment of proton exchange membrane fuel cells (PEMFCs). We report a high-performance atomic Fe catalyst derived from chemically Fe-doped zeolitic imidazolate frameworks (ZIFs) by directly bonding Fe ions to imidazolate ligands within 3D frameworks. Although the ZIF was identified as a promising precursor, the new synthetic chemistry enables the creation of well-dispersed atomic Fe sites embedded into porous carbon without the formation of aggregates. The size of catalyst particles is tunablemore » through synthesizing Fe-doped ZIF nanocrystal precursors in a wide range from 20 to 1000 nm followed by one-step thermal activation. Similar to Pt nanoparticles, the unique size control without altering chemical properties afforded by this approach is able to increase the number of PGM-free active sites. The best ORR activity is measured with the catalyst at a size of 50 nm. Further size reduction to 20 nm leads to significant particle agglomeration, thus decreasing the activity. In using the homogeneous atomic Fe model catalysts, we elucidated the active site formation process through correlating measured ORR activity with the change of chemical bonds in precursors during thermal activation up to 1100 °C. The critical temperature to form active sites is 800 °C, which is associated with a new Fe species with a reduced oxidation number (from Fe 3+ to Fe 2+) likely bonded with pyridinic N (FeN 4) embedded into the carbon planes. Further increasing the temperature leads to continuously enhanced activity, linked to the rise of graphitic N and Fe–N species. The new atomic Fe catalyst has achieved respectable ORR activity in challenging acidic media (0.5 M H 2SO 4), showing a half-wave potential of 0.85 V vs RHE and leaving only a 30 mV gap with Pt/C (60 μg Pt/cm 2). Finally, enhanced stability is attained with the same catalyst, which loses only 20 mV after 10 000 potential cycles (0.6–1.0 V) in O 2 saturated acid. The high-performance atomic Fe PGM-free catalyst holds great promise as a replacement for Pt in future PEMFCs.« less

Single Atomic Iron Catalysts for Oxygen Reduction in Acidic Media: Particle Size Control and Thermal Activation

DOE PAGES

Zhang, Hanguang; Hwang, Sooyeon; Wang, Maoyu; ...

2017-09-13

It remains a grand challenge to replace platinum group metal (PGM) catalysts with earth-abundant materials for the oxygen reduction reaction (ORR) in acidic media, which is crucial for large-scale deployment of proton exchange membrane fuel cells (PEMFCs). We report a high-performance atomic Fe catalyst derived from chemically Fe-doped zeolitic imidazolate frameworks (ZIFs) by directly bonding Fe ions to imidazolate ligands within 3D frameworks. Although the ZIF was identified as a promising precursor, the new synthetic chemistry enables the creation of well-dispersed atomic Fe sites embedded into porous carbon without the formation of aggregates. The size of catalyst particles is tunablemore » through synthesizing Fe-doped ZIF nanocrystal precursors in a wide range from 20 to 1000 nm followed by one-step thermal activation. Similar to Pt nanoparticles, the unique size control without altering chemical properties afforded by this approach is able to increase the number of PGM-free active sites. The best ORR activity is measured with the catalyst at a size of 50 nm. Further size reduction to 20 nm leads to significant particle agglomeration, thus decreasing the activity. In using the homogeneous atomic Fe model catalysts, we elucidated the active site formation process through correlating measured ORR activity with the change of chemical bonds in precursors during thermal activation up to 1100 °C. The critical temperature to form active sites is 800 °C, which is associated with a new Fe species with a reduced oxidation number (from Fe 3+ to Fe 2+) likely bonded with pyridinic N (FeN 4) embedded into the carbon planes. Further increasing the temperature leads to continuously enhanced activity, linked to the rise of graphitic N and Fe–N species. The new atomic Fe catalyst has achieved respectable ORR activity in challenging acidic media (0.5 M H 2SO 4), showing a half-wave potential of 0.85 V vs RHE and leaving only a 30 mV gap with Pt/C (60 μg Pt/cm 2). Finally, enhanced stability is attained with the same catalyst, which loses only 20 mV after 10 000 potential cycles (0.6–1.0 V) in O 2 saturated acid. The high-performance atomic Fe PGM-free catalyst holds great promise as a replacement for Pt in future PEMFCs.« less

Synthesis of iron based hydrocracking catalysts

DOEpatents

Farcasiu, Malvina; Eldredge, Patricia A.; Ladner, Edward P.

1993-01-01

A method of preparing a fine particle iron based hydrocracking catalyst and the catalyst prepared thereby. An iron (III) oxide powder and elemental sulfur are reacted with a liquid hydrogen donor having a hydroaromatic structure present in the range of from about 5 to about 50 times the weight of iron (III) oxide at a temperature in the range of from about 180.degree. C. to about 240.degree. C. for a time in the range of from about 0 to about 8 hours. Various specific hydrogen donors are disclosed. The catalysts are active at low temperature (<350.degree. C.) and low pressure.

Tailoring the synthesis of supported Pd catalysts towards desired structure and size of metal particles.

PubMed

Suresh, Gatla; Radnik, Jörg; Kalevaru, Venkata Narayana; Pohl, Marga-Martina; Schneider, Matthias; Lücke, Bernhard; Martin, Andreas; Madaan, Neetika; Brückner, Angelika

2010-05-14

In a systematic study, the influence of different preparation parameters on phase composition and size of metal crystallites and particles in Pd-Cu/TiO(2) and Pd-Sb/TiO(2) catalyst materials has been explored. Temperature and atmosphere of thermal pretreatment (pure He or 10% H(2)/He), nature of metal precursors (chlorides, nitrates or acetates) as well as of ammonium additives (ammonium sulfate, nitrate, carbonate) and urea were varied with the aim of tailoring the synthesis procedure for the preferential formation of metal particles with similar size and structure as observed recently in active catalysts after long-term equilibration under catalytic reaction conditions in acetoxylation of toluene to benzylacetate. Among the metal precursors and additives, the chloride metal precursors and (NH(4))(2)SO(4) were most suitable. Upon thermal pretreatment of Pd-Sb or Pd-Cu precursors, chloroamine complexes of Pd and Cu are formed, which decompose above 220 degrees C to metallic phases independent of the atmosphere. In He, metallic Pd particles were formed with both the co-components. In H(2)/He flow, Pd-Cu precursors were converted to core-shell particles with a Cu shell and a Pd core, while Sb(1)Pd(1) and Sb(7)Pd(20) alloy phases were formed in the presence of Sb. Metal crystallites of about 40 nm agglomerate to particles of up to 150 nm in He and to even larger size in H(2)/He.

Crack-resistant polyimide coating for high-capacity battery anodes

NASA Astrophysics Data System (ADS)

Li, Yingshun; Wang, Shuo; Lee, Pui-Kit; He, Jieqing; Yu, Denis Y. W.

2017-10-01

Electrode cracking is a serious problem that hinders the application of many next-generation high-capacity anode materials for lithium-ion batteries. Even though nano-sizing the material can reduce fracturing of individual particles, capacity fading is still observed due to large volume change and loss of contact in the electrode during lithium insertion and extraction. In this study, we design a crack-resistant high-modulus polyimide coating with high compressive strength which can hold multiple particles together during charge and discharge to maintain contact. The effectiveness of the coating is demonstrated on tin dioxide, a high-capacity large-volume-change material that undergoes both alloy and conversion reactions. The polyimide coating improves capacity retention of SnO2 from 80% to 100% after 80 cycles at 250 mA g-1. Stable capacity of 585 mAh g-1 can be obtained even at 500 mA g-1 after 300 cycles. Scanning electron microscopy and in-situ dilatometry confirm that electrode cracking is suppressed and thickness change is reduced with the coating. In addition, the chemically-stable polyimide film can separate the surface from direct contact with electrolyte, improving coulombic efficiency to ∼100%. We expect the novel strategy of suppressing electrode degradation with a crack-resistant coating can also be used for other alloy and conversion-based anodes.

PFC2D simulation of thermally induced cracks in concrete specimens

NASA Astrophysics Data System (ADS)

Liu, Xinghong; Chang, Xiaolin; Zhou, Wei; Li, Shuirong

2013-06-01

The appearance of cracks exposed to severe environmental conditions can be critical for concrete structures. The research is to validate Particle Flow Code(PFC2D) method in the context of concrete thermally-induced cracking simulations. First, concrete was discreted as meso-level units of aggregate, cement mortar and the interfaces between them. Parallel bonded-particle model in PFC2D was adapted to describe the constitutive relation of the cementing material. Then, the concrete mechanics meso-parameters were obtained through several groups of biaxial tests, in order to make the numerical results comply with the law of the indoor test. The concrete thermal meso-parameters were determined by compared with the parameters in the empirical formula through the simulations imposing a constant heat flow to the left margin of concrete specimens. At last, a case of 1000mm×500mm concrete specimen model was analyzed. It simulated the formation and development process of the thermally-induced cracks under the cold waves of different durations and temperature decline. Good agreements in fracture morphology and process were observed between the simulations, previous studies and laboratory data. The temperature decline limits during cold waves were obtained when its tensile strength was given as 3MPa. And it showed the feasibility of using PFC2D to simulate concrete thermally-induced cracking.

A Model for Determining Strength for Embedded Elliptical Crack in Ultra-high-temperature Ceramics

PubMed Central

Wang, Ruzhuan; Li, Weiguo

2015-01-01

A fracture strength model applied at room temperature for embedded elliptical crack in brittle solid was obtained. With further research on the effects of various physical mechanisms on material strength, a thermo-damage strength model for ultra-high-temperature ceramics was applied to each temperature phase. Fracture strength of TiC and the changing trends with elliptical crack shape variations under different temperatures were studied. The study showed that under low temperature, the strength is sensitive to the crack shape variation; as the temperature increases, the sensitivities become smaller. The size of ellipse’s minor axes has great effect on the material strength when the ratio of ellipse’s minor and major axes is lower than 0.5, even under relatively high temperatures. The effect of the minor axes of added particle on material properties thus should be considered under this condition. As the crack area is set, the fracture strength decreases firstly and then increases with the increase of ratio of ellipse’s minor and major axes, and the turning point is 0.5. It suggests that for the added particles the ratio of ellipse’s minor and major axes should not be 0.5. All conclusions significantly coincided with the results obtained by using the finite element software ABAQUS. PMID:28793488

A Model for Determining Strength for Embedded Elliptical Crack in Ultra-high-temperature Ceramics.

PubMed

Wang, Ruzhuan; Li, Weiguo

2015-08-05

A fracture strength model applied at room temperature for embedded elliptical crack in brittle solid was obtained. With further research on the effects of various physical mechanisms on material strength, a thermo-damage strength model for ultra-high-temperature ceramics was applied to each temperature phase. Fracture strength of TiC and the changing trends with elliptical crack shape variations under different temperatures were studied. The study showed that under low temperature, the strength is sensitive to the crack shape variation; as the temperature increases, the sensitivities become smaller. The size of ellipse's minor axes has great effect on the material strength when the ratio of ellipse's minor and major axes is lower than 0.5, even under relatively high temperatures. The effect of the minor axes of added particle on material properties thus should be considered under this condition. As the crack area is set, the fracture strength decreases firstly and then increases with the increase of ratio of ellipse's minor and major axes, and the turning point is 0.5. It suggests that for the added particles the ratio of ellipse's minor and major axes should not be 0.5. All conclusions significantly coincided with the results obtained by using the finite element software ABAQUS.

Novel nanodispersed coal liquefaction catalysts: Molecular design via microemulsion-based synthesis. Final technical report, October 1990--December 1994

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

Osseo-Asare, K.; Boakye, E.; Vittal, M.

1995-04-01

This report described the synthesis of Molybdenum Sulfides in microemulsions by acidification of ammonium tetrathiomolybdate. Molybdenum Sulfides have been shown to be potential coal liquefaction catalysts. The importance of particle size, temperature effects, and coal surface chemistry to impregnation are discussed.

Identifying the role of N-heteroatom location in the activity of metal catalysts for alcohol oxidation

DOE PAGES

Chan-Thaw, Carine E.; Veith, Gabriel M.; Villa, Alberto; ...

2015-04-02

Here, this work focuses on understanding how the bonding of nitrogen heteroatoms contained on/in a activated carbon support influence the stability and reactivity of a supported Pd catalyst for the oxidation of alcohols in solution. The results show that simply adding N groups via solution chemistry is insufficient to improve catalytic properties. Instead a strongly bound N moiety is required to activate the catalyst and stabilize the metal particles.

Selective catalytic reduction system and process for treating NOx emissions using a palladium and rhodium or ruthenium catalyst

DOEpatents

Sobolevskiy, Anatoly [Orlando, FL; Rossin, Joseph A [Columbus, OH; Knapke, Michael J [Columbus, OH

2011-07-12

A process for the catalytic reduction of nitrogen oxides (NOx) in a gas stream (29) in the presence of H.sub.2 is provided. The process comprises contacting the gas stream with a catalyst system (38) comprising zirconia-silica washcoat particles (41), a pre-sulfated zirconia binder (44), and a catalyst combination (40) comprising palladium and at least one of rhodium, ruthenium, or a mixture of ruthenium and rhodium.

I. Hole-transporting dendrimers and their use in organic light-emitting devices (OLEDs) and II. Novel layered catalysts containing bipyridinium and zero-valent metal species

NASA Astrophysics Data System (ADS)

Koene, Shannon Carol

A series of polyaromatic ether/ester dendrimers containing a hole transporting naphthylphenylbenzyl amine at the periphery and a variety of fluorescent dyes at the core has been studied in an effort to observe energy transfer in these species. The dyes incorporated in these dendrimers include 1,4-dihydroxyanthraquinone (quinizarin), Coumarin 343, and a benzopentathiophene. These dendrimers have been incorporated into both single layer and heterostructure organic light emitting devices (OLEDs). In the case of first generation dendrimer OLEDs, excimer/exciplex formation was predominant. In third generation dendrimers, complete energy transfer from the periphery to the dye at the core was observed both in photoluminescence spectra and electroluminescence in OLEDs. Dendrimers containing different dye cores can be combined to achieve color mixing/tuning. In addition, layered catalysts were prepared via both covalent and electrostatic means to achieve the catalytic production of hydrogen peroxide from hydrogen and oxygen. Covalent catalysts were prepared by first growing layers of zirconium and a bipyridinium containing bisphosphonate onto silica particles. Palladium and/or platinum was ion-exchanged into the structure and reduced to the zero valent metal by hydrogen gas. A second set of catalysts was prepared by electrostatically depositing polycations/polyanions onto carboxylate or amine functionalized polystyrene microspheres. Anionic colloidal particles were adsorbed to the polycationic surface. An octacationic viologen oligomer was used in an attempt to increase the affinity of adsorption of the Pd particles to the surface of the microspheres. Catalytic studies of both types of catalysts are herein reported.

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

Short-crack growth behaviour in an aluminum alloy: An AGARD cooperative test program

NASA Technical Reports Server (NTRS)

Newman, J. C., Jr.; Edwards, P. R.

1988-01-01

An AGARD Cooperative Test Program on the growth of short fatigue cracks was conducted to define the significance of the short-crack effect, to compare test results from various laboratories, and to evaluate an existing analytical crack-growth prediction model. The initiation and growth of short fatigue cracks (5 micrometer to 2 mm) from the surface of a semi-circular notch in 2024-T3 aluminum alloy sheet material were monitored under various load histories. The cracks initiated from inclusion particle clusters or voids on the notch surface and generally grew as surface cracks. Tests were conducted under several constant-amplitude (stress ratios of -2, -1, 0, and 0.5) and spectrum (FALSTAFF and Gaussian) loading conditions at 3 stress levels each. Short crack growth was recorded using a plastic-replica technique. Over 250 edge-notched specimens were fatigue tested and nearly 950 cracks monitored by 12 participants from 9 countries. Long crack-growth rate data for cracks greater than 2 mm in length were obtained over a wide range in rates (10 to the -8 to 10 to the -1 mm/cycle) for all constant-amplitude loading conditions. Long crack-growth rate data for the FALSTAFF and Gaussian load sequences were also obtained.

Thermoelastic analysis of matrix crack growth in particulate composites

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

Sridhar, N.; Rickman, J.M.; Srolovitz, D.J.

1995-04-01

The authors examine the conditions under which differences in thermal expansion between a particle and the matrix lead to crack growth within the matrix. Using linear elasticity fracture mechanics, they obtain closed-form, analytical results for the case of a penny shaped crack present in the matrix interacting with a spherical inclusion which is misfitting with respect to the matrix. A simple and direct relationship is established between the strain energy release rate, the crack size, the crack orientation with respect to the inclusion, the crack/inclusion separation, the degree of thermal expansion mismatch and the elastic properties of the medium. Themore » authors also analyze the size to which these cracks can grow and find that for a given misfit strain and material properties, crack growth is inhibited beyond a certain critical crack size. They find that beyond this critical size, the elastic strain energy released upon crack growth is no longer sufficient to compensate for the energy expended in extending the crack, since the crack is growing into the rapidly decreasing stress field. The modification of the above conditions for crack growth due to the superposition of an external stress field has also been analyzed. The preferred orientation of these cracks as a function of misfit strain is predicted. The implication of these results for thermal cycling are analyzed.« 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...