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

Code of Federal Regulations, 2012 CFR

2012-07-01

... 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...) and (d) of this section. (c) Any fluid catalytic cracking unit catalyst regenerator under paragraph (b...

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

Code of Federal Regulations, 2010 CFR

2010-07-01

... 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...) and (d) of this section. (c) Any fluid catalytic cracking unit catalyst regenerator under paragraph (b...

40 CFR 60.103 - Standard for carbon monoxide.

Code of Federal Regulations, 2011 CFR

2011-07-01

... Refineries § 60.103 Standard for carbon monoxide. Each owner or operator of any fluid catalytic cracking unit... the fluid catalytic cracking unit catalyst regenerator will be operated, or 180 days after initial... discharge or cause the discharge into the atmosphere from any fluid catalytic cracking unit catalyst...

40 CFR 60.103 - Standard for carbon monoxide.

Code of Federal Regulations, 2010 CFR

2010-07-01

... Refineries § 60.103 Standard for carbon monoxide. Each owner or operator of any fluid catalytic cracking unit... the fluid catalytic cracking unit catalyst regenerator will be operated, or 180 days after initial... discharge or cause the discharge into the atmosphere from any fluid catalytic cracking unit catalyst...

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

NASA Astrophysics Data System (ADS)

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

2014-10-01

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

Process to convert biomass and refuse derived fuel to ethers and/or alcohols

DOEpatents

Diebold, James P.; Scahill, John W.; Chum, Helena L.; Evans, Robert J.; Rejai, Bahman; Bain, Richard L.; Overend, Ralph P.

1996-01-01

A process for conversion of a feedstock selected from the group consisting of biomass and refuse derived fuel (RDF) to provide reformulated gasoline components comprising a substantial amount of materials selected from the group consisting of ethers, alcohols, or mixtures thereof, comprising: drying said feedstock; subjecting said dried feedstock to fast pyrolysis using a vortex reactor or other means; catalytically cracking vapors resulting from said pyrolysis using a zeolite catalyst; condensing any aromatic byproduct fraction; catalytically alkylating any benzene present in said vapors after condensation; catalytically oligomerizing any remaining ethylene and propylene to higher olefins; isomerizing said olefins to reactive iso-olefins; and catalytically reacting said iso-olefins with an alcohol to form ethers or with water to form alcohols.

40 CFR 63.1563 - When do I have to comply with this subpart?

Code of Federal Regulations, 2011 CFR

2011-07-01

... National Emission Standards for Hazardous Air Pollutants for Petroleum Refineries: Catalytic Cracking Units... for an existing catalytic cracking unit allowing additional time to meet the emission limitations and work practice standards for catalytic cracking units in §§ 63.1564 and 63.1565 if you commit to...

40 CFR 63.1563 - When do I have to comply with this subpart?

Code of Federal Regulations, 2010 CFR

2010-07-01

... National Emission Standards for Hazardous Air Pollutants for Petroleum Refineries: Catalytic Cracking Units... for an existing catalytic cracking unit allowing additional time to meet the emission limitations and work practice standards for catalytic cracking units in §§ 63.1564 and 63.1565 if you commit to...

40 CFR Table 8 to Subpart Uuu of... - Organic HAP Emission Limits for Catalytic Cracking Units

Code of Federal Regulations, 2014 CFR

2014-07-01

... 40 Protection of Environment 13 2014-07-01 2014-07-01 false Organic HAP Emission Limits for Catalytic Cracking Units 8 Table 8 to Subpart UUU of Part 63 Protection of Environment ENVIRONMENTAL..., Subpt. UUU, Table 8 Table 8 to Subpart UUU of Part 63—Organic HAP Emission Limits for Catalytic Cracking...

40 CFR Table 8 to Subpart Uuu of... - Organic HAP Emission Limits for Catalytic Cracking Units

Code of Federal Regulations, 2013 CFR

2013-07-01

... 40 Protection of Environment 13 2013-07-01 2012-07-01 true Organic HAP Emission Limits for Catalytic Cracking Units 8 Table 8 to Subpart UUU of Part 63 Protection of Environment ENVIRONMENTAL..., Subpt. UUU, Table 8 Table 8 to Subpart UUU of Part 63—Organic HAP Emission Limits for Catalytic Cracking...

40 CFR Table 8 to Subpart Uuu of... - Organic HAP Emission Limits for Catalytic Cracking Units

Code of Federal Regulations, 2012 CFR

2012-07-01

... 40 Protection of Environment 13 2012-07-01 2012-07-01 false Organic HAP Emission Limits for Catalytic Cracking Units 8 Table 8 to Subpart UUU of Part 63 Protection of Environment ENVIRONMENTAL..., Subpt. UUU, Table 8 Table 8 to Subpart UUU of Part 63—Organic HAP Emission Limits for Catalytic Cracking...

40 CFR 63.1568 - What are my requirements for HAP emissions from sulfur recovery units?

Code of Federal Regulations, 2012 CFR

2012-07-01

... emissions from sulfur recovery units? 63.1568 Section 63.1568 Protection of Environment ENVIRONMENTAL... Petroleum Refineries: Catalytic Cracking Units, Catalytic Reforming Units, and Sulfur Recovery Units Catalytic Cracking Units, Catalytic Reforming Units, Sulfur Recovery Units, and Bypass Lines § 63.1568 What...

Process to convert biomass and refuse derived fuel to ethers and/or alcohols

DOEpatents

Diebold, J.P.; Scahill, J.W.; Chum, H.L.; Evans, R.J.; Rejai, B.; Bain, R.L.; Overend, R.P.

1996-04-02

A process is described for conversion of a feedstock selected from the group consisting of biomass and refuse derived fuel (RDF) to provide reformulated gasoline components comprising a substantial amount of materials selected from the group consisting of ethers, alcohols, or mixtures thereof, comprising: drying said feedstock; subjecting said dried feedstock to fast pyrolysis using a vortex reactor or other means; catalytically cracking vapors resulting from said pyrolysis using a zeolite catalyst; condensing any aromatic byproduct fraction; catalytically alkylating any benzene present in said vapors after condensation; catalytically oligomerizing any remaining ethylene and propylene to higher olefins; isomerizing said olefins to reactive iso-olefins; and catalytically reacting said iso-olefins with an alcohol to form ethers or with water to form alcohols. 35 figs.

Petroleum Refineries (Catalytic Cracking, Catalytic Reforming and Sulfur Recovery Units): National Emission Standards for Hazardous Air Pollutants (NESHAP)

EPA Pesticide Factsheets

learn more about the NESHAP for catalytic cracking and reforming units, as well as sulfur recovery units in petroleum refineries by reading the rule history, rule summary, background information documents, and compliance information

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...

40 CFR 63.1561 - Am I subject to this subpart?

Code of Federal Regulations, 2011 CFR

2011-07-01

... Standards for Hazardous Air Pollutants for Petroleum Refineries: Catalytic Cracking Units, Catalytic..., and fuel oils), or lubricants; (ii) Separating petroleum; or (iii) Separating, cracking, reacting, or...

40 CFR 63.1561 - Am I subject to this subpart?

Code of Federal Regulations, 2010 CFR

2010-07-01

... Standards for Hazardous Air Pollutants for Petroleum Refineries: Catalytic Cracking Units, Catalytic..., and fuel oils), or lubricants; (ii) Separating petroleum; or (iii) Separating, cracking, reacting, or...

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.

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

Erdemir, Ali; Eryilmaz, Osman Levent; Urgen, Mustafa

A nanocomposite coating and method of making and using the coating. The nanocomposite coating is disposed on a base material, such as a metal or ceramic; and the nanocomposite consists essentially of a matrix of an alloy selected from the group of Cu, Ni, Pd, Pt and Re which are catalytically active for cracking of carbon bonds in oils and greases and a grain structure selected from the group of borides, carbides and nitrides.

40 CFR 63.1576 - What records must I keep, in what form, and for how long?

Code of Federal Regulations, 2010 CFR

2010-07-01

... Cracking Units, Catalytic Reforming Units, and Sulfur Recovery Units Notifications, Reports, and Records... keep records required by Tables 6, 7, 13, and 14 of this subpart (for catalytic cracking units); Tables...

40 CFR 63.1576 - What records must I keep, in what form, and for how long?

Code of Federal Regulations, 2011 CFR

2011-07-01

... Cracking Units, Catalytic Reforming Units, and Sulfur Recovery Units Notifications, Reports, and Records... keep records required by Tables 6, 7, 13, and 14 of this subpart (for catalytic cracking units); Tables...

40 CFR Table 11 to Subpart Uuu of... - Requirements for Performance Tests for Organic HAP Emissions From Catalytic Cracking Units Not...

Code of Federal Regulations, 2010 CFR

2010-07-01

...) for Carbon Monoxide (CO) 11 Table 11 to Subpart UUU of Part 63 Protection of Environment ENVIRONMENTAL... Refineries: Catalytic Cracking Units, Catalytic Reforming Units, and Sulfur Recovery Units Pt. 63, Subpt. UUU, Table 11 Table 11 to Subpart UUU of Part 63—Requirements for Performance Tests for Organic HAP Emissions...

40 CFR Table 11 to Subpart Uuu of... - Requirements for Performance Tests for Organic HAP Emissions From Catalytic Cracking Units Not...

Code of Federal Regulations, 2011 CFR

2011-07-01

...) for Carbon Monoxide (CO) 11 Table 11 to Subpart UUU of Part 63 Protection of Environment ENVIRONMENTAL... Refineries: Catalytic Cracking Units, Catalytic Reforming Units, and Sulfur Recovery Units Pt. 63, Subpt. UUU, Table 11 Table 11 to Subpart UUU of Part 63—Requirements for Performance Tests for Organic HAP Emissions...

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...

Forecasting the zeolite-containing catalyst activity in catalytic cracking technology taking into account the feedstock composition

NASA Astrophysics Data System (ADS)

Ivashkina, Elena; Nazarova, Galina; Shafran, Tatyana; Stebeneva, Valeriya

2017-08-01

The effect of the feedstock composition and the process conditions on the current catalyst activity in catalytic cracking technology using a mathematical model is performed in this research. The mathematical model takes into account the catalyst deactivation by coke for primary and secondary cracking reactions. The investigation results have shown that the feedstock has significant effect on the yield and the content of coke on the catalyst. Thus, the relative catalyst activity is significantly reduced by 7.5-10.7 %. With increasing the catalytic cracking temperature due to the catalyst flow temperature rising, the coke content and the yield per feedstock increase and the catalyst activity decreases by 5.3-7.7%. Rising the process temperature together with the catalyst circulation ratio contributes to increase of the coke yield per feedstock in the catalytic cracking and decrease of the coke content on the catalyst. It is connected with the catalyst flow rising to the riser and the contact time decreasing in the reaction zone. Also, the catalyst activity decreases in the range of 3.8-5.5% relatively to the regenerated catalyst activity (83 %).

Rapid starting methanol reactor system

DOEpatents

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

1984-01-01

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

Multifunctional two-stage riser fluid catalytic cracking process.

PubMed

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

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

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

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.

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

Supercritical Catalytic Cracking of Hydrocarbon Feeds Insight

DTIC Science & Technology

2016-04-21

University teamed with Spectral Energies, LLC to develop appropriate spatiotemporal imaging capabilities in single body zeolites to describe beneficial...We demonstrated the ability to follow in a spatiotemporal fashion, the decomposition of the structure-directing agent used to template the zeolite ...appropriate spatiotemporal imaging capabilities in single body zeolites to describe beneficial and parasitic catalytic cracking pathways. Beneficial

40 CFR Table 10 to Subpart Uuu of... - Continuous Monitoring Systems for Organic HAP Emissions From Catalytic Cracking Units

Code of Federal Regulations, 2014 CFR

2014-07-01

... 40 Protection of Environment 13 2014-07-01 2014-07-01 false Continuous Monitoring Systems for Organic HAP Emissions From Catalytic Cracking Units 10 Table 10 to Subpart UUU of Part 63 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) AIR PROGRAMS (CONTINUED) NATIONAL EMISSION STANDARDS FOR HAZARDOUS AIR POLLUTANTS FOR SOURCE...

40 CFR Table 10 to Subpart Uuu of... - Continuous Monitoring Systems for Organic HAP Emissions From Catalytic Cracking Units

Code of Federal Regulations, 2013 CFR

2013-07-01

... 40 Protection of Environment 13 2013-07-01 2012-07-01 true Continuous Monitoring Systems for Organic HAP Emissions From Catalytic Cracking Units 10 Table 10 to Subpart UUU of Part 63 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) AIR PROGRAMS (CONTINUED) NATIONAL EMISSION STANDARDS FOR HAZARDOUS AIR POLLUTANTS FOR SOURCE...

40 CFR Table 10 to Subpart Uuu of... - Continuous Monitoring Systems for Organic HAP Emissions From Catalytic Cracking Units

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 12 2010-07-01 2010-07-01 true Continuous Monitoring Systems for Organic HAP Emissions From Catalytic Cracking Units 10 Table 10 to Subpart UUU of Part 63 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) AIR PROGRAMS (CONTINUED) NATIONAL EMISSION STANDARDS FOR HAZARDOUS AIR POLLUTANTS FOR SOURCE...

40 CFR Table 10 to Subpart Uuu of... - Continuous Monitoring Systems for Organic HAP Emissions From Catalytic Cracking Units

Code of Federal Regulations, 2012 CFR

2012-07-01

... 40 Protection of Environment 13 2012-07-01 2012-07-01 false Continuous Monitoring Systems for Organic HAP Emissions From Catalytic Cracking Units 10 Table 10 to Subpart UUU of Part 63 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) AIR PROGRAMS (CONTINUED) NATIONAL EMISSION STANDARDS FOR HAZARDOUS AIR POLLUTANTS FOR SOURCE...

40 CFR Table 10 to Subpart Uuu of... - Continuous Monitoring Systems for Organic HAP Emissions From Catalytic Cracking Units

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 12 2011-07-01 2009-07-01 true Continuous Monitoring Systems for Organic HAP Emissions From Catalytic Cracking Units 10 Table 10 to Subpart UUU of Part 63 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) AIR PROGRAMS (CONTINUED) NATIONAL EMISSION STANDARDS FOR HAZARDOUS AIR POLLUTANTS FOR SOURCE...

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.

40 CFR Table 14 to Subpart Uuu of... - Continuous Compliance With Operating Limits for Organic HAP Emissions From Catalytic Cracking Units

Code of Federal Regulations, 2013 CFR

2013-07-01

... 40 Protection of Environment 13 2013-07-01 2012-07-01 true Continuous Compliance With Operating Limits for Organic HAP Emissions From Catalytic Cracking Units 14 Table 14 to Subpart UUU of Part 63... Reforming Units, and Sulfur Recovery Units Pt. 63, Subpt. UUU, Table 14 Table 14 to Subpart UUU of Part 63...

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

Code of Federal Regulations, 2014 CFR

2014-07-01

... 40 Protection of Environment 13 2014-07-01 2014-07-01 false Continous Monitoring Systems for Metal HAP Emissions From Catalytic Cracking Units 3 Table 3 to Subpart UUU of Part 63 Protection of... Sulfur Recovery Units Pt. 63, Subpt. UUU, Table 3 Table 3 to Subpart UUU of Part 63—Continous Monitoring...

40 CFR Table 13 to Subpart Uuu of... - Continuous Compliance With Organic HAP Emission Limits for Catalytic Cracking Units

Code of Federal Regulations, 2014 CFR

2014-07-01

... 40 Protection of Environment 13 2014-07-01 2014-07-01 false Continuous Compliance With Organic HAP Emission Limits for Catalytic Cracking Units 13 Table 13 to Subpart UUU of Part 63 Protection of... Sulfur Recovery Units Pt. 63, Subpt. UUU, Table 13 Table 13 to Subpart UUU of Part 63—Continuous...

40 CFR Table 14 to Subpart Uuu of... - Continuous Compliance With Operating Limits for Organic HAP Emissions From Catalytic Cracking Units

Code of Federal Regulations, 2014 CFR

2014-07-01

... 40 Protection of Environment 13 2014-07-01 2014-07-01 false Continuous Compliance With Operating Limits for Organic HAP Emissions From Catalytic Cracking Units 14 Table 14 to Subpart UUU of Part 63... Reforming Units, and Sulfur Recovery Units Pt. 63, Subpt. UUU, Table 14 Table 14 to Subpart UUU of Part 63...

40 CFR Table 13 to Subpart Uuu of... - Continuous Compliance With Organic HAP Emission Limits for Catalytic Cracking Units

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 12 2011-07-01 2009-07-01 true Continuous Compliance With Organic HAP Emission Limits for Catalytic Cracking Units 13 Table 13 to Subpart UUU of Part 63 Protection of... Units Pt. 63, Subpt. UUU, Table 13 Table 13 to Subpart UUU of Part 63—Continuous Compliance With Organic...

40 CFR Table 12 to Subpart Uuu of... - Initial Compliance With Organic HAP Emission Limits for Catalytic Cracking Units

Code of Federal Regulations, 2013 CFR

2013-07-01

... 40 Protection of Environment 13 2013-07-01 2012-07-01 true Initial Compliance With Organic HAP Emission Limits for Catalytic Cracking Units 12 Table 12 to Subpart UUU of Part 63 Protection of... Sulfur Recovery Units Pt. 63, Subpt. UUU, Table 12 Table 12 to Subpart UUU of Part 63—Initial Compliance...

40 CFR Table 12 to Subpart Uuu of... - Initial Compliance With Organic HAP Emission Limits for Catalytic Cracking Units

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 12 2011-07-01 2009-07-01 true Initial Compliance With Organic HAP Emission Limits for Catalytic Cracking Units 12 Table 12 to Subpart UUU of Part 63 Protection of... Units Pt. 63, Subpt. UUU, Table 12 Table 12 to Subpart UUU of Part 63—Initial Compliance With Organic...

40 CFR Table 12 to Subpart Uuu of... - Initial Compliance With Organic HAP Emission Limits for Catalytic Cracking Units

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 12 2010-07-01 2010-07-01 true Initial Compliance With Organic HAP Emission Limits for Catalytic Cracking Units 12 Table 12 to Subpart UUU of Part 63 Protection of... Units Pt. 63, Subpt. UUU, Table 12 Table 12 to Subpart UUU of Part 63—Initial Compliance With Organic...

40 CFR Table 7 to Subpart Uuu of... - Continuous Compliance With Operating Limits for Metal HAP Emissions From Catalytic Cracking Units

Code of Federal Regulations, 2012 CFR

2012-07-01

... 40 Protection of Environment 13 2012-07-01 2012-07-01 false Continuous Compliance With Operating Limits for Metal HAP Emissions From Catalytic Cracking Units 7 Table 7 to Subpart UUU of Part 63... Reforming Units, and Sulfur Recovery Units Pt. 63, Subpt. UUU, Table 7 Table 7 to Subpart UUU of Part 63...

40 CFR Table 7 to Subpart Uuu of... - Continuous Compliance With Operating Limits for Metal HAP Emissions From Catalytic Cracking Units

Code of Federal Regulations, 2013 CFR

2013-07-01

... 40 Protection of Environment 13 2013-07-01 2012-07-01 true Continuous Compliance With Operating Limits for Metal HAP Emissions From Catalytic Cracking Units 7 Table 7 to Subpart UUU of Part 63... Reforming Units, and Sulfur Recovery Units Pt. 63, Subpt. UUU, Table 7 Table 7 to Subpart UUU of Part 63...

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

Code of Federal Regulations, 2012 CFR

2012-07-01

... 40 Protection of Environment 13 2012-07-01 2012-07-01 false Operating Limits for Metal HAP Emissions From Catalytic Cracking Units 2 Table 2 to Subpart UUU of Part 63 Protection of Environment... Units Pt. 63, Subpt. UUU, Table 2 Table 2 to Subpart UUU of Part 63—Operating Limits for Metal HAP...

40 CFR Table 13 to Subpart Uuu of... - Continuous Compliance With Organic HAP Emission Limits for Catalytic Cracking Units

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 12 2010-07-01 2010-07-01 true Continuous Compliance With Organic HAP Emission Limits for Catalytic Cracking Units 13 Table 13 to Subpart UUU of Part 63 Protection of... Units Pt. 63, Subpt. UUU, Table 13 Table 13 to Subpart UUU of Part 63—Continuous Compliance With Organic...

40 CFR Table 14 to Subpart Uuu of... - Continuous Compliance With Operating Limits for Organic HAP Emissions From Catalytic Cracking Units

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 12 2011-07-01 2009-07-01 true Continuous Compliance With Operating Limits for Organic HAP Emissions From Catalytic Cracking Units 14 Table 14 to Subpart UUU of Part 63... Sulfur Recovery Units Pt. 63, Subpt. UUU, Table 14 Table 14 to Subpart UUU of Part 63—Continuous...

40 CFR Table 9 to Subpart Uuu of... - Operating Limits for Organic HAP Emissions From Catalytic Cracking Units

Code of Federal Regulations, 2013 CFR

2013-07-01

... 40 Protection of Environment 13 2013-07-01 2012-07-01 true Operating Limits for Organic HAP Emissions From Catalytic Cracking Units 9 Table 9 to Subpart UUU of Part 63 Protection of Environment... Units Pt. 63, Subpt. UUU, Table 9 Table 9 to Subpart UUU of Part 63—Operating Limits for Organic HAP...

40 CFR Table 13 to Subpart Uuu of... - Continuous Compliance With Organic HAP Emission Limits for Catalytic Cracking Units

Code of Federal Regulations, 2012 CFR

2012-07-01

... 40 Protection of Environment 13 2012-07-01 2012-07-01 false Continuous Compliance With Organic HAP Emission Limits for Catalytic Cracking Units 13 Table 13 to Subpart UUU of Part 63 Protection of... Sulfur Recovery Units Pt. 63, Subpt. UUU, Table 13 Table 13 to Subpart UUU of Part 63—Continuous...

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

Code of Federal Regulations, 2013 CFR

2013-07-01

... 40 Protection of Environment 13 2013-07-01 2012-07-01 true Operating Limits for Metal HAP Emissions From Catalytic Cracking Units 2 Table 2 to Subpart UUU of Part 63 Protection of Environment... Units Pt. 63, Subpt. UUU, Table 2 Table 2 to Subpart UUU of Part 63—Operating Limits for Metal HAP...

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

Code of Federal Regulations, 2013 CFR

2013-07-01

... 40 Protection of Environment 13 2013-07-01 2012-07-01 true Continous Monitoring Systems for Metal HAP Emissions From Catalytic Cracking Units 3 Table 3 to Subpart UUU of Part 63 Protection of... Sulfur Recovery Units Pt. 63, Subpt. UUU, Table 3 Table 3 to Subpart UUU of Part 63—Continous Monitoring...

40 CFR Table 9 to Subpart Uuu of... - Operating Limits for Organic HAP Emissions From Catalytic Cracking Units

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 12 2010-07-01 2010-07-01 true Operating Limits for Organic HAP Emissions From Catalytic Cracking Units 9 Table 9 to Subpart UUU of Part 63 Protection of Environment..., Subpt. UUU, Table 9 Table 9 to Subpart UUU of Part 63—Operating Limits for Organic HAP Emissions From...

40 CFR Table 13 to Subpart Uuu of... - Continuous Compliance With Organic HAP Emission Limits for Catalytic Cracking Units

Code of Federal Regulations, 2013 CFR

2013-07-01

... 40 Protection of Environment 13 2013-07-01 2012-07-01 true Continuous Compliance With Organic HAP Emission Limits for Catalytic Cracking Units 13 Table 13 to Subpart UUU of Part 63 Protection of... Sulfur Recovery Units Pt. 63, Subpt. UUU, Table 13 Table 13 to Subpart UUU of Part 63—Continuous...

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

Code of Federal Regulations, 2014 CFR

2014-07-01

... 40 Protection of Environment 13 2014-07-01 2014-07-01 false Operating Limits for Metal HAP Emissions From Catalytic Cracking Units 2 Table 2 to Subpart UUU of Part 63 Protection of Environment... Units Pt. 63, Subpt. UUU, Table 2 Table 2 to Subpart UUU of Part 63—Operating Limits for Metal HAP...

40 CFR Table 12 to Subpart Uuu of... - Initial Compliance With Organic HAP Emission Limits for Catalytic Cracking Units

Code of Federal Regulations, 2014 CFR

2014-07-01

... 40 Protection of Environment 13 2014-07-01 2014-07-01 false Initial Compliance With Organic HAP Emission Limits for Catalytic Cracking Units 12 Table 12 to Subpart UUU of Part 63 Protection of... Sulfur Recovery Units Pt. 63, Subpt. UUU, Table 12 Table 12 to Subpart UUU of Part 63—Initial Compliance...

40 CFR Table 9 to Subpart Uuu of... - Operating Limits for Organic HAP Emissions From Catalytic Cracking Units

Code of Federal Regulations, 2014 CFR

2014-07-01

... 40 Protection of Environment 13 2014-07-01 2014-07-01 false Operating Limits for Organic HAP Emissions From Catalytic Cracking Units 9 Table 9 to Subpart UUU of Part 63 Protection of Environment... Units Pt. 63, Subpt. UUU, Table 9 Table 9 to Subpart UUU of Part 63—Operating Limits for Organic HAP...

40 CFR Table 12 to Subpart Uuu of... - Initial Compliance With Organic HAP Emission Limits for Catalytic Cracking Units

Code of Federal Regulations, 2012 CFR

2012-07-01

... 40 Protection of Environment 13 2012-07-01 2012-07-01 false Initial Compliance With Organic HAP Emission Limits for Catalytic Cracking Units 12 Table 12 to Subpart UUU of Part 63 Protection of... Sulfur Recovery Units Pt. 63, Subpt. UUU, Table 12 Table 12 to Subpart UUU of Part 63—Initial Compliance...

40 CFR Table 14 to Subpart Uuu of... - Continuous Compliance With Operating Limits for Organic HAP Emissions From Catalytic Cracking Units

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 12 2010-07-01 2010-07-01 true Continuous Compliance With Operating Limits for Organic HAP Emissions From Catalytic Cracking Units 14 Table 14 to Subpart UUU of Part 63... Sulfur Recovery Units Pt. 63, Subpt. UUU, Table 14 Table 14 to Subpart UUU of Part 63—Continuous...

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

Code of Federal Regulations, 2012 CFR

2012-07-01

... 40 Protection of Environment 13 2012-07-01 2012-07-01 false Continous Monitoring Systems for Metal HAP Emissions From Catalytic Cracking Units 3 Table 3 to Subpart UUU of Part 63 Protection of... Sulfur Recovery Units Pt. 63, Subpt. UUU, Table 3 Table 3 to Subpart UUU of Part 63—Continous Monitoring...

40 CFR Table 9 to Subpart Uuu of... - Operating Limits for Organic HAP Emissions From Catalytic Cracking Units

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 12 2011-07-01 2009-07-01 true Operating Limits for Organic HAP Emissions From Catalytic Cracking Units 9 Table 9 to Subpart UUU of Part 63 Protection of Environment..., Subpt. UUU, Table 9 Table 9 to Subpart UUU of Part 63—Operating Limits for Organic HAP Emissions From...

40 CFR Table 9 to Subpart Uuu of... - Operating Limits for Organic HAP Emissions From Catalytic Cracking Units

Code of Federal Regulations, 2012 CFR

2012-07-01

... 40 Protection of Environment 13 2012-07-01 2012-07-01 false Operating Limits for Organic HAP Emissions From Catalytic Cracking Units 9 Table 9 to Subpart UUU of Part 63 Protection of Environment... Units Pt. 63, Subpt. UUU, Table 9 Table 9 to Subpart UUU of Part 63—Operating Limits for Organic HAP...

40 CFR Table 7 to Subpart Uuu of... - Continuous Compliance With Operating Limits for Metal HAP Emissions From Catalytic Cracking Units

Code of Federal Regulations, 2014 CFR

2014-07-01

... 40 Protection of Environment 13 2014-07-01 2014-07-01 false Continuous Compliance With Operating Limits for Metal HAP Emissions From Catalytic Cracking Units 7 Table 7 to Subpart UUU of Part 63... Reforming Units, and Sulfur Recovery Units Pt. 63, Subpt. UUU, Table 7 Table 7 to Subpart UUU of Part 63...

40 CFR Table 14 to Subpart Uuu of... - Continuous Compliance With Operating Limits for Organic HAP Emissions From Catalytic Cracking Units

Code of Federal Regulations, 2012 CFR

2012-07-01

... 40 Protection of Environment 13 2012-07-01 2012-07-01 false Continuous Compliance With Operating Limits for Organic HAP Emissions From Catalytic Cracking Units 14 Table 14 to Subpart UUU of Part 63... Reforming Units, and Sulfur Recovery Units Pt. 63, Subpt. UUU, Table 14 Table 14 to Subpart UUU of Part 63...

40 CFR Table 22 to Subpart Uuu of... - Inorganic HAP Emission Limits for Catalytic Reforming Units

Code of Federal Regulations, 2011 CFR

2011-07-01

... Catalytic Reforming Units 22 Table 22 to Subpart UUU of Part 63 Protection of Environment ENVIRONMENTAL... Refineries: Catalytic Cracking Units, Catalytic Reforming Units, and Sulfur Recovery Units Pt. 63, Subpt. UUU, Table 22 Table 22 to Subpart UUU of Part 63—Inorganic HAP Emission Limits for Catalytic Reforming Units...

40 CFR Table 22 to Subpart Uuu of... - Inorganic HAP Emission Limits for Catalytic Reforming Units

Code of Federal Regulations, 2010 CFR

2010-07-01

... Catalytic Reforming Units 22 Table 22 to Subpart UUU of Part 63 Protection of Environment ENVIRONMENTAL... Refineries: Catalytic Cracking Units, Catalytic Reforming Units, and Sulfur Recovery Units Pt. 63, Subpt. UUU, Table 22 Table 22 to Subpart UUU of Part 63—Inorganic HAP Emission Limits for Catalytic Reforming Units...

40 CFR Table 15 to Subpart Uuu of... - Organic HAP Emission Limits for Catalytic Reforming Units

Code of Federal Regulations, 2010 CFR

2010-07-01

... Catalytic Reforming Units 15 Table 15 to Subpart UUU of Part 63 Protection of Environment ENVIRONMENTAL... Refineries: Catalytic Cracking Units, Catalytic Reforming Units, and Sulfur Recovery Units Pt. 63, Subpt. UUU, Table 15 Table 15 to Subpart UUU of Part 63—Organic HAP Emission Limits for Catalytic Reforming Units As...

40 CFR Table 15 to Subpart Uuu of... - Organic HAP Emission Limits for Catalytic Reforming Units

Code of Federal Regulations, 2011 CFR

2011-07-01

... Catalytic Reforming Units 15 Table 15 to Subpart UUU of Part 63 Protection of Environment ENVIRONMENTAL... Refineries: Catalytic Cracking Units, Catalytic Reforming Units, and Sulfur Recovery Units Pt. 63, Subpt. UUU, Table 15 Table 15 to Subpart UUU of Part 63—Organic HAP Emission Limits for Catalytic Reforming Units As...

Too much FCC catalyst activity can cut yields

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

Wichers, W.R.; Upson, L.

1984-03-19

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

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

PubMed

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

2013-09-09

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

Catalytic processes towards the production of biofuels in a palm oil and oil palm biomass-based biorefinery.

PubMed

Chew, Thiam Leng; Bhatia, Subhash

2008-11-01

In Malaysia, there has been interest in the utilization of palm oil and oil palm biomass for the production of environmental friendly biofuels. A biorefinery based on palm oil and oil palm biomass for the production of biofuels has been proposed. The catalytic technology plays major role in the different processing stages in a biorefinery for the production of liquid as well as gaseous biofuels. There are number of challenges to find suitable catalytic technology to be used in a typical biorefinery. These challenges include (1) economic barriers, (2) catalysts that facilitate highly selective conversion of substrate to desired products and (3) the issues related to design, operation and control of catalytic reactor. Therefore, the catalytic technology is one of the critical factors that control the successful operation of biorefinery. There are number of catalytic processes in a biorefinery which convert the renewable feedstocks into the desired biofuels. These include biodiesel production from palm oil, catalytic cracking of palm oil for the production of biofuels, the production of hydrogen as well as syngas from biomass gasification, Fischer-Tropsch synthesis (FTS) for the conversion of syngas into liquid fuels and upgrading of liquid/gas fuels obtained from liquefaction/pyrolysis of biomass. The selection of catalysts for these processes is essential in determining the product distribution (olefins, paraffins and oxygenated products). The integration of catalytic technology with compatible separation processes is a key challenge for biorefinery operation from the economic point of view. This paper focuses on different types of catalysts and their role in the catalytic processes for the production of biofuels in a typical palm oil and oil palm biomass-based biorefinery.

Life and death of a single catalytic cracking particle

PubMed Central

Meirer, Florian; Kalirai, Sam; Morris, Darius; Soparawalla, Santosh; Liu, Yijin; Mesu, Gerbrand; Andrews, Joy C.; Weckhuysen, Bert M.

2015-01-01

Fluid catalytic cracking (FCC) particles account for 40 to 45% of worldwide gasoline production. The hierarchical complex particle pore structure allows access of long-chain feedstock molecules into active catalyst domains where they are cracked into smaller, more valuable hydrocarbon products (for example, gasoline). In this process, metal deposition and intrusion is a major cause for irreversible catalyst deactivation and shifts in product distribution. We used x-ray nanotomography of industrial FCC particles at differing degrees of deactivation to quantify changes in single-particle macroporosity and pore connectivity, correlated to iron and nickel deposition. Our study reveals that these metals are incorporated almost exclusively in near-surface regions, severely limiting macropore accessibility as metal concentrations increase. Because macropore channels are “highways” of the pore network, blocking them prevents feedstock molecules from reaching the catalytically active domains. Consequently, metal deposition reduces conversion with time on stream because the internal pore volume, although itself unobstructed, becomes largely inaccessible. PMID:26601160

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.

40 CFR 63.1560 - What is the purpose of this subpart?

Code of Federal Regulations, 2010 CFR

2010-07-01

... Standards for Hazardous Air Pollutants for Petroleum Refineries: Catalytic Cracking Units, Catalytic... from petroleum refineries. This subpart also establishes requirements to demonstrate initial and continuous compliance with the emission limitations and work practice standards. ...

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.

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

PubMed Central

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

2014-01-01

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

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.

Packed-bed catalytic cracking of oak derived pyrolytic vapors

USDA-ARS?s Scientific Manuscript database

Catalytic upgrading of pyrolysis vapors derived from oak was carried out using a fixed-bed catalytic column at 425 deg C. The vapors were drawn by splitting a fraction from the full stream of vapors produced at 500 deg C in a 5 kg/hr bench-scale fast pyrolysis reactor system downstream the cyclone s...

[Selective catalytic reduction of NOx over Pd/CeZr/TiO2/Al2O3 wire-mesh honeycomb catalysts].

PubMed

Sun, Hong; Quan, Xie; Zhang, Yao-bin; Zhao, Ya-zhi

2008-06-01

Pd/CeZr/TiO2/Al2O3 wire-mesh honeycomb catalyst was prepared by sol-gel and impregnation. Furthermore, selective catalytic reduction of NOx over Pd/CeZr/TiO2/Al2O3 wire-mesh honeycomb catalyst with propylene under lean burn condition was studied. The effects of the concentration of tetra-n-butyl titanate and dipcoat cycles on TiO2 washcoat were studied by SEM, and the effects of Pd concentration, O2 concentration and gas velocity on catalytic activity were investigated. The experimental results showed that the TiO2 washcoat on wire-mesh support is even and crack-free when the support is impregnated in 20.0% tetra- n-butyl titanate sol for 2 cycles. The NOx conversion decreases with Pd concentration increase. When Pd concentration is 0.23%, NOx conversion is highest. NOx conversion increases with oxygen concentration increase in the range of 1.5%-6.0%. However, when oxygen concentration is higher than 6.0%, NOx conversion decreases with increasing oxygen concentration. The NOx conversion decreases with gas velocity increase and its effect is severer at high temperature than low temperature.

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

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

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

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

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

DOE PAGES

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

2017-01-31

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

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

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

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

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

X-ray Fluorescence Tomography of Aged Fluid-Catalytic-Cracking Catalyst Particles Reveals Insight into Metal Deposition Processes.

PubMed

Kalirai, Sam; Boesenberg, Ulrike; Falkenberg, Gerald; Meirer, Florian; Weckhuysen, Bert M

2015-11-01

Microprobe X-ray fluorescence tomography was used to investigate metal poison deposition in individual, intact and industrially deactivated fluid catalytic cracking (FCC) particles at two differing catalytic life-stages. 3 D multi-element imaging, at submicron resolution was achieved by using a large-array Maia fluorescence detector. Our results show that Fe, Ni and Ca have significant concentration at the exterior of the FCC catalyst particle and are highly co-localized. As concentrations increase as a function of catalytic life-stage, the deposition profiles of Fe, Ni, and Ca do not change significantly. V has been shown to penetrate deeper into the particle with increasing catalytic age. Although it has been previously suggested that V is responsible for damaging the zeolite components of FCC particles, no spatial correlation was found for V and La, which was used as a marker for the embedded zeolite domains. This suggests that although V is known to be detrimental to zeolites in FCC particles, a preferential interaction does not exist between the two.

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

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

Sabyrov, Kairat; Musselwhite, Nathan; Melaet, Gérôme

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

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

DOE PAGES

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

2017-01-01

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

Catalytic thermal cracking of post-consumer waste plastics to fuels: Part 1 - Kinetics and optimization

USDA-ARS?s Scientific Manuscript database

Thermogravimetric analysis (TGA) was used to investigate thermal and catalytic pyrolysis of waste plastics such as prescription bottles (polypropylene/PP), high density polyethylene, landfill liners (polyethylene/PE), packing materials (polystyrene/PS), and foams (polyurethane/PU) into crude plastic...

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

Honghong Shan; Jianfang Zhang; Guohe Que

The physical-chemical properties and catalytic cracking behaviors of Gudao VR and Gudao VRDS VR were studied. The properties are structural parameters show that the C/H, Mw, R{sub A}, f{sub A} values and nitrogen, sulfur, nickel, resin contents of the Gudao VRDS VR are obviously lower than those of Gudao VR, and that the content of saturates of Gudao VRDS VR are considerably higher than that of Gudao VR. The catalytic cracking experiments of Gudao VRDS VR in laboratory scale show that VRDS VR has good cracking behaviour. The research and industry scale results indicate that the VRDS process using Gudaomore » VR as feedstock is a kind of high efficiency hydrotreating process, and that VRDS-FCC complex technology can realize the deep processing of the crude, increase the light oil yields and enhance the economical profit of the enterprise.« less

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

PubMed

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

2014-11-01

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

Screening acidic zeolites for catalytic fast pyrolysis of biomass and its components

USDA-ARS?s Scientific Manuscript database

Zeolites have been shown to effectively promote cracking reactions during pyrolysis resulting in highly deoxygenated and hydrocarbon-rich compounds and stable pyrolysis oil product. Py/GC-MS was employed to study the catalytic fast pyrolysis of lignocellulosic biomass samples comprising oak, corn...

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 thermal cracking of postconsumer waste plastics to fuels. 2. Pilot-scale thermochemical conversion

USDA-ARS?s Scientific Manuscript database

Synthetic gasoline and diesel fuels were prepared via catalytic and noncatalytic pyrolysis of waste polyethylene and polypropylene plastics followed by distillation of plastic crude oils. Reaction conditions optimized using a 2 L batch reactor were applied to pilot-scale production of plastic crude ...

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.

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.

40 CFR Table 37 to Subpart Uuu of... - Requirements for Performance Tests for Bypass Lines

Code of Federal Regulations, 2012 CFR

2012-07-01

... Bypass Lines 37 Table 37 to Subpart UUU of Part 63 Protection of Environment ENVIRONMENTAL PROTECTION... Refineries: Catalytic Cracking Units, Catalytic Reforming Units, and Sulfur Recovery Units Pt. 63, Subpt. UUU, Table 37 Table 37 to Subpart UUU of Part 63—Requirements for Performance Tests for Bypass Lines As...

40 CFR Table 37 to Subpart Uuu of... - Requirements for Performance Tests for Bypass Lines

Code of Federal Regulations, 2014 CFR

2014-07-01

... Bypass Lines 37 Table 37 to Subpart UUU of Part 63 Protection of Environment ENVIRONMENTAL PROTECTION... Refineries: Catalytic Cracking Units, Catalytic Reforming Units, and Sulfur Recovery Units Pt. 63, Subpt. UUU, Table 37 Table 37 to Subpart UUU of Part 63—Requirements for Performance Tests for Bypass Lines As...

40 CFR Table 29 to Subpart Uuu of... - HAP Emission Limits for Sulfur Recovery Units

Code of Federal Regulations, 2014 CFR

2014-07-01

... Recovery Units 29 Table 29 to Subpart UUU of Part 63 Protection of Environment ENVIRONMENTAL PROTECTION... Refineries: Catalytic Cracking Units, Catalytic Reforming Units, and Sulfur Recovery Units Pt. 63, Subpt. UUU, Table 29 Table 29 to Subpart UUU of Part 63—HAP Emission Limits for Sulfur Recovery Units As stated in...

40 CFR Table 42 to Subpart Uuu of... - Additional Information for Initial Notification of Compliance Status

Code of Federal Regulations, 2010 CFR

2010-07-01

... Notification of Compliance Status 42 Table 42 to Subpart UUU of Part 63 Protection of Environment ENVIRONMENTAL... Refineries: Catalytic Cracking Units, Catalytic Reforming Units, and Sulfur Recovery Units Pt. 63, Subpt. UUU, Table 42 Table 42 to Subpart UUU of Part 63—Additional Information for Initial Notification of...

40 CFR Table 30 to Subpart Uuu of... - Operating Limits for HAP Emissions From Sulfur Recovery Units

Code of Federal Regulations, 2011 CFR

2011-07-01

... Sulfur Recovery Units 30 Table 30 to Subpart UUU of Part 63 Protection of Environment ENVIRONMENTAL... Refineries: Catalytic Cracking Units, Catalytic Reforming Units, and Sulfur Recovery Units Pt. 63, Subpt. UUU, Table 30 Table 30 to Subpart UUU of Part 63—Operating Limits for HAP Emissions From Sulfur Recovery...

40 CFR Table 40 to Subpart Uuu of... - Requirements for Installation, Operation, and Maintenance of Continuous Opacity Monitoring...

Code of Federal Regulations, 2013 CFR

2013-07-01

... Systems 40 Table 40 to Subpart UUU of Part 63 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY...: Catalytic Cracking Units, Catalytic Reforming Units, and Sulfur Recovery Units Pt. 63, Subpt. UUU, Table 40 Table 40 to Subpart UUU of Part 63—Requirements for Installation, Operation, and Maintenance of...

40 CFR Table 40 to Subpart Uuu of... - Requirements for Installation, Operation, and Maintenance of Continuous Opacity Monitoring...

Code of Federal Regulations, 2014 CFR

2014-07-01

... Systems 40 Table 40 to Subpart UUU of Part 63 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY...: Catalytic Cracking Units, Catalytic Reforming Units, and Sulfur Recovery Units Pt. 63, Subpt. UUU, Table 40 Table 40 to Subpart UUU of Part 63—Requirements for Installation, Operation, and Maintenance of...

40 CFR Table 40 to Subpart Uuu of... - Requirements for Installation, Operation, and Maintenance of Continuous Opacity Monitoring...

Code of Federal Regulations, 2012 CFR

2012-07-01

... Systems 40 Table 40 to Subpart UUU of Part 63 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY...: Catalytic Cracking Units, Catalytic Reforming Units, and Sulfur Recovery Units Pt. 63, Subpt. UUU, Table 40 Table 40 to Subpart UUU of Part 63—Requirements for Installation, Operation, and Maintenance of...

40 CFR Table 42 to Subpart Uuu of... - Additional Information for Initial Notification of Compliance Status

Code of Federal Regulations, 2011 CFR

2011-07-01

... Notification of Compliance Status 42 Table 42 to Subpart UUU of Part 63 Protection of Environment ENVIRONMENTAL... Refineries: Catalytic Cracking Units, Catalytic Reforming Units, and Sulfur Recovery Units Pt. 63, Subpt. UUU, Table 42 Table 42 to Subpart UUU of Part 63—Additional Information for Initial Notification of...

40 CFR Table 37 to Subpart Uuu of... - Requirements for Performance Tests for Bypass Lines

Code of Federal Regulations, 2013 CFR

2013-07-01

... Bypass Lines 37 Table 37 to Subpart UUU of Part 63 Protection of Environment ENVIRONMENTAL PROTECTION... Refineries: Catalytic Cracking Units, Catalytic Reforming Units, and Sulfur Recovery Units Pt. 63, Subpt. UUU, Table 37 Table 37 to Subpart UUU of Part 63—Requirements for Performance Tests for Bypass Lines As...

40 CFR Table 29 to Subpart Uuu of... - HAP Emission Limits for Sulfur Recovery Units

Code of Federal Regulations, 2012 CFR

2012-07-01

... Recovery Units 29 Table 29 to Subpart UUU of Part 63 Protection of Environment ENVIRONMENTAL PROTECTION... Refineries: Catalytic Cracking Units, Catalytic Reforming Units, and Sulfur Recovery Units Pt. 63, Subpt. UUU, Table 29 Table 29 to Subpart UUU of Part 63—HAP Emission Limits for Sulfur Recovery Units As stated in...

Phosphorus promotion and poisoning in zeolite-based materials: synthesis, characterisation and catalysis

PubMed Central

van der Bij, Hendrik E.

2015-01-01

Phosphorus and microporous aluminosilicates, better known as zeolites, have a unique but poorly understood relationship. For example, phosphatation of the industrially important zeolite H-ZSM-5 is a well-known, relatively inexpensive and seemingly straightforward post-synthetic modification applied by the chemical industry not only to alter its hydrothermal stability and acidity, but also to increase its selectivity towards light olefins in hydrocarbon catalysis. On the other hand, phosphorus poisoning of zeolite-based catalysts, which are used for removing nitrogen oxides from exhaust fuels, poses a problem for their use in diesel engine catalysts. Despite the wide impact of phosphorus–zeolite chemistry, the exact physicochemical processes that take place require a more profound understanding. This review article provides the reader with a comprehensive and state-of-the-art overview of the academic literature, from the first reports in the late 1970s until the most recent studies. In the first part an in-depth analysis is undertaken, which will reveal universal physicochemical and structural effects of phosphorus–zeolite chemistry on the framework structure, accessibility, and strength of acid sites. The second part discusses the hydrothermal stability of zeolites and clarifies the promotional role that phosphorus plays. The third part of the review paper links the structural and physicochemical effects of phosphorus on zeolite materials with their catalytic performance in a variety of catalytic processes, including alkylation of aromatics, catalytic cracking, methanol-to-hydrocarbon processing, dehydration of bioalcohol, and ammonia selective catalytic reduction (SCR) of NOx. Based on these insights, we discuss potential applications and important directions for further research. PMID:26051875

Phosphorus promotion and poisoning in zeolite-based materials: synthesis, characterisation and catalysis.

PubMed

van der Bij, Hendrik E; Weckhuysen, Bert M

2015-10-21

Phosphorus and microporous aluminosilicates, better known as zeolites, have a unique but poorly understood relationship. For example, phosphatation of the industrially important zeolite H-ZSM-5 is a well-known, relatively inexpensive and seemingly straightforward post-synthetic modification applied by the chemical industry not only to alter its hydrothermal stability and acidity, but also to increase its selectivity towards light olefins in hydrocarbon catalysis. On the other hand, phosphorus poisoning of zeolite-based catalysts, which are used for removing nitrogen oxides from exhaust fuels, poses a problem for their use in diesel engine catalysts. Despite the wide impact of phosphorus-zeolite chemistry, the exact physicochemical processes that take place require a more profound understanding. This review article provides the reader with a comprehensive and state-of-the-art overview of the academic literature, from the first reports in the late 1970s until the most recent studies. In the first part an in-depth analysis is undertaken, which will reveal universal physicochemical and structural effects of phosphorus-zeolite chemistry on the framework structure, accessibility, and strength of acid sites. The second part discusses the hydrothermal stability of zeolites and clarifies the promotional role that phosphorus plays. The third part of the review paper links the structural and physicochemical effects of phosphorus on zeolite materials with their catalytic performance in a variety of catalytic processes, including alkylation of aromatics, catalytic cracking, methanol-to-hydrocarbon processing, dehydration of bioalcohol, and ammonia selective catalytic reduction (SCR) of NOx. Based on these insights, we discuss potential applications and important directions for further research.

Biodiesel synthesis using chicken manure biochar and waste cooking oil.

PubMed

Jung, Jong-Min; Lee, Sang-Ryong; Lee, Jechan; Lee, Taewoo; Tsang, Daniel C W; Kwon, Eilhann E

2017-11-01

This study laid an emphasis on the possible employment of biochar generated from pyrolysis of chicken manure to establish a green platform for producing biodiesel. To this end, the pseudo-catalytic transesterification reaction using chicken manure biochar and waste cooking oil was investigated. Compared with a commercial porous material (SiO 2 ), chicken manure biochar generated from 350°C showed better performance, resulting in 95.6% of the FAME yield at 350°C. The Ca species in chicken manure biochar imparted strong catalytic capability by providing the basicity for transesterification. The identified catalytic effect also led to the thermal cracking of unsaturated FAMEs, which decreased the overall FAME yield. For example, 40-60% of converted FAMEs were thermally degraded. To avoid undesirable thermal cracking arising from the high content of the Ca species in chicken manure biochar, the fabrication of chicken manure biochar at temperatures ≥350°C was highly recommended. Copyright © 2017 Elsevier Ltd. All rights reserved.

40 CFR Table 29 to Subpart Uuu of... - HAP Emission Limits for Sulfur Recovery Units

Code of Federal Regulations, 2013 CFR

2013-07-01

... Units 29 Table 29 to Subpart UUU of Part 63 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY...: Catalytic Cracking Units, Catalytic Reforming Units, and Sulfur Recovery Units Pt. 63, Subpt. UUU, Table 29 Table 29 to Subpart UUU of Part 63—HAP Emission Limits for Sulfur Recovery Units As stated in § 63.1568...

40 CFR Table 37 to Subpart Uuu of... - Requirements for Performance Tests for Bypass Lines

Code of Federal Regulations, 2010 CFR

2010-07-01

... Bypass Lines 37 Table 37 to Subpart UUU of Part 63 Protection of Environment ENVIRONMENTAL PROTECTION...: Catalytic Cracking Units, Catalytic Reforming Units, and Sulfur Recovery Units Pt. 63, Subpt. UUU, Table 37 Table 37 to Subpart UUU of Part 63—Requirements for Performance Tests for Bypass Lines As stated in § 63...

40 CFR Table 44 to Subpart Uuu of... - Applicability of NESHAP General Provisions to Subpart UUU

Code of Federal Regulations, 2011 CFR

2011-07-01

... Provisions to Subpart UUU 44 Table 44 to Subpart UUU of Part 63 Protection of Environment ENVIRONMENTAL... Refineries: Catalytic Cracking Units, Catalytic Reforming Units, and Sulfur Recovery Units Pt. 63, Subpt. UUU, Table 44 Table 44 to Subpart UUU of Part 63—Applicability of NESHAP General Provisions to Subpart UUU As...

40 CFR Table 44 to Subpart Uuu of... - Applicability of NESHAP General Provisions to Subpart UUU

Code of Federal Regulations, 2010 CFR

2010-07-01

... Provisions to Subpart UUU 44 Table 44 to Subpart UUU of Part 63 Protection of Environment ENVIRONMENTAL... Refineries: Catalytic Cracking Units, Catalytic Reforming Units, and Sulfur Recovery Units Pt. 63, Subpt. UUU, Table 44 Table 44 to Subpart UUU of Part 63—Applicability of NESHAP General Provisions to Subpart UUU As...

40 CFR Table 36 to Subpart Uuu of... - Work Practice Standards for HAP Emissions From Bypass Lines

Code of Federal Regulations, 2011 CFR

2011-07-01

... Emissions From Bypass Lines 36 Table 36 to Subpart UUU of Part 63 Protection of Environment ENVIRONMENTAL... Refineries: Catalytic Cracking Units, Catalytic Reforming Units, and Sulfur Recovery Units Pt. 63, Subpt. UUU, Table 36 Table 36 to Subpart UUU of Part 63—Work Practice Standards for HAP Emissions From Bypass Lines...

40 CFR Table 37 to Subpart Uuu of... - Requirements for Performance Tests for Bypass Lines

Code of Federal Regulations, 2011 CFR

2011-07-01

... Bypass Lines 37 Table 37 to Subpart UUU of Part 63 Protection of Environment ENVIRONMENTAL PROTECTION...: Catalytic Cracking Units, Catalytic Reforming Units, and Sulfur Recovery Units Pt. 63, Subpt. UUU, Table 37 Table 37 to Subpart UUU of Part 63—Requirements for Performance Tests for Bypass Lines As stated in § 63...

40 CFR Table 36 to Subpart Uuu of... - Work Practice Standards for HAP Emissions From Bypass Lines

Code of Federal Regulations, 2010 CFR

2010-07-01

... Emissions From Bypass Lines 36 Table 36 to Subpart UUU of Part 63 Protection of Environment ENVIRONMENTAL... Refineries: Catalytic Cracking Units, Catalytic Reforming Units, and Sulfur Recovery Units Pt. 63, Subpt. UUU, Table 36 Table 36 to Subpart UUU of Part 63—Work Practice Standards for HAP Emissions From Bypass Lines...

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.

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 Table 32 to Subpart Uuu of... - Requirements for Performance Tests for HAP Emissions From Sulfur Recovery Units Not Subject to...

Code of Federal Regulations, 2011 CFR

2011-07-01

... Sulfur Oxides 32 Table 32 to Subpart UUU of Part 63 Protection of Environment ENVIRONMENTAL PROTECTION...: Catalytic Cracking Units, Catalytic Reforming Units, and Sulfur Recovery Units Pt. 63, Subpt. UUU, Table 32 Table 32 to Subpart UUU of Part 63—Requirements for Performance Tests for HAP Emissions From Sulfur...

40 CFR Table 32 to Subpart Uuu of... - Requirements for Performance Tests for HAP Emissions From Sulfur Recovery Units Not Subject to...

Code of Federal Regulations, 2014 CFR

2014-07-01

... Sulfur Oxides 32 Table 32 to Subpart UUU of Part 63 Protection of Environment ENVIRONMENTAL PROTECTION... Refineries: Catalytic Cracking Units, Catalytic Reforming Units, and Sulfur Recovery Units Pt. 63, Subpt. UUU, Table 32 Table 32 to Subpart UUU of Part 63—Requirements for Performance Tests for HAP Emissions From...

40 CFR Table 32 to Subpart Uuu of... - Requirements for Performance Tests for HAP Emissions From Sulfur Recovery Units Not Subject to...

Code of Federal Regulations, 2013 CFR

2013-07-01

... Sulfur Oxides 32 Table 32 to Subpart UUU of Part 63 Protection of Environment ENVIRONMENTAL PROTECTION... Refineries: Catalytic Cracking Units, Catalytic Reforming Units, and Sulfur Recovery Units Pt. 63, Subpt. UUU, Table 32 Table 32 to Subpart UUU of Part 63—Requirements for Performance Tests for HAP Emissions From...

40 CFR Table 32 to Subpart Uuu of... - Requirements for Performance Tests for HAP Emissions From Sulfur Recovery Units Not Subject to...

Code of Federal Regulations, 2012 CFR

2012-07-01

... Sulfur Oxides 32 Table 32 to Subpart UUU of Part 63 Protection of Environment ENVIRONMENTAL PROTECTION... Refineries: Catalytic Cracking Units, Catalytic Reforming Units, and Sulfur Recovery Units Pt. 63, Subpt. UUU, Table 32 Table 32 to Subpart UUU of Part 63—Requirements for Performance Tests for HAP Emissions From...

Catalytic Fast Pyrolysis of Cellulose by Integrating Dispersed Nickel Catalyst with HZSM-5 Zeolite

NASA Astrophysics Data System (ADS)

Lei, Xiaojuan; Bi, Yadong; Zhou, Wei; Chen, Hui; Hu, Jianli

2018-01-01

The effect of integrating dispersed nickel catalyst with HZSM-5 zeolite on upgrading of vapors produced from pyrolysis of lignocellulosic biomass was investigated. The active component nickel nitrate was introduced onto the cellulose substrate by impregnation technique. Based on TGA experimental results, we discovered that nickel nitrate first released crystallization water, and then successively decomposed into nickel oxide which was reduced in-situ to metallic nickel through carbothermal reduction reaction. In-situ generated nickel nanoparticles were found highly dispersed over carbon substrate, which were responsible for catalyzing reforming and cracking of tars. In catalytic fast pyrolysis of cellulose, the addition of nickel nitrate caused more char formation at the expense of the yield of the condensable liquid products. In addition, the selectivity of linear oxygenates was increased whereas the yield of laevoglucose was reduced. Oxygen-containing compounds in pyrolysis vapors were deoxygenated into aromatics using HZSM-5. Moreover, the amount of condensable liquid products was decreased with the addition of HZSM-5.

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.

Coal liquefaction process

DOEpatents

Karr, Jr., Clarence

1977-04-19

An improved coal liquefaction process is provided which enables conversion of a coal-oil slurry to a synthetic crude refinable to produce larger yields of gasoline and diesel oil. The process is characterized by a two-step operation applied to the slurry prior to catalytic desulfurization and hydrogenation in which the slurry undergoes partial hydrogenation to crack and hydrogenate asphaltenes and the partially hydrogenated slurry is filtered to remove minerals prior to subsequent catalytic hydrogenation.

40 CFR 63.1578 - Who implements and enforces this subpart?

Code of Federal Regulations, 2010 CFR

2010-07-01

... National Emission Standards for Hazardous Air Pollutants for Petroleum Refineries: Catalytic Cracking Units.... (1) Approval of alternatives to the non-opacity emission limitations and work practice standards in...

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.

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

Types of Refined Petroleum Products

EPA Pesticide Factsheets

These are derived from crude oils through processes such as catalytic cracking and fractional distillation. Examples described here are gasoline, kerosene, no. 2 fuel oil, no. 4 fuel oil, no. 5 fuel oil, no. 6 fuel oil, and lubricating oil.

Advances of two-stage riser catalytic cracking of heavy oil for maximizing propylene yield (TMP) process.

PubMed

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

Two-stage riser catalytic cracking of heavy oil for maximizing propylene yield (TMP) process proposed by State Key Laboratory of Heavy oil Processing, China University of Petroleum, can remarkably enhance the propylene yield and minimize the dry gas and coke yields, and obtain high-quality light oils (gasoline and diesel). It has been commercialized since 2006. Up to now, three TMP commercial units have been put into production and other four commercial units are under design and construction. The commercial data showed that taking paraffinic based Daqing (China) atmospheric residue as the feedstock, the propylene yield reached 20.31 wt%, the liquid products yield (the total yield of liquefied petroleum gas, gasoline, and diesel) was 82.66 wt%, and the total yield of dry gas and coke was 14.28 wt%. Moreover, the research octane number of gasoline could be up to 96.

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

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

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.

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.

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.

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

75 FR 44236 - Agency Information Collection Activities; Submission to OMB for Review and Approval; Comment...

Federal Register 2010, 2011, 2012, 2013, 2014

2010-07-28

..., Catalytic Cracking, Reforming and Sulfur Units (Renewal); EPA ICR Number 1844.04, OMB Control Number 2060... ICR Number 1844.04, OMB Control Number 2060-0554. ICR Status: This ICR is scheduled to expire on...

Reaction pathways for the deoxygenation of vegetable oils and related model compounds.

PubMed

Gosselink, Robert W; Hollak, Stefan A W; Chang, Shu-Wei; van Haveren, Jacco; de Jong, Krijn P; Bitter, Johannes H; van Es, Daan S

2013-09-01

Vegetable oil-based feeds are regarded as an alternative source for the production of fuels and chemicals. Paraffins and olefins can be produced from these feeds through catalytic deoxygenation. The fundamentals of this process are mostly studied by using model compounds such as fatty acids, fatty acid esters, and specific triglycerides because of their structural similarity to vegetable oils. In this Review we discuss the impact of feedstock, reaction conditions, and nature of the catalyst on the reaction pathways of the deoxygenation of vegetable oils and its derivatives. As such, we conclude on the suitability of model compounds for this reaction. It is shown that the type of catalyst has a significant effect on the deoxygenation pathway, that is, group 10 metal catalysts are active in decarbonylation/decarboxylation whereas metal sulfide catalysts are more selective to hydrodeoxygenation. Deoxygenation studies performed under H2 showed similar pathways for fatty acids, fatty acid esters, triglycerides, and vegetable oils, as mostly deoxygenation occurs indirectly via the formation of fatty acids. Deoxygenation in the absence of H2 results in significant differences in reaction pathways and selectivities depending on the feedstock. Additionally, using unsaturated feedstocks under inert gas results in a high selectivity to undesired reactions such as cracking and the formation of heavies. Therefore, addition of H2 is proposed to be essential for the catalytic deoxygenation of vegetable oil feeds. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

[Progress in synthesis technologies and application of aviation biofuels].

PubMed

Sun, Xiaoying; Liu, Xiang; Zhao, Xuebing; Yang, Ming; Liu, Dehua

2013-03-01

Development of aviation biofuels has attracted great attention worldwide because that the shortage of fossil resources has become more and more serious. In the present paper, the development background, synthesis technologies, current application status and existing problems of aviation biofuels were reviewed. Several preparation routes of aviation biofuels were described, including Fischer-Tropsch process, catalytic hydrogenation and catalytic cracking of bio-oil. The status of flight tests and commercial operation were also introduced. Finally the problems for development and application of aviation biofuels were stated, and some accommodation were proposed.

Pyrogenic transformation of Nannochloropsis oceanica into fatty acid methyl esters without oil extraction for estimating total lipid content.

PubMed

Kim, Jieun; Jung, Jong-Min; Lee, Jechan; Kim, Ki-Hyun; Choi, Tae O; Kim, Jae-Kon; Jeon, Young Jae; Kwon, Eilhann E

2016-07-01

This study fundamentally investigated the pseudo-catalytic transesterification of dried Nannochloropsis oceanica into fatty acid methyl esters (FAMEs) without oil extraction, which was achieved in less than 5min via a thermo-chemical pathway. This study presented that the pseudo-catalytic transesterification reaction was achieved in the presence of silica and that its main driving force was identified as temperature: pores in silica provided the numerous reaction space like a micro-reactor, where the heterogeneous reaction was developed. The introduced FAME derivatization showed an extraordinarily high tolerance of impurities (i.e., pyrolytic products and various extractives). This study also explored the thermal cracking of FAMEs derived from N. oceanica: the thermal cracking of saturated FAMEs was invulnerable at temperatures lower than 400°C. Lastly, this study reported that N. oceanica contained 14.4wt.% of dried N. oceanica and that the introduced methylation technique could be applicable to many research fields sharing the transesterification platform. Copyright © 2016 Elsevier Ltd. All rights reserved.

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

Application of mesoporous Al-MCM-48 material to the conversion of lignin.

PubMed

Lee, Hyung Won; Lee, In-Gu; Park, Sung Hoon; Jeon, Jong-Ki; Suh, Dong Jin; Jung, Jinho; Park, Young-Kwon

2014-04-01

Al-MCM-48 was applied to the catalytic pyrolysis of lignin for the first time. The pyrolysis reaction and in-situ product were analyzed by pyrolysis gas chromatography/mass spectrometry. The main products of the non-catalytic pyrolysis of lignin were phenols. The use of Al-MCM-48 increased the production of light phenols considerably. The yields of high-value-added compounds, such as hydrocarbons and aromatics, were also increased by catalytic upgrading. Al-MCM-48 is believed to promote cracking, aromatization and deoxygenation, such as decarbonylation. On the other hand, Si-MCM-48, which has no acid sites, showed lower deoxygenation efficiency than Al-MCM-48. Al-MCM-48 could be regenerated by calcining in air.

Catalytic cracking of fast and tail gas reactive pyrolysis bio-oils over HZSM-5

USDA-ARS?s Scientific Manuscript database

While hydrodeoxygenation (HDO) of pyrolysis oil is well understood as an upgrading method, the high processing pressures associated with it alone justify the exploration of alternative upgrading solutions, especially those that could adapt pyrolysis oils into the existing refinery infrastructure. Ca...

Multifaceted effects of HZSM-5 (Proton-exchanged Zeolite Socony Mobil-5) on catalytic cracking of pinewood pyrolysis vapor in a two-stage fixed bed reactor.

PubMed

Wang, Yimeng; Wang, Jie

2016-08-01

The pinewood was pyrolyzed in the first reactor at a heating rate of 10°Cmin(-1) from room temperature to 700°C, and the vapor was allowed to be cracked through the second reactor in a temperature range of 450-750°C without and with HZSM-5. Attempts were made to determine a wide spectrum of gaseous and liquid products, as well as the mass and element partitions to gas, water, bio-oil, coke and char. HZSM-5 showed a preferential deoxygenation effect via the facilitated decarbonylation and decarboxylation with the inhibited dehydration at 550-600°C. This catalyst also displayed a high selectivity for the formations of aromatic hydrocarbons and olefins by the promoted hydrogen transfer to these products at 550-600°C. The bio-oil produced with HZSM-5 at 500-600°C had the yields of 14.5-16.8%, the high heat values of 39.1-42.4MJkg(-1), and the energy recoveries of 33-35% (all dry biomass basis). Copyright © 2016 Elsevier Ltd. All rights reserved.

Method and apparatus for monitoring a hydrocarbon-selective catalytic reduction device

DOEpatents

Schmieg, Steven J; Viola, Michael B; Cheng, Shi-Wai S; Mulawa, Patricia A; Hilden, David L; Sloane, Thompson M; Lee, Jong H

2014-05-06

A method for monitoring a hydrocarbon-selective catalytic reactor device of an exhaust aftertreatment system of an internal combustion engine operating lean of stoichiometry includes injecting a reductant into an exhaust gas feedstream upstream of the hydrocarbon-selective catalytic reactor device at a predetermined mass flowrate of the reductant, and determining a space velocity associated with a predetermined forward portion of the hydrocarbon-selective catalytic reactor device. When the space velocity exceeds a predetermined threshold space velocity, a temperature differential across the predetermined forward portion of the hydrocarbon-selective catalytic reactor device is determined, and a threshold temperature as a function of the space velocity and the mass flowrate of the reductant is determined. If the temperature differential across the predetermined forward portion of the hydrocarbon-selective catalytic reactor device is below the threshold temperature, operation of the engine is controlled to regenerate the hydrocarbon-selective catalytic reactor device.

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

Yuan Zhang; Jin-hu Wu; Dong-ke Zhang

The cracking of oil refinery off-gas, simulated with a gas mixture containing methane (51%), ethylene (21.4%), ethane (21.1%), and propane (6.5%), over a coal char, petroleum coke, and quartz, respectively, has been studied in a fixed bed reactor. The experiments were performed at temperatures between 850 and 1000{sup o}C and at atmospheric pressure. The results show that the conversions of all species considered increased with increasing temperature. Ethane and propane completely decomposed over all three bed materials in the temperature range investigated. However, the higher initial conversion rates of methane and ethylene cracking at all temperatures were observed only overmore » the coal char and not on the petroleum coke and quartz, indicating a significant catalytic effect of the coal char on methane and ethylene cracking. Methane and ethylene conversions decreased with reaction time due to deactivation of the coal char by carbon deposition on the char surface and, in the later stage of a cracking experiment, became negative, suggesting that methane and ethylene had been formed during the cracking of ethane and propane. 16 refs., 13 figs., 2 tabs.« less

Gum formation tendencies of olefinic structures in gasoline and synergistic effect of sulphur compounds

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

Nagpal, J.M.; Joshi, G.C.; Aswal, D.S.

1995-04-01

The high octane gasoline pool contains varying amounts of cracked naphthas as an important ingredient in formulating high octane lead free gasoline. The cracked naphthas are largely from Fluidized Catalytic Cracking (FCC) units and to lesser extend from thermal cracking units. While the role of olefinic unsaturation in gum formation during storage of gasoline has been extensively studied, there is little published work on contribution of individual olefin types in storage stability and gum formation tendency of gasoline containing these compound types. In the present work we report our results on storage stability and gum formation tendency of different olefinmore » types present in cracked naphthas through model compound matrix. It is found that cyclic olefins and cyclic diolefins are the most prolific gum formers. We have also studied the role of sulfur compounds present in the gasolines on gum formation tendency of olefins. While thiols enhance gum formation from all olefinic types, sulfides and disulfides interact depending on the structure of olefins. These can have either an accelerating, or inhibiting effect on gum formation.« less

40 CFR Table 11 to Subpart Uuu of... - Requirements for Performance Tests for Organic HAP Emissions From Catalytic Cracking Units Not...

Code of Federal Regulations, 2012 CFR

2012-07-01

...) for Carbon Monoxide (CO) 11 Table 11 to Subpart UUU of Part 63 Protection of Environment ENVIRONMENTAL..., Subpt. UUU, Table 11 Table 11 to Subpart UUU of Part 63—Requirements for Performance Tests for Organic...

40 CFR Table 11 to Subpart Uuu of... - Requirements for Performance Tests for Organic HAP Emissions From Catalytic Cracking Units Not...

Code of Federal Regulations, 2013 CFR

2013-07-01

...) for Carbon Monoxide (CO) 11 Table 11 to Subpart UUU of Part 63 Protection of Environment ENVIRONMENTAL..., Subpt. UUU, Table 11 Table 11 to Subpart UUU of Part 63—Requirements for Performance Tests for Organic...

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, 2013 CFR

2013-07-01

... (NSPS) for Particulate Matter (PM) 4 Table 4 to Subpart UUU of Part 63 Protection of Environment... Units Pt. 63, Subpt. UUU, Table 4 Table 4 to Subpart UUU of Part 63—Requirements for Performance Tests...

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, 2012 CFR

2012-07-01

... (NSPS) for Particulate Matter (PM) 4 Table 4 to Subpart UUU of Part 63 Protection of Environment... Units Pt. 63, Subpt. UUU, Table 4 Table 4 to Subpart UUU of Part 63—Requirements for Performance Tests...

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, 2014 CFR

2014-07-01

... (NSPS) for Particulate Matter (PM) 4 Table 4 to Subpart UUU of Part 63 Protection of Environment... Units Pt. 63, Subpt. UUU, Table 4 Table 4 to Subpart UUU of Part 63—Requirements for Performance Tests...

40 CFR Table 11 to Subpart Uuu of... - Requirements for Performance Tests for Organic HAP Emissions From Catalytic Cracking Units Not...

Code of Federal Regulations, 2014 CFR

2014-07-01

...) for Carbon Monoxide (CO) 11 Table 11 to Subpart UUU of Part 63 Protection of Environment ENVIRONMENTAL..., Subpt. UUU, Table 11 Table 11 to Subpart UUU of Part 63—Requirements for Performance Tests for Organic...

Selective methylative homologation: an alternate route to alkane upgrading.

PubMed

Bercaw, John E; Hazari, Nilay; Labinger, Jay A; Scott, Valerie J; Sunley, Glenn J

2008-09-10

InI3 catalyzes the reaction of branched alkanes with methanol to produce heavier and more highly branched alkanes, which are more valuable fuels. The reaction of 2,3-dimethylbutane with methanol in the presence of InI3 at 180-200 degrees C affords the maximally branched C7 alkane, 2,2,3-trimethylbutane (triptane). With the addition of catalytic amounts of adamantane the selectivity of this transformation can be increased up to 60%. The lighter branched alkanes isobutane and isopentane also react with methanol to generate triptane, while 2-methylpentane is converted into 2,3-dimethylpentane and other more highly branched species. Observations implicate a chain mechanism in which InI3 activates branched alkanes to produce tertiary carbocations which are in equilibrium with olefins. The latter react with a methylating species generated from methanol and InI3 to give the next-higher carbocation, which accepts a hydride from the starting alkane to form the homologated alkane and regenerate the original carbocation. Adamantane functions as a hydride transfer agent and thus helps to minimize competing side reactions, such as isomerization and cracking, that are detrimental to selectivity.

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

A numerical investigation of the scale-up effects on flow, heat transfer, and kinetics processes of FCC units.

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

Chang, S. L.

1998-08-25

Fluid Catalytic Cracking (FCC) technology is the most important process used by the refinery industry to convert crude oil to valuable lighter products such as gasoline. Process development is generally very time consuming especially when a small pilot unit is being scaled-up to a large commercial unit because of the lack of information to aide in the design of scaled-up units. Such information can now be obtained by analysis based on the pilot scale measurements and computer simulation that includes controlling physics of the FCC system. A Computational fluid dynamic (CFD) code, ICRKFLO, has been developed at Argonne National Laboratorymore » (ANL) and has been successfully applied to the simulation of catalytic petroleum cracking risers. It employs hybrid hydrodynamic-chemical kinetic coupling techniques, enabling the analysis of an FCC unit with complex chemical reaction sets containing tens or hundreds of subspecies. The code has been continuously validated based on pilot-scale experimental data. It is now being used to investigate the effects of scaled-up FCC units. Among FCC operating conditions, the feed injection conditions are found to have a strong impact on the product yields of scaled-up FCC units. The feed injection conditions appear to affect flow and heat transfer patterns and the interaction of hydrodynamics and cracking kinetics causes the product yields to change accordingly.« less

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.

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.

Methodology for extracting local constants from petroleum cracking flows

DOEpatents

Chang, Shen-Lin; Lottes, Steven A.; Zhou, Chenn Q.

2000-01-01

A methodology provides for the extraction of local chemical kinetic model constants for use in a reacting flow computational fluid dynamics (CFD) computer code with chemical kinetic computations to optimize the operating conditions or design of the system, including retrofit design improvements to existing systems. The coupled CFD and kinetic computer code are used in combination with data obtained from a matrix of experimental tests to extract the kinetic constants. Local fluid dynamic effects are implicitly included in the extracted local kinetic constants for each particular application system to which the methodology is applied. The extracted local kinetic model constants work well over a fairly broad range of operating conditions for specific and complex reaction sets in specific and complex reactor systems. While disclosed in terms of use in a Fluid Catalytic Cracking (FCC) riser, the inventive methodology has application in virtually any reaction set to extract constants for any particular application and reaction set formulation. The methodology includes the step of: (1) selecting the test data sets for various conditions; (2) establishing the general trend of the parametric effect on the measured product yields; (3) calculating product yields for the selected test conditions using coupled computational fluid dynamics and chemical kinetics; (4) adjusting the local kinetic constants to match calculated product yields with experimental data; and (5) validating the determined set of local kinetic constants by comparing the calculated results with experimental data from additional test runs at different operating conditions.

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…

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.

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...

40 CFR 63.1565 - What are my requirements for organic HAP emissions from catalytic cracking units?

Code of Federal Regulations, 2013 CFR

2013-07-01

... operate at all times according to the procedures in the plan. (4) The emission limitations and operating... compliance with the emission limitations and work practice standards? You must: (1) Install, operate, and... ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) AIR PROGRAMS (CONTINUED) NATIONAL EMISSION STANDARDS FOR HAZARDOUS...

40 CFR Table 43 to Subpart Uuu of... - Requirements for Reports

Code of Federal Regulations, 2014 CFR

2014-07-01

... to Subpart UUU of Part 63 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) AIR... Cracking Units, Catalytic Reforming Units, and Sulfur Recovery Units Pt. 63, Subpt. UUU, Table 43 Table 43 to Subpart UUU of Part 63—Requirements for Reports As stated in § 63.1575(a), you shall meet each...

40 CFR Table 43 to Subpart Uuu of... - Requirements for Reports

Code of Federal Regulations, 2012 CFR

2012-07-01

... to Subpart UUU of Part 63 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) AIR... Cracking Units, Catalytic Reforming Units, and Sulfur Recovery Units Pt. 63, Subpt. UUU, Table 43 Table 43 to Subpart UUU of Part 63—Requirements for Reports As stated in § 63.1575(a), you shall meet each...

Palliative effects of H2 on SOFCs operating with carbon containing fuels

NASA Astrophysics Data System (ADS)

Reeping, Kyle W.; Bohn, Jessie M.; Walker, Robert A.

2017-12-01

Chlorine can accelerate degradation of solid oxide fuel cell (SOFC) Ni-based anodes operating on carbon containing fuels through several different mechanisms. However, supplementing the fuel with a small percentage of excess molecular hydrogen effectively masks the degradation to the catalytic activity of the Ni and carbon fuel cracking reaction reactions. Experiments described in this work explore the chemistry behind the "palliative" effect of hydrogen on SOFCs operating with chlorine-contaminated, carbon-containing fuels using a suite of independent, complementary techniques. Operando Raman spectroscopy is used to monitor carbon accumulation and, by inference, Ni catalytic activity while electrochemical techniques including electrochemical impedance spectroscopy and voltammetry are used to monitor overall cell performance. Briefly, hydrogen not only completely hides degradation observed with chlorine-contaminated carbon-containing fuels, but also actively removes adsorbed chlorine from the surface of the Ni, allowing for the methane cracking reaction to continue, albeit at a slower rate. When hydrogen is removed from the fuel stream the cell fails immediately due to chlorine occupation of methane/biogas reaction sites.

Aquatic hazard and biodegradability of light and middle atmospheric distillate petroleum streams.

PubMed

Swigert, James P; Lee, Carol; Wong, Diana C L; Podhasky, Paula

2014-08-01

Light and middle atmospheric distillate petroleum substances are blended to produce fuels used in transportation and heating. These substances represent the majority by volume of crude oil refined products in the United States. The goal of this research was to develop biodegradability and aquatic toxicity data for four substances; heavy, straight-run naphtha (HSRN), hydro-desulfurized kerosene (HDK), hydro-cracked gas oil (HCGO), and catalytic-cracked gas oil (CCGO). Ready biodegradability tests demonstrated rapid and extensive microbial oxidation of these test substances, indicating a lack of persistence in the aquatic environment. Differences in biodegradation patterns reflected compositional differences in the constituent hydrocarbons. Results of aquatic toxicity tests on alga, cladocera, and fish demonstrated that toxicity was greatest for catalytic-cracked gas oil, which contained a high proportion of aromatic hydrocarbons. Aromatic hydrocarbons are more soluble, and hence more bioavailable, resulting in higher toxicity. When expressed on the basis of loading rates, acute toxicity values (LL/EL50) ranged between 0.3 and 5.5 mg L(-1) for all three species, while chronic no-observed-effect loading rates (NOELR) ranged between 0.05 and 0.64 mg L(-1). PETROTOX estimates for acute and chronic toxicity ranged from 0.18 to 2.3 mg L(-1) and 0.06 to 0.14 mg L(-1), respectively, which were generally more conservative than experimental data. Copyright © 2014 The Authors. Published by Elsevier Ltd.. All rights reserved.

Finite element techniques applied to cracks interacting with selected singularities

NASA Technical Reports Server (NTRS)

Conway, J. C.

1975-01-01

The finite-element method for computing the extensional stress-intensity factor for cracks approaching selected singularities of varied geometry is described. Stress-intensity factors are generated using both displacement and J-integral techniques, and numerical results are compared to those obtained experimentally in a photoelastic investigation. The selected singularities considered are a colinear crack, a circular penetration, and a notched circular penetration. Results indicate that singularities greatly influence the crack-tip stress-intensity factor as the crack approaches the singularity. In addition, the degree of influence can be regulated by varying the overall geometry of the singularity. Local changes in singularity geometry have little effect on the stress-intensity factor for the cases investigated.

N- versus C-domain selectivity of catalytic inactivation of human angiotensin converting enzyme by lisinopril-coupled transition metal chelates.

PubMed

Hocharoen, Lalintip; Joyner, Jeff C; Cowan, J A

2013-12-27

The N- and C-terminal domains of human somatic angiotensin I converting enzyme (sACE-1) demonstrate distinct physiological functions, with resulting interest in the development of domain-selective inhibitors for specific therapeutic applications. Herein, the activity of lisinopril-coupled transition metal chelates was tested for both reversible binding and irreversible catalytic inactivation of each domain of sACE-1. C/N domain binding selectivity ratios ranged from 1 to 350, while rates of irreversible catalytic inactivation of the N- and C-domains were found to be significantly greater for the N-domain, suggesting a more optimal orientation of M-chelate-lisinopril complexes within the active site of the N-domain of sACE-1. Finally, the combined effect of binding selectivity and inactivation selectivity was assessed for each catalyst (double-filter selectivity factors), and several catalysts were found to cause domain-selective catalytic inactivation. The results of this study demonstrate the ability to optimize the target selectivity of catalytic metallopeptides through both binding and catalytic factors (double-filter effect).

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.

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...

40 CFR 63.1565 - What are my requirements for organic HAP emissions from catalytic cracking units?

Code of Federal Regulations, 2010 CFR

2010-07-01

... according to the procedures in the plan. (4) The emission limitations and operating limits for organic HAP... work practice standards? You must: (1) Install, operate, and maintain a continuous monitoring system... operating limit in Table 9 of this subpart that applies to you according to the procedures in Table 11 of...

40 CFR 63.1565 - What are my requirements for organic HAP emissions from catalytic cracking units?

Code of Federal Regulations, 2011 CFR

2011-07-01

... according to the procedures in the plan. (4) The emission limitations and operating limits for organic HAP... work practice standards? You must: (1) Install, operate, and maintain a continuous monitoring system... operating limit in Table 9 of this subpart that applies to you according to the procedures in Table 11 of...

40 CFR Table 40 to Subpart Uuu of... - Requirements for Installation, Operation, and Maintenance of Continuous Opacity Monitoring...

Code of Federal Regulations, 2011 CFR

2011-07-01

... Systems 40 Table 40 to Subpart UUU of Part 63 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Cracking Units, Catalytic Reforming Units, and Sulfur Recovery Units Pt. 63, Subpt. UUU, Table 40 Table 40 to Subpart UUU of Part 63—Requirements for Installation, Operation, and Maintenance of Continuous...

40 CFR Table 40 to Subpart Uuu of... - Requirements for Installation, Operation, and Maintenance of Continuous Opacity Monitoring...

Code of Federal Regulations, 2010 CFR

2010-07-01

... Systems 40 Table 40 to Subpart UUU of Part 63 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Cracking Units, Catalytic Reforming Units, and Sulfur Recovery Units Pt. 63, Subpt. UUU, Table 40 Table 40 to Subpart UUU of Part 63—Requirements for Installation, Operation, and Maintenance of Continuous...

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.

Crack Path Selection in Thermally Loaded Borosilicate/Steel Bibeam Specimen

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

Grutzik, Scott Joseph; Reedy, Jr., E. D.

Here, we have developed a novel specimen for studying crack paths in glass. Under certain conditions, the specimen reaches a state where the crack must select between multiple paths satisfying the K II = 0 condition. This path selection is a simple but challenging benchmark case for both analytical and numerical methods of predicting crack propagation. We document the development of the specimen, using an uncracked and instrumented test case to study the effect of adhesive choice and validate the accuracy of both a simple beam theory model and a finite element model. In addition, we present preliminary fracture testmore » results and provide a comparison to the path predicted by two numerical methods (mesh restructuring and XFEM). The directional stability of the crack path and differences in kink angle predicted by various crack kinking criteria is analyzed with a finite element model.« less

Crack Path Selection in Thermally Loaded Borosilicate/Steel Bibeam Specimen

DOE PAGES

Grutzik, Scott Joseph; Reedy, Jr., E. D.

2017-08-04

Here, we have developed a novel specimen for studying crack paths in glass. Under certain conditions, the specimen reaches a state where the crack must select between multiple paths satisfying the K II = 0 condition. This path selection is a simple but challenging benchmark case for both analytical and numerical methods of predicting crack propagation. We document the development of the specimen, using an uncracked and instrumented test case to study the effect of adhesive choice and validate the accuracy of both a simple beam theory model and a finite element model. In addition, we present preliminary fracture testmore » results and provide a comparison to the path predicted by two numerical methods (mesh restructuring and XFEM). The directional stability of the crack path and differences in kink angle predicted by various crack kinking criteria is analyzed with a finite element model.« less

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.

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.

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

PubMed

Musselwhite, Nathan; Na, Kyungsu; Sabyrov, Kairat; Alayoglu, Selim; Somorjai, Gabor A

2015-08-19

Several types of mesoporous aluminosilicates were synthesized and evaluated in the catalytic isomerization of n-hexane, both with and without Pt nanoparticles loaded into the mesopores. The materials investigated included mesoporous MFI and BEA type zeolites, MCF-17 mesoporous silica, and an aluminum modified MCF-17. The acidity of the materials was investigated through pyridine adsorption and Fourier Transform-Infrared Spectroscopy (FT-IR). It was found that the strong Brönsted acid sites in the micropores of the zeolite catalysts facilitated the cracking of hexane. However, the medium strength acid sites on the Al modified MCF-17 mesoporous silica greatly enhanced the isomerization reaction. Through the loading of different amounts of Pt into the mesopores of the Al modified MCF-17, the relationship between the metal nanoparticles and acidic sites on the support was revealed.

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

Gianetto, A.; Farag, H.I.; Blasetti, A.P.

Changes of the relative importance of intradiffusion on USY zeolite crystals were studied as a way of affecting selectivity of catalytic cracking reactions. Zeolite crystals were synthesized (Si/Al = 2.4), activated and stabilized using ion exchange and steam calcination to obtain USSY (Ultra Stable Submicron Y) zeolites. After the activation the zeolites were pelletized (45--60 [mu]m particles). USSYs were tested in a novel Riser Simulator. Results obtained show that total aromatics (BTX), benzene, C[sub 4] olefins, and coke were significantly affected with the change of zeolite crystal sizes. Gasolines produced with USSY zeolites contain less aromatics and particularly lower benzenemore » levels. Experimental results were analyzed with a model including several lumps: unconverted gas oil, gasoline, light gases, and coke. This model also accounts for catalyst deactivation as a function of coke on catalyst. Various kinetic parameters were determined with their corresponding spans for the 95% level of confidence.« less

Efficient catalytic decomposition of formic acid for the selective generation of H2 and H/D exchange with a water-soluble rhodium complex in aqueous solution.

PubMed

Fukuzumi, Shunichi; Kobayashi, Takeshi; Suenobu, Tomoyoshi

2008-01-01

Formic acid (HCOOH) decomposes efficiently to afford H2 and CO2 selectively in the presence of a catalytic amount of a water-soluble rhodium aqua complex, [Rh(III)(Cp*)(bpy)(H2O)]2+ (Cp*=pentamethylcyclopentadienyl, bpy=2,2'-bipyridine) in aqueous solution at 298 K. No CO was produced in this catalytic decomposition of HCOOH. The decomposition rate reached a maximum value at pH 3.8. No deterioration of the catalyst was observed during the catalytic decomposition of HCOOH, and the catalytic activity remained the same for the repeated addition of HCOOH. The rhodium-hydride complex was detected as the catalytic active species that undergoes efficient H/D exchange with water. When the catalytic decomposition of HCOOH was performed in D2O, D2 was produced selectively. Such an efficient H/D exchange and the observation of a deuterium kinetic isotope effect in the catalytic decomposition of DCOOH in H2O provide valuable mechanistic insight into this efficient and selective decomposition process.

40 CFR Table 1 to Subpart Uuu of... - Metal HAP Emission Limits for Catalytic Cracking Units

Code of Federal Regulations, 2012 CFR

2012-07-01

... incinerator or waste heat boiler in which you burn auxiliary or in supplemental liquid or solid fossil fuel... fossil fuel; and the opacity of emissions must not exceed 30 percent, except for one 6-minute average... burn auxiliary or supplemental liquid or solid fossil fuel, the incremental rate of PM must not exceed...

40 CFR Table 1 to Subpart Uuu of... - Metal HAP Emission Limits for Catalytic Cracking Units

Code of Federal Regulations, 2013 CFR

2013-07-01

... waste heat boiler in which you burn auxiliary or in supplemental liquid or solid fossil fuel, the... British thermal units (lb/million Btu) of heat input attributable to the liquid or solid fossil fuel; and... auxiliary or supplemental liquid or solid fossil fuel, the incremental rate of PM must not exceed 43.0 g/GJ...

40 CFR Table 1 to Subpart Uuu of... - Metal HAP Emission Limits for Catalytic Cracking Units

Code of Federal Regulations, 2014 CFR

2014-07-01

... incinerator or waste heat boiler in which you burn auxiliary or in supplemental liquid or solid fossil fuel... fossil fuel; and the opacity of emissions must not exceed 30 percent, except for one 6-minute average... burn auxiliary or supplemental liquid or solid fossil fuel, the incremental rate of PM must not exceed...

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

Code of Federal Regulations, 2012 CFR

2012-07-01

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

40 CFR Table 29 to Subpart Uuu of... - HAP Emission Limits for Sulfur Recovery Units

Code of Federal Regulations, 2011 CFR

2011-07-01

... Units 29 Table 29 to Subpart UUU of Part 63 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Cracking Units, Catalytic Reforming Units, and Sulfur Recovery Units Pt. 63, Subpt. UUU, Table 29 Table 29 to Subpart UUU of Part 63—HAP Emission Limits for Sulfur Recovery Units As stated in § 63.1568(a)(1...

40 CFR Table 29 to Subpart Uuu of... - HAP Emission Limits for Sulfur Recovery Units

Code of Federal Regulations, 2010 CFR

2010-07-01

... Units 29 Table 29 to Subpart UUU of Part 63 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Cracking Units, Catalytic Reforming Units, and Sulfur Recovery Units Pt. 63, Subpt. UUU, Table 29 Table 29 to Subpart UUU of Part 63—HAP Emission Limits for Sulfur Recovery Units As stated in § 63.1568(a)(1...

Thermal Shock Resistance of Si3N4/h -BN Composites Prepared via Catalytic Reaction-Bonding Route

NASA Astrophysics Data System (ADS)

Yang, Wanli; Peng, Zhigang; Dai, Lina; Shi, Zhongqi; Jin, Zhihao

2017-09-01

Si3N4/h-BN ceramic matrix composites were prepared via a catalytic reaction-bonding route by using ZrO2 as nitridation catalyst, and the water quenching (fast cooling) and molten aluminum quenching tests (fast heating) were carried out to evaluate the thermal shock resistance of the composites. The results showed that the thermal shock resistance was improved obviously with the increase in h-BN content, and the critical thermal shock temperature difference (Δ T c) reaches as high as 780 °C when the h-BN content was 30 wt.%. The improvement of thermal shock resistance of the composites was mainly due to the crack tending to quasi static propagating at weak bonding interface between Si3N4 and h-BN with the increase in h-BN content. For the molten aluminum quenching test, the residual strength showed no obvious decrease compared with water quenching test, which could be caused by the mild stress condition on the surface. In addition, a calculated parameter, volumetric crack density ( N f), was presented to quantitative evaluating the thermal shock resistance of the composites in contrast to the conventional R parameter.

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

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.

Method to monitor HC-SCR catalyst NOx reduction performance for lean exhaust applications

DOEpatents

Viola, Michael B [Macomb Township, MI; Schmieg, Steven J [Troy, MI; Sloane, Thompson M [Oxford, MI; Hilden, David L [Shelby Township, MI; Mulawa, Patricia A [Clinton Township, MI; Lee, Jong H [Rochester Hills, MI; Cheng, Shi-Wai S [Troy, MI

2012-05-29

A method for initiating a regeneration mode in selective catalytic reduction device utilizing hydrocarbons as a reductant includes monitoring a temperature within the aftertreatment system, monitoring a fuel dosing rate to the selective catalytic reduction device, monitoring an initial conversion efficiency, selecting a determined equation to estimate changes in a conversion efficiency of the selective catalytic reduction device based upon the monitored temperature and the monitored fuel dosing rate, estimating changes in the conversion efficiency based upon the determined equation and the initial conversion efficiency, and initiating a regeneration mode for the selective catalytic reduction device based upon the estimated changes in conversion efficiency.

Effect of preparation procedures on catalytic activity and selectivity of copper-based mixed oxides in selective catalytic oxidation of ammonia into nitrogen and water vapour

NASA Astrophysics Data System (ADS)

Jabłońska, Magdalena; Nocuń, Marek; Gołąbek, Kinga; Palkovits, Regina

2017-11-01

The selective oxidation of ammonia into nitrogen and water vapour (NH3-SCO) was studied over Cu-Mg(Zn)-Al-(Zr) mixed metal oxides, obtained by coprecipitation and their subsequent calcination. The effect of acid-base properties of Cu-Mg-Al-Ox on catalytic activity was investigated by changing the Mg/Al molar ratio. Other Cu-containing oxides were prepared by rehydration of calcined Mg-Al hydrotalcite-like compounds or thermal decomposition of metal nitrate precursors. XRD, BET, NH3-TPD, H2-TPR, XPS, FTIR with adsorption of pyridine and CO as well as TEM techniques were used for catalysts characterization. The results of catalytic tests revealed a crucial role of easily reducible highly dispersed copper oxide species to obtain enhanced activity and N2 selectivity in NH3-SCO. The selective catalytic reduction of NO by NH3 (NH3-SCR) and in situ DRIFT of NH3 sorption indicated that NH3-SCO proceeds according to the internal selective catalytic reduction mechanism (i-SCR).

Model based Inverse Methods for Sizing Cracks of Varying Shape and Location in Bolt hole Eddy Current (BHEC) Inspections (Postprint)

DTIC Science & Technology

2016-02-10

using bolt hole eddy current (BHEC) techniques. Data was acquired for a wide range of crack sizes and shapes, including mid- bore , corner and through...to select the most appropriate VIC-3D surrogate model for subsequent crack sizing inversion step. Inversion results for select mid- bore , through and...the flaw. 15. SUBJECT TERMS Bolt hole eddy current (BHEC); mid- bore , corner and through-thickness crack types; VIC-3D generated surrogate models

Use of lightweight concrete for reducing cracks in bridge decks.

DOT National Transportation Integrated Search

2016-04-01

Cracks in bridge decks can be due to many factors related to environmental effects, chemical reactions, and structural : loads. Careful selection of materials and mixture proportions can minimize cracking to some degree. To reduce cracking, : shrinka...

N- vs. C-Domain Selectivity of Catalytic Inactivation of Human Angiotensin Converting Enzyme by Lisinopril-Coupled Transition Metal Chelates

PubMed Central

Hocharoen, Lalintip; Joyner, Jeff C.; Cowan, J. A.

2014-01-01

The N- and C-terminal domains of human somatic Angiotensin I Converting Enzyme (sACE-1) demonstrate distinct physiological functions, with resulting interest in the development of domain-selective inhibitors for specific therapeutic applications. Herein, the activity of lisinopril-coupled transition metal chelates were tested for both reversible binding and irreversible catalytic inactivation of sACE-1. C/N domain binding selectivity ratios ranged from 1 to 350, while rates of irreversible catalytic inactivation of the N- and C-domains were found to be significantly greater for the N-domain, suggesting a more optimal orientation of the M-chelate-lisinopril complexes within the active site of the N-domain of sACE-1. Finally, the combined effect of binding selectivity and inactivation selectivity was assessed for each catalyst (double-filter selectivity factors), and several catalysts were found to cause domain-selective catalytic inactivation. The results of this study demonstrate the ability to optimize the target selectivity of catalytic metallopeptides through both binding and orientation factors (double-filter effect). PMID:24228790

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

PubMed

Hancsók, Jenő; Sági, Dániel; Valyon, József

2018-06-11

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

A viscoplastic study of crack-tip deformation and crack growth in a nickel-based superalloy at elevated temperature

NASA Astrophysics Data System (ADS)

Zhao, L. G.; Tong, J.

Viscoplastic crack-tip deformation behaviour in a nickel-based superalloy at elevated temperature has been studied for both stationary and growing cracks in a compact tension (CT) specimen using the finite element method. The material behaviour was described by a unified viscoplastic constitutive model with non-linear kinematic and isotropic hardening rules, and implemented in the finite element software ABAQUS via a user-defined material subroutine (UMAT). Finite element analyses for stationary cracks showed distinctive strain ratchetting behaviour near the crack tip at selected load ratios, leading to progressive accumulation of tensile strain normal to the crack-growth plane. Results also showed that low frequencies and superimposed hold periods at peak loads significantly enhanced strain accumulation at crack tip. Finite element simulation of crack growth was carried out under a constant Δ K-controlled loading condition, again ratchetting was observed ahead of the crack tip, similar to that for stationary cracks. A crack-growth criterion based on strain accumulation is proposed where a crack is assumed to grow when the accumulated strain ahead of the crack tip reaches a critical value over a characteristic distance. The criterion has been utilized in the prediction of crack-growth rates in a CT specimen at selected loading ranges, frequencies and dwell periods, and the predictions were compared with the experimental results.

40 CFR Table 6 to Subpart Uuu of... - Continuous Compliance With Metal HAP Emission Limits for Catalytic Cracking Units

Code of Federal Regulations, 2011 CFR

2011-07-01

... incinerator or waste heat boiler in which you burn auxiliary or supplemental liquid or solid fossil fuel, the... liquid or solid fossil fuel; and the opacity of emissions must not exceed 30 percent, except for one 6... liquid or solid fossil fuels (liters/hour or kilograms/hour) and the hours of operation during which...

40 CFR Table 1 to Subpart Uuu of... - Metal HAP Emission Limits for Catalytic Cracking Units

Code of Federal Regulations, 2010 CFR

2010-07-01

... heat boiler in which you burn auxiliary or in supplemental liquid or solid fossil fuel, the incremental... thermal units (lb/million Btu) of heat input attributable to the liquid or solid fossil fuel; and the... supplemental liquid or solid fossil fuel, the incremental rate of PM must not exceed 43.0 g/GJ (0.10 lb/million...

40 CFR Table 5 to Subpart Uuu of... - Initial Compliance With Metal HAP Emission Limits for Catalytic Cracking Units

Code of Federal Regulations, 2011 CFR

2011-07-01

... waste heat boiler in which you burn auxiliary or supplemental liquid or solid fossil fuel, the... thermal units (lb/million Btu) of heat input attributable to the liquid or solid fossil fuel; and the.../million Btu) of heat input attributable to the liquid or solid fossil fuel. As part of the Notification of...

40 CFR Table 1 to Subpart Uuu of... - Metal HAP Emission Limits for Catalytic Cracking Units

Code of Federal Regulations, 2011 CFR

2011-07-01

... heat boiler in which you burn auxiliary or in supplemental liquid or solid fossil fuel, the incremental... thermal units (lb/million Btu) of heat input attributable to the liquid or solid fossil fuel; and the... supplemental liquid or solid fossil fuel, the incremental rate of PM must not exceed 43.0 g/GJ (0.10 lb/million...

40 CFR Table 6 to Subpart Uuu of... - Continuous Compliance With Metal HAP Emission Limits for Catalytic Cracking Units

Code of Federal Regulations, 2010 CFR

2010-07-01

... incinerator or waste heat boiler in which you burn auxiliary or supplemental liquid or solid fossil fuel, the... liquid or solid fossil fuel; and the opacity of emissions must not exceed 30 percent, except for one 6... liquid or solid fossil fuels (liters/hour or kilograms/hour) and the hours of operation during which...

40 CFR Table 5 to Subpart Uuu of... - Initial Compliance With Metal HAP Emission Limits for Catalytic Cracking Units

Code of Federal Regulations, 2010 CFR

2010-07-01

... waste heat boiler in which you burn auxiliary or supplemental liquid or solid fossil fuel, the... thermal units (lb/million Btu) of heat input attributable to the liquid or solid fossil fuel; and the.../million Btu) of heat input attributable to the liquid or solid fossil fuel. As part of the Notification of...

40 CFR Table 7 to Subpart Uuu of... - Continuous Compliance With Operating Limits for Metal HAP Emissions From Catalytic Cracking Units

Code of Federal Regulations, 2010 CFR

2010-07-01

...-gas ratio above the limit established during the performance test. 4. Option 3: Ni lb/hr not subject to the NSPS for PM in 40 CFR 60.102. a. Continuous opacity monitoring system. The daily average Ni operating value must not exceed the site-specific Ni operating limit established during the performance test...

40 CFR Table 7 to Subpart Uuu of... - Continuous Compliance With Operating Limits for Metal HAP Emissions From Catalytic Cracking Units

Code of Federal Regulations, 2011 CFR

2011-07-01

...-gas ratio above the limit established during the performance test. 4. Option 3: Ni lb/hr not subject to the NSPS for PM in 40 CFR 60.102. a. Continuous opacity monitoring system. The daily average Ni operating value must not exceed the site-specific Ni operating limit established during the performance test...

Charge Transfer and Catalysis at the Metal Support Interface

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

Baker, Lawrence Robert

Kinetic, electronic, and spectroscopic characterization of model Pt–support systems are used to demonstrate the relationship between charge transfer and catalytic activity and selectivity. The results show that charge flow controls the activity and selectivity of supported metal catalysts. This dissertation builds on extensive existing knowledge of metal–support interactions in heterogeneous catalysis. The results show the prominent role of charge transfer at catalytic interfaces to determine catalytic activity and selectivity. Further, this research demonstrates the possibility of selectively driving catalytic chemistry by controlling charge flow and presents solid-state devices and doped supports as novel methods for obtaining electronic control over catalyticmore » reaction kinetics.« less

Characterization of low temperature creep properties of crack sealants using bending beam rehometry.

DOT National Transportation Integrated Search

2009-11-01

Crack sealing has been widely used as a routine preventative maintenance practice. Given its proper installation, crack sealants can extend : pavement service life by three to five years. However, current specifications for the selection of crack sea...

Characterization of low temperature mechanical properties of crack sealants utilizing direct tension test.

DOT National Transportation Integrated Search

2008-11-01

Crack sealing has been widely used as a routine preventative maintenance practice. Given its proper : installation, crack sealants can extend pavement service life by three to five years. However, current : specifications for the selection of crack s...

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

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.

Refiners have several options for reducing gasoline benzene

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

Goelzer, A.R.; Hernandez-Robinson, A.; Ram, S.

1993-09-13

Although the linkage between gasoline benzene content and evaporative, running, and tailpipe emission is not yet defined, the U.S. 1990 Clean Air Act Amendments mandate a benzene content of less than 1.0 vol% in reformulated gasolines. Likewise, the California Air Resources Board plans to restrict benzene to less than about 0.8 vol %. Mobil Research and Development Corp. and Badger Co. Inc. have developed several alternatives for reducing benzene levels in gasoline. Where benzene extraction is viable and maximum catalytic reformer hydrogen is needed, the companies' cumene and ethylbenzene processes are desirable. Mobil's benzene reduction process can be an alternativemore » to benzene hydrosaturation. All of these processes utilize low-value offgas from the fluid catalytic cracking (FCC) unit.« less

A comparative investigation of SO2 oxidative transfer over CuO with a CeO2 surface

NASA Astrophysics Data System (ADS)

Liu, Yifeng; Shen, Benxian; Pi, Zhipeng; Chen, Hua; Zhao, Jigang

2017-04-01

To further improve the catalytic desulfurization function of the Mg-Al spinel sulfur transfer agent in a fluid catalytic cracking (FCC) unit, the reaction paths of SO2 oxidation by O2 over the metal oxide surface of CuO (111) and CeO2 (111) were investigated. In reference to the fact that SO2 reacting with O2 over CuO was a Mars-van Krevelen cycle, a similar reaction law for SO2 oxidation over CeO2 was also verified by characterization methods (e.g., IR, XPS). Meanwhile, the molecular simulation results indicated that the rate-control step of SO2 oxidation over CeO2 (111) and CuO (111) was a SO3 desorption step. The lower energy barrier in the rate-control step corresponded to better catalytic performance; hence, it could explain the reason that CeO2 had a better sulfur oxidization transfer performance than CuO.

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.

Catalysis of aptamer-modified AuPd nanoalloy probe and its application to resonance scattering detection of trace UO(2)2+.

PubMed

Liang, Aihui; Zhang, Yi; Fan, Yanyan; Chen, Chunqiang; Wen, Guiqing; Liu, Qingye; Kang, Caiyan; Jiang, Zhiliang

2011-08-01

AuPd nanoalloy and nanopalladium with a diameter of 5 nm were prepared, using sodium citrate as the stabilizing agent and NaBH(4) as the reductant. The nanocatalyst containing palladium on the surface exhibited a strong catalytic effect on the slow NiP particle reaction between NiCl(2) and NaH(2)PO(2), and the NiP particle system showed a resonance scattering (RS) peak at 508 nm. The RS results showed that the Pd atom on AuPd nanoalloy surface is the catalytic center. Combining the aptamer cracking reaction of double-stranded DNA (dsDNA)-UO(2)(2+), AuPd nanoalloy aggregation, and AuPd nanoalloy catalysis, both AuPd nanoalloy RS probe and AuPd nanoalloy catalytic RS assays were developed for the determination of 40-250 pmol L(-1) UO(2)(2+) and 5.0-50 pmol L(-1) UO(2)(2+), respectively. This journal is © The Royal Society of Chemistry 2011

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

40 CFR Table 5 to Subpart Uuu of... - Initial Compliance With Metal HAP Emission Limits for Catalytic Cracking Units

Code of Federal Regulations, 2013 CFR

2013-07-01

... fossil fuel, the incremental rate of PM must not exceed 43.0 grams per Gigajoule (g/GJ) or 0.10 pounds... fossil fuel; and the opacity of emissions must not exceed 30 percent, except for one 6-minute average... lb/million Btu) of heat input attributable to the liquid or solid fossil fuel. As part of the...

40 CFR Table 6 to Subpart Uuu of... - Continuous Compliance With Metal HAP Emission Limits for Catalytic Cracking Units

Code of Federal Regulations, 2012 CFR

2012-07-01

... fossil fuel, the incremental rate of PM must not exceed 43.0 g/GJ (0.10 lb/million Btu) of heat input attributable to the liquid or solid fossil fuel; and the opacity of emissions must not exceed 30 percent... combustion of liquid or solid fossil fuels (liters/hour or kilograms/hour) and the hours of operation during...

40 CFR Table 6 to Subpart Uuu of... - Continuous Compliance With Metal HAP Emission Limits for Catalytic Cracking Units

Code of Federal Regulations, 2013 CFR

2013-07-01

... fossil fuel, the incremental rate of PM must not exceed 43.0 g/GJ (0.10 lb/million Btu) of heat input attributable to the liquid or solid fossil fuel; and the opacity of emissions must not exceed 30 percent... combustion of liquid or solid fossil fuels (liters/hour or kilograms/hour) and the hours of operation during...

40 CFR Table 5 to Subpart Uuu of... - Initial Compliance With Metal HAP Emission Limits for Catalytic Cracking Units

Code of Federal Regulations, 2014 CFR

2014-07-01

... fossil fuel, the incremental rate of PM must not exceed 43.0 grams per Gigajoule (g/GJ) or 0.10 pounds... fossil fuel; and the opacity of emissions must not exceed 30 percent, except for one 6-minute average... lb/million Btu) of heat input attributable to the liquid or solid fossil fuel. As part of the...

40 CFR Table 6 to Subpart Uuu of... - Continuous Compliance With Metal HAP Emission Limits for Catalytic Cracking Units

Code of Federal Regulations, 2014 CFR

2014-07-01

... fossil fuel, the incremental rate of PM must not exceed 43.0 g/GJ (0.10 lb/million Btu) of heat input attributable to the liquid or solid fossil fuel; and the opacity of emissions must not exceed 30 percent... combustion of liquid or solid fossil fuels (liters/hour or kilograms/hour) and the hours of operation during...

40 CFR Table 5 to Subpart Uuu of... - Initial Compliance With Metal HAP Emission Limits for Catalytic Cracking Units

Code of Federal Regulations, 2012 CFR

2012-07-01

... fossil fuel, the incremental rate of PM must not exceed 43.0 grams per Gigajoule (g/GJ) or 0.10 pounds... fossil fuel; and the opacity of emissions must not exceed 30 percent, except for one 6-minute average... lb/million Btu) of heat input attributable to the liquid or solid fossil fuel. As part of the...

40 CFR 63.1564 - What are my requirements for metal HAP emissions from catalytic cracking units?

Code of Federal Regulations, 2013 CFR

2013-07-01

... coke burn-off emission limit (Option 4). (2) Comply with each operating limit in Table 2 of this... the PM emission rate (lb/1,000 lbs of coke burn-off) for each run using Equations 1, 2, and 3 (if applicable) of this section as follows: ER11AP02.000 Where: Rc = Coke burn-off rate, kg/hr (lb/hr); Qr...

40 CFR 63.1564 - What are my requirements for metal HAP emissions from catalytic cracking units?

Code of Federal Regulations, 2014 CFR

2014-07-01

... coke burn-off emission limit (Option 4). (2) Comply with each operating limit in Table 2 of this... the PM emission rate (lb/1,000 lbs of coke burn-off) for each run using Equations 1, 2, and 3 (if applicable) of this section as follows: ER11AP02.000 Where: Rc = Coke burn-off rate, kg/hr (lb/hr); Qr...

40 CFR 63.1564 - What are my requirements for metal HAP emissions from catalytic cracking units?

Code of Federal Regulations, 2012 CFR

2012-07-01

... coke burn-off emission limit (Option 4). (2) Comply with each operating limit in Table 2 of this... the PM emission rate (lb/1,000 lbs of coke burn-off) for each run using Equations 1, 2, and 3 (if applicable) of this section as follows: ER11AP02.000 Where: Rc = Coke burn-off rate, kg/hr (lb/hr); Qr...

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

DOE PAGES

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

2016-10-15

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

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

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

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

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

Brittle fracture in viscoelastic materials as a pattern-formation process

NASA Astrophysics Data System (ADS)

Fleck, M.; Pilipenko, D.; Spatschek, R.; Brener, E. A.

2011-04-01

A continuum model of crack propagation in brittle viscoelastic materials is presented and discussed. Thereby, the phenomenon of fracture is understood as an elastically induced nonequilibrium interfacial pattern formation process. In this spirit, a full description of a propagating crack provides the determination of the entire time dependent shape of the crack surface, which is assumed to be extended over a finite and self-consistently selected length scale. The mechanism of crack propagation, that is, the motion of the crack surface, is then determined through linear nonequilibrium transport equations. Here we consider two different mechanisms, a first-order phase transformation and surface diffusion. We give scaling arguments showing that steady-state solutions with a self-consistently selected propagation velocity and crack shape can exist provided that elastodynamic or viscoelastic effects are taken into account, whereas static elasticity alone is not sufficient. In this respect, inertial effects as well as viscous damping are identified to be sufficient crack tip selection mechanisms. Exploring the arising description of brittle fracture numerically, we study steady-state crack propagation in the viscoelastic and inertia limit as well as in an intermediate regime, where both effects are important. The arising free boundary problems are solved by phase field methods and a sharp interface approach using a multipole expansion technique. Different types of loading, mode I, mode III fracture, as well as mixtures of them, are discussed.

NOX REMOVAL WITH COMBINED SELECTIVE CATALYTIC REDUCTION AND SELECTIVE NONCATALYTIC REDUCTION: PILOT- SCALE TEST RESULTS

EPA Science Inventory

Pilot-scale tests were conducted to develop a combined nitrogen oxide (NOx) reduction technology using both selective catalytic reduction (SCR) and selective noncatalytic reduction (SNCR). A commercially available vanadium-and titatnium-based composite honeycomb catalyst and enh...

Elevated temperature crack growth

NASA Technical Reports Server (NTRS)

Kim, K. S.; Vanstone, R. H.; Malik, S. N.; Laflen, J. H.

1988-01-01

A study was performed to examine the applicability of path-independent (P-I) integrals to crack growth problems in hot section components of gas turbine aircraft engines. Alloy 718 was used and the experimental parameters included combined temperature and strain cycling, thermal gradients, elastic-plastic strain levels, and mean strains. A literature review was conducted of proposed P-I integrals, and those capable of analyzing hot section component problems were selected and programmed into the postprocessor of a finite element code. Detailed elastic-plastic finite element analyses were conducted to simulate crack growth and crack closure of the test specimen, and to evaluate the P-I integrals. It was shown that the selected P-I integrals are very effective for predicting crack growth for isothermal conditions.

Catalytic Destruction of a Surrogate Organic Hazardous Air Pollutant as a Potential Co-benefit for Coal-fired Selective Catalyst Reduction Systems

EPA Science Inventory

Catalytic destruction of benzene (C6H6), a surrogate for organic hazardous air pollutants (HAPs) produced from coal combustion, was investigated using a commercial selective catalytic reduction (SCR) catalyst for evaluating the potential co-benefit of the SCR technology for reduc...

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

Effect of water addition in a microwave assisted thermal cracking of biomass tar gasification

NASA Astrophysics Data System (ADS)

Warsita, A.; Surya, I.

2018-02-01

Producer gas from biomass gasification is plagued by the presence of tar which causes pipe blockages. Thermal and catalytic treatments in a microwave reactor have been shown to be effective methods for removing tar from producer gas. A question arises as to the possibility of enhancing the removal mechanism by adding water into the reactor. Thermal treatment with a various amount of water was added at temperatures in the range of 800-1200°C. The tar removal efficiency obtained 96.32% at the optimum temperature of 1200°C at the water to tar ratio (W/T) of 0.3. This study shows that the removal of tar by microwave irradiation with water addition is a significant and effective method in tar cracking.

INDUSTRIAL BOILER RETROFIT FOR NOX CONTROL: COMBINED SELECTIVE NONCATALYTIC REDUCTION AND SELECTIVE CATALYTIC REDUCTION

EPA Science Inventory

The paper describes retrofitting and testing a 590 kW (2 MBtu/hr), oil-fired, three-pass, fire-tube package boiler with a combined selective noncatalytic reduction (SNCR) and selective catalytic reduction (SCR) system. The system demonstrated 85% nitrogen oxides (NOx) reduction w...

Advanced Low-Emissions Catalytic-Combustor Program, phase 1. [aircraft gas turbine engines

NASA Technical Reports Server (NTRS)

Sturgess, G. J.

1981-01-01

Six catalytic combustor concepts were defined, analyzed, and evaluated. Major design considerations included low emissions, performance, safety, durability, installations, operations and development. On the basis of these considerations the two most promising concepts were selected. Refined analysis and preliminary design work was conducted on these two concepts. The selected concepts were required to fit within the combustor chamber dimensions of the reference engine. This is achieved by using a dump diffuser discharging into a plenum chamber between the compressor discharge and the turbine inlet, with the combustors overlaying the prediffuser and the rear of the compressor. To enhance maintainability, the outer combustor case for each concept is designed to translate forward for accessibility to the catalytic reactor, liners and high pressure turbine area. The catalytic reactor is self-contained with air-cooled canning on a resilient mounting. Both selected concepts employed integrated engine-starting approaches to raise the catalytic reactor up to operating conditions. Advanced liner schemes are used to minimize required cooling air. The two selected concepts respectively employ fuel-rich initial thermal reaction followed by rapid quench and subsequent fuel-lean catalytic reaction of carbon monoxide, and, fuel-lean thermal reaction of some fuel in a continuously operating pilot combustor with fuel-lean catalytic reaction of remaining fuel in a radially-staged main combustor.

SELECTIVE CATALYTIC REDUCTION MERCURY FIELD SAMPLING PROJECT

EPA Science Inventory

The report details an investigation on the effect of selective catalytic reduction (SCR), selective noncatalytic reduction (SNCR), and flue gas conditioning on the speciation and removal of mercury at power plants. If SCR and/or SNCR systems enhance mercury conversion/capture, t...

Automotive and Construction Equipment for Arctic Use: Heating and Cold Starting

DTIC Science & Technology

1991-04-01

heater. Catalytic combustion heaters similar to that shown in Figure 12 produce flameless heat using gasoline, benzene or a similar fuel and have... combustion chamber; physical scientist, is a • engine compartment air; and member of CRREL’s * personnel and cargo compartments. Applied Research Wind...component warping and thermal cracking. When coolant is pumped, heat is not only provided to the cylinders, thereby warming the combustion cha iber and the

40 CFR 63.1564 - What are my requirements for metal HAP emissions from catalytic cracking units?

Code of Federal Regulations, 2010 CFR

2010-07-01

... with the PM emission limit (Option 2); (iii) You can elect to comply with the Nickel (Ni) lb/hr emission limit (Option 3); or (iv) You can elect to comply with the Ni lb/1,000 lbs of coke burn-off... coke burn. ER11AP02.004 (iii) If you elect Option 3 in paragraph (a)(1)(iii) of this section, the Ni lb...

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

Code of Federal Regulations, 2010 CFR

2010-07-01

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

40 CFR 63.1564 - What are my requirements for metal HAP emissions from catalytic cracking units?

Code of Federal Regulations, 2011 CFR

2011-07-01

... with the PM emission limit (Option 2); (iii) You can elect to comply with the Nickel (Ni) lb/hr emission limit (Option 3); or (iv) You can elect to comply with the Ni lb/1,000 lbs of coke burn-off... coke burn. ER11AP02.004 (iii) If you elect Option 3 in paragraph (a)(1)(iii) of this section, the Ni lb...

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

Code of Federal Regulations, 2011 CFR

2011-07-01

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

In situ generation of Ni nanoparticles from metal-organic framework precursors and their use for biomass hydrodeoxygenation.

PubMed

Čelič, Tadeja Birsa; Grilc, Miha; Likozar, Blaž; Tušar, Nataša Novak

2015-05-22

So far, in situ-generated Ni nanoparticles have been reported to be efficient catalysts for tar cracking during wood liquefaction by pyrolysis. Herein, their performance in further bio-oil conversion steps is evaluated. Nanoparticles were generated for the first time from a Ni-containing metal-organic framework, MIL-77, during the hydrotreatment of glycerol-solvolyzed lignocellulosic (LC) biomass. Reactions were conducted at 300 °C and the H2 pressure was 8 MPa in a slurry reactor. The catalytic activity and selectivity of the deoxygenation and hydrocracking reactions for real biomass-derived feedstock using in situ-generated nanoparticles was compared with Ni nanoparticles dispersed on a silica-alumina support (commercial Ni/SiO2 -Al2 O3 catalyst). The mass activity of the in situ-generated nanoparticles for hydrogenolysis was more than ten times higher in comparison to their commercial analogues, and their potential for the use in LC biorefinery is discussed. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Multidimensional gas chromatography for the characterization of permanent gases and light hydrocarbons in catalytic cracking process.

PubMed

Luong, J; Gras, R; Cortes, H J; Shellie, R A

2013-01-04

An integrated gas chromatographic system has been successfully developed and implemented for the measurement of oxygen, nitrogen, carbon monoxide, carbon dioxide and light hydrocarbons in one single analysis. These analytes are frequently encountered in critical industrial petrochemical and chemical processes like catalytic cracking of naphtha or diesel fuel to lighter components used in gasoline. The system employs a practical, effective configuration consisting of two three-port planar microfluidic devices in series with each other, having built-in fluidic gates, and a mid-point pressure source. The use of planar microfluidic devices offers intangible advantages like in-oven switching with no mechanical moving parts, an inert sample flow path, and a leak-free operation even with multiple thermal cycles. In this way, necessary features such as selectivity enhancement, column isolation, column back-flushing, and improved system cleanliness were realized. Porous layer open tubular capillary columns were employed for the separation of hydrocarbons followed by flame ionization detection. After separation has occurred, carbon monoxide and carbon dioxide were converted to methane with the use of a nickel-based methanizer for detection with flame ionization. Flow modulated thermal conductivity detection was employed to measure oxygen and nitrogen. Separation of all the target analytes was achieved in one single analysis of less than 12 min. Reproducibility of retention times for all compounds were found to be less than 0.1% (n=20). Reproducibility of area counts at two levels, namely 100 ppm(v) and 1000 ppm(v) over a period of two days were found to be less than 5.5% (n=20). Oxygen and nitrogen were found to be linear over a range from 20 ppm(v) to 10,000 ppm(v) with correlation coefficients of at least 0.998 and detection limits of less than 10 ppm(v). Hydrocarbons of interest were found to be linear over a range from 200 ppb(v) to 1000 ppm(v) with correlation coefficients of greater than 0.999 and detection limits of less than 100 ppb(v). Copyright © 2012 Elsevier B.V. All rights reserved.

Nanocrystalline Precursors for the Co-Assembly of Crack-Free Metal Oxide Inverse Opals.

PubMed

Phillips, Katherine R; Shirman, Tanya; Shirman, Elijah; Shneidman, Anna V; Kay, Theresa M; Aizenberg, Joanna

2018-05-01

Inorganic microstructured materials are ubiquitous in nature. However, their formation in artificial self-assembly systems is challenging as it involves a complex interplay of competing forces during and after assembly. For example, colloidal assembly requires fine-tuning of factors such as the size and surface charge of the particles and electrolyte strength of the solvent to enable successful self-assembly and minimize crack formation. Co-assembly of templating colloidal particles together with a sol-gel matrix precursor material helps to release stresses that accumulate during drying and solidification, as previously shown for the formation of high-quality inverse opal (IO) films out of amorphous silica. Expanding this methodology to crystalline materials would result in microscale architectures with enhanced photonic, electronic, and catalytic properties. This work describes tailoring the crystallinity of metal oxide precursors that enable the formation of highly ordered, large-area (mm 2 ) crack-free titania, zirconia, and alumina IO films. The same bioinspired approach can be applied to other crystalline materials as well as structures beyond IOs. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

SELECTIVE CATALYTIC REDUCTION MERCURY FIELD SAMPLING PROJECT

EPA Science Inventory

A lack of data still exists as to the effect of selective catalytic reduction (SCR), selective noncatalytic reduction (SNCR), and flue gas conditioning on the speciation and removal of mercury (Hg) at power plants. This project investigates the impact that SCR, SNCR, and flue gas...

Understanding the mechanism of catalytic fast pyrolysis by unveiling reactive intermediates in heterogeneous catalysis

NASA Astrophysics Data System (ADS)

Hemberger, Patrick; Custodis, Victoria B. F.; Bodi, Andras; Gerber, Thomas; van Bokhoven, Jeroen A.

2017-06-01

Catalytic fast pyrolysis is a promising way to convert lignin into fine chemicals and fuels, but current approaches lack selectivity and yield unsatisfactory conversion. Understanding the pyrolysis reaction mechanism at the molecular level may help to make this sustainable process more economic. Reactive intermediates are responsible for product branching and hold the key to unveiling these mechanisms, but are notoriously difficult to detect isomer-selectively. Here, we investigate the catalytic pyrolysis of guaiacol, a lignin model compound, using photoelectron photoion coincidence spectroscopy with synchrotron radiation, which allows for isomer-selective detection of reactive intermediates. In combination with ambient pressure pyrolysis, we identify fulvenone as the central reactive intermediate, generated by catalytic demethylation to catechol and subsequent dehydration. The fulvenone ketene is responsible for the phenol formation. This technique may open unique opportunities for isomer-resolved probing in catalysis, and holds the potential for achieving a mechanistic understanding of complex, real-life catalytic processes.

Preparation of raspberry-like γ-Fe2O3/crackled nitrogen-doped carbon capsules and their application as supports to improve catalytic activity.

PubMed

Zhang, Junshuai; Yao, Tongjie; Zhang, Hui; Zhang, Xiao; Wu, Jie

2016-11-10

In this manuscript, we have introduced a novel method to improve the catalytic activity of metal nanoparticles via optimizing the support structure. To this end, raspberry-like γ-Fe 2 O 3 /crackled nitrogen-doped carbon (CNC) capsules were prepared by a two-step method. Compared with traditional magnetic capsules, in γ-Fe 2 O 3 /CNC capsules, the γ-Fe 2 O 3 nanoparticles were embedded in a CNC shell; therefore, they neither occupied the anchoring sites for metal nanoparticles nor came into contact with them, which was beneficial for increasing the metal nanoparticle loading. Numerous tiny cracks appeared on the porous CNC shell, which effectively improved the mass diffusion and transport in catalytic reactions. Additionally, the coordination interaction could be generated between the precursor metal ions and doped-nitrogen atoms in the capsule shell. With the help of these structural merits, γ-Fe 2 O 3 /CNC capsules were ideal supports for Pd nanoparticles, because they were beneficial for improving the Pd loading, reducing the nanoparticle size, increasing their dispersity and maximizing the catalytic performance of Pd nanoparticles anchored on the inner shell surface. As expected, γ-Fe 2 O 3 /CNC@Pd catalysts exhibited a dramatically enhanced catalytic activity towards hydrophilic 4-nitrophenol and hydrophobic nitrobenzene. The reaction rate constant k was compared with recent work and the corresponding reference samples. Moreover, they could be easily recycled by using a magnet and reused without an obvious loss of catalytic activity.

Methods of cracking a crude product to produce additional crude products

DOEpatents

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

2009-09-08

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

Topography, surface features, and flooding of Rogers Lake playa, California

USGS Publications Warehouse

Dinehart, Randal L.; McPherson, Kelly R.

1998-01-01

Rogers Lake is a desert playa used as a military airport for Edwards Air Force Base in the Antelope Valley of southern California. Previous measurements of land subsidence and ground-water levels in the study area indicated that ground-water pumping induced tensional stresses in the playa, which were sporadically relieved through the formation of long cracks. Drying of the sediments beneath the playa also may have accelerated the natural formation of giant desiccation polygons. When water flows across the playa, the cracks erode into fissures of sufficient width and depth to endanger traffic on the playa. Topographic surveys of the playa were made to derive a contour map that would allow examination of erosive flow paths. Crack networks were surveyed in selected areas during 1995 and compared with cracks visible in aerial photographs taken in 1990. Crack networks remained visible in their positions following several inundations of the playa. The density of the crack networks increased in all of the selected areas.

Obtaining Crack-free WC-Co Alloys by Selective Laser Melting

NASA Astrophysics Data System (ADS)

Khmyrov, R. S.; Safronov, V. A.; Gusarov, A. V.

Standard hardmetals of WC-Co system are brittle and often crack at selective laser melting (SLM). The objective of this study is to estimate the range of WC/Co ratio where cracking can be avoided. Micron-sized Co powder was mixed with WC nanopowder in a ball mill to obtain uniform distribution of WC over the surface of Co particles. Continuous layers of remelted material on the surface of a hardmetal plate were obtained from this composite powder by SLM at 1.07μm wavelength. The layers have satisfactory porosity and are well bound to the substrate. The chemical composition of the layers matches the composition of the initial powder mixtures. The powder mixture with 25wt.%WC can be used for SLM to obtain materials without cracks. The powder mixture with 50wt.%WC cracks because of formation of brittle W3Co3C phase. Cracking can considerably reduce the mechanical strength, so that the use of this composition is not advised.

Do chimpanzees use weight to select hammer tools?

PubMed

Schrauf, Cornelia; Call, Josep; Fuwa, Koki; Hirata, Satoshi

2012-01-01

The extent to which tool-using animals take into account relevant task parameters is poorly understood. Nut cracking is one of the most complex forms of tool use, the choice of an adequate hammer being a critical aspect in success. Several properties make a hammer suitable for nut cracking, with weight being a key factor in determining the impact of a strike; in general, the greater the weight the fewer strikes required. This study experimentally investigated whether chimpanzees are able to encode the relevance of weight as a property of hammers to crack open nuts. By presenting chimpanzees with three hammers that differed solely in weight, we assessed their ability to relate the weight of the different tools with their effectiveness and thus select the most effective one(s). Our results show that chimpanzees use weight alone in selecting tools to crack open nuts and that experience clearly affects the subjects' attentiveness to the tool properties that are relevant for the task at hand. Chimpanzees can encode the requirements that a nut-cracking tool should meet (in terms of weight) to be effective.

Thermal Catalytic Syngas Cleanup for High-Efficiency Waste-to-Energy Converters

DTIC Science & Technology

2015-12-01

characteristics for a full-scale WEC based on the collected experimental data. 20 RESULTS AND DISCUSSION Task 1 – Tar-Cracking Reactor...prepared to show the effect of reaching the target throughput rate of 50 lb/hr on conversion efficiency. In scaling up the experimental results , the...Midmoisture Full Moisture Fuel Feed Rate, kg/hr 22.3 22.3 22.3 Results Using the Experimental Recuperator Effectiveness Fuel Energy In, kWth 160 136 121

The effect of positioning cations on acidity and stability of the framework structure of Y zeolite

PubMed Central

Deng, Changshun; Zhang, Junji; Dong, Lihui; Huang, Meina; Bin Li; Jin, Guangzhou; Gao, Junbin; Zhang, Feiyue; Fan, Minguang; Zhang, Luoming; Gong, Yanjun

2016-01-01

The investigation on the modification of NaY zeolite on LaHY and AEHY (AE refers Ca and Sr and the molar ratio of Ca and Sr is 1:1) zeolites was proformed by XRD, N2-physisorption (BET), XRF, XPS, NH3-TPD, Py-IR, hydrothermal stability, and catalytic cracking test. These results indicate that HY zeolite with ultra low content Na can be obtained from NaY zeolite through four exchange four calcination method. The positioning capability of La3+ in sodalite cage is much better than that of AE2+ and about 12 La3+ can be well coordinated in sodalite cages of one unit cell of Y zeolite. Appropriate acid amount and strength favor the formation of propylene and La3+ is more suitable for the catalytic cracking of cyclohexane than that of AE2+. Our results not only elaborate the variation of the strong and weak acid sites as well as the Brönsted and Lewis acid sites with the change of exchanged ion content but also explore the influence of hydrothermal aging of LaHY and AEHY zeolites and find the optimum ion exchange content for the most reserved acid sites. At last, the coordination state and stabilization of ion exchanged Y zeolites were discussed in detail. PMID:26987306

Biobased methacrylic acid via selective catalytic decarboxylation of itaconic acid

USDA-ARS?s Scientific Manuscript database

We report a bio-based route to methacrylic acid via selective decarboxylation of itaconic acid utilizing catalytic ruthenium carbonyl propionate in an aqueous solvent system. High selectivity (>90%) was achieved at low catalyst loading (0.1 mol %) with high substrate concentration (5.5 M) at low tem...

Transition of Corner Cracks at Holes into Through-The-Thickness Cracks

DTIC Science & Technology

1983-12-01

upon an imaginary crack depth, which is arrived at by allowing the flaw to continually grow in the same elliptical shape it had when it penetrated the...approximately 0.75, and then they deteriorate rapidly . This value of 0.75 agrees with the value selected as the start of the transition region along the bore of...a corner crack emanating from a hole as it grows until it reaches final fracture. However, in a region near where the corner crack penetrates the back

A Sinter-Resistant Catalytic System Based on Platinum Nanoparticles Supported on TiO2 Nanofibers and Covered by Porous Silica

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

Dai, Yunqian; Lim, Byungkwon; Yang, Yong

2010-10-25

Platinum is a key catalyst that is invaluable in many important industrial processes such as CO oxidation in catalytic converters, oxidation and reduction reactions in fuel cells, nitric acid production, and petroleum cracking.[1] Many of these applications utilize Pt nanoparticles supported on oxides or porous carbon.[2] However, in practical applications that involve high temperatures (typically higher than 3008C), the Pt nanoparticles tend to lose their specific surface area and thus catalytic activity during operation because of sintering. Recent studies have shown that a porous oxide shell can act as a physical barrier to prevent sintering of unsupported metal nanoparticles and,more » at the same time, provide channels for chemical species to reach the surface of the nanoparticles, thus allowing the catalytic reaction to occur. This concept has been demonstrated in several systems, including Pt@SiO2,[3] Pt@CoO,[4] Pt/CeO2@SiO2,[5] Pd@SiO2,[6] Au@SiO2,[7] Au@SnO2 [8] and Au@ZrO2 [9] core– shell nanostructures. Despite these results, a sinter-resistant system has not been realized in supported Pt nanoparticle catalysts.« less

Gold nanoparticle-catalyzed environmentally benign deoxygenation of epoxides to alkenes.

PubMed

Noujima, Akifumi; Mitsudome, Takato; Mizugaki, Tomoo; Jitsukawa, Koichiro; Kaneda, Kiyotomi

2011-09-28

We have developed a highly efficient and green catalytic deoxygenation of epoxides to alkenes using gold nanoparticles (NPs) supported on hydrotalcite [HT: Mg(6)Al(2)CO(3)(OH)(16)] (Au/HT) with alcohols, CO/H(2)O or H(2) as the reducing reagent. Various epoxides were selectively converted to the corresponding alkenes. Among the novel metal NPs on HT, Au/HT was found to exhibit outstanding catalytic activity for the deoxygenation reaction. Moreover, Au/HT can be separated from the reaction mixture and reused with retention of its catalytic activity and selectivity. The high catalytic performance of Au/HT was attributed to the selective formation of Au-hydride species by the cooperative effect between Au NPs and HT.

Catalytic nanoporous membranes

DOEpatents

Pellin, Michael J; Hryn, John N; Elam, Jeffrey W

2013-08-27

A nanoporous catalytic membrane which displays several unique features Including pores which can go through the entire thickness of the membrane. The membrane has a higher catalytic and product selectivity than conventional catalysts. Anodic aluminum oxide (AAO) membranes serve as the catalyst substrate. This substrate is then subjected to Atomic Layer Deposition (ALD), which allows the controlled narrowing of the pores from 40 nm to 10 nm in the substrate by deposition of a preparatory material. Subsequent deposition of a catalytic layer on the inner surfaces of the pores reduces pore sizes to less than 10 nm and allows for a higher degree of reaction selectivity. The small pore sizes allow control over which molecules enter the pores, and the flow-through feature can allow for partial oxidation of reactant species as opposed to complete oxidation. A nanoporous separation membrane, produced by ALD is also provided for use in gaseous and liquid separations. The membrane has a high flow rate of material with 100% selectivity. Also provided is a method for producing a catalytic membrane having flow-through pores and discreet catalytic clusters adhering to the inside surfaces of the pores.

Assessment of Crack Path Prediction in Non-Proportional Mixed-Mode Fatigue

NASA Technical Reports Server (NTRS)

Highsmith, Shelby, Jr.; Johnson, Steve; Swanson, Gregory; Sayyah, Tarek; Pettit, Richard

2008-01-01

Non-proportional mixed-mode loading is present in many systems and a growing crack can experience any manner of mixed-mode loading. Prediction of the resulting crack path is important when assessing potential failure modes or when performing a failure investigation. Current crack path selection criteria are presented along with data for Inconel 718 under non-proportional mixed-mode loading. Mixed-mode crack growth can transition between path deflection mechanisms with very different orientations. Non-proportional fatigue loadings lack a single parameter for input to current crack path criteria. Crack growth transitions were observed in proportional and non-proportional FCG tests. Different paths displayed distinct fracture surface morphologies. New crack path drivers & transition criteria must be developed.

Calculation of Stress Intensity Factors for Interfacial Cracks in Fiber Metal Laminates

NASA Technical Reports Server (NTRS)

Wang, John T.

2009-01-01

Stress intensity factors for interfacial cracks in Fiber Metal Laminates (FML) are computed by using the displacement ratio method recently developed by Sun and Qian (1997, Int. J. Solids. Struct. 34, 2595-2609). Various FML configurations with single and multiple delaminations subjected to different loading conditions are investigated. The displacement ratio method requires the total energy release rate, bimaterial parameters, and relative crack surface displacements as input. Details of generating the energy release rates, defining bimaterial parameters with anisotropic elasticity, and selecting proper crack surface locations for obtaining relative crack surface displacements are discussed in the paper. Even though the individual energy release rates are nonconvergent, mesh-size-independent stress intensity factors can be obtained. This study also finds that the selection of reference length can affect the magnitudes and the mode mixity angles of the stress intensity factors; thus, it is important to report the reference length used with the calculated stress intensity factors.

Understanding fast macroscale fracture from microcrack post mortem patterns

PubMed Central

Guerra, Claudia; Scheibert, Julien; Bonamy, Daniel; Dalmas, Davy

2012-01-01

Dynamic crack propagation drives catastrophic solid failures. In many amorphous brittle materials, sufficiently fast crack growth involves small-scale, high-frequency microcracking damage localized near the crack tip. The ultrafast dynamics of microcrack nucleation, growth, and coalescence is inaccessible experimentally and fast crack propagation was therefore studied only as a macroscale average. Here, we overcome this limitation in polymethylmethacrylate, the archetype of brittle amorphous materials: We reconstruct the complete spatiotemporal microcracking dynamics, with micrometer/nanosecond resolution, through post mortem analysis of the fracture surfaces. We find that all individual microcracks propagate at the same low, load-independent velocity. Collectively, the main effect of microcracks is not to slow down fracture by increasing the energy required for crack propagation, as commonly believed, but on the contrary to boost the macroscale velocity through an acceleration factor selected on geometric grounds. Our results emphasize the key role of damage-related internal variables in the selection of macroscale fracture dynamics. PMID:22203962

Reactive Silicate Coatings for Protecting and Bonding Reinforcing Steel in Cement-Based Composites

DTIC Science & Technology

2008-12-01

wire. Selected sections of cracked enamel were maintained in the wet condition and examine periodical for evidence of gel formation and crack ... enamel containing portland cement will protect the underlying reinforcing steel in an aggressive environment. d) If the enamel coating is cracked ...oxidized. The increase in volume cracks the concrete around the reinforcement and weakens the steel members. When the steel is separated from the

Adsorbent catalytic nanoparticles and methods of using the same

DOEpatents

Slowing, Igor Ivan; Kandel, Kapil

2017-01-31

The present invention provides an adsorbent catalytic nanoparticle including a mesoporous silica nanoparticle having at least one adsorbent functional group bound thereto. The adsorbent catalytic nanoparticle also includes at least one catalytic material. In various embodiments, the present invention provides methods of using and making the adsorbent catalytic nanoparticles. In some examples, the adsorbent catalytic nanoparticles can be used to selectively remove fatty acids from feedstocks for biodiesel, and to hydrotreat the separated fatty acids.

Fire blocking systems for aircraft seat cushions

NASA Technical Reports Server (NTRS)

Parker, J. A.; Kourtides, D. A. (Inventor)

1984-01-01

A configuration and method for reducing the flammability of bodies of organic materials that thermally decompose to give flammable gases comprises covering the body with a flexible matrix that catalytically cracks the flammable gases to less flammable species. Optionally, the matrix is covered with a gas impermeable outer layer. In a preferred embodiment, the invention takes the form of an aircraft seat in which the body is a poly(urethane) seat cushion, the matrix is an aramid fabric or felt and the outer layer is an aluminum film.

Enzymatic Detoxication, Conformational Selection, and the Role of Molten Globule Active Sites*

PubMed Central

Honaker, Matthew T.; Acchione, Mauro; Zhang, Wei; Mannervik, Bengt; Atkins, William M.

2013-01-01

The role of conformational ensembles in enzymatic reactions remains unclear. Discussion concerning “induced fit” versus “conformational selection” has, however, ignored detoxication enzymes, which exhibit catalytic promiscuity. These enzymes dominate drug metabolism and determine drug-drug interactions. The detoxication enzyme glutathione transferase A1–1 (GSTA1–1), exploits a molten globule-like active site to achieve remarkable catalytic promiscuity wherein the substrate-free conformational ensemble is broad with barrierless transitions between states. A quantitative index of catalytic promiscuity is used to compare engineered variants of GSTA1–1 and the catalytic promiscuity correlates strongly with characteristics of the thermodynamic partition function, for the substrate-free enzymes. Access to chemically disparate transition states is encoded by the substrate-free conformational ensemble. Pre-steady state catalytic data confirm an extension of the conformational selection model, wherein different substrates select different starting conformations. The kinetic liability of the conformational breadth is minimized by a smooth landscape. We propose that “local” molten globule behavior optimizes detoxication enzymes. PMID:23649628

Understanding the mechanism of catalytic fast pyrolysis by unveiling reactive intermediates in heterogeneous catalysis

PubMed Central

Hemberger, Patrick; Custodis, Victoria B. F.; Bodi, Andras; Gerber, Thomas; van Bokhoven, Jeroen A.

2017-01-01

Catalytic fast pyrolysis is a promising way to convert lignin into fine chemicals and fuels, but current approaches lack selectivity and yield unsatisfactory conversion. Understanding the pyrolysis reaction mechanism at the molecular level may help to make this sustainable process more economic. Reactive intermediates are responsible for product branching and hold the key to unveiling these mechanisms, but are notoriously difficult to detect isomer-selectively. Here, we investigate the catalytic pyrolysis of guaiacol, a lignin model compound, using photoelectron photoion coincidence spectroscopy with synchrotron radiation, which allows for isomer-selective detection of reactive intermediates. In combination with ambient pressure pyrolysis, we identify fulvenone as the central reactive intermediate, generated by catalytic demethylation to catechol and subsequent dehydration. The fulvenone ketene is responsible for the phenol formation. This technique may open unique opportunities for isomer-resolved probing in catalysis, and holds the potential for achieving a mechanistic understanding of complex, real-life catalytic processes. PMID:28660882

Base-Controlled Completely Selective Linear or Branched Rhodium(I)-Catalyzed C-H ortho-Alkylation of Azines without Preactivation.

PubMed

Tran, Gaël; Hesp, Kevin D; Mascitti, Vincent; Ellman, Jonathan A

2017-05-15

A [Rh I ]/bisphosphine/base catalytic system for the ortho-selective C-H alkylation of azines by acrylates and acrylamides is reported. This catalytic system features an unprecedented complete linear or branched selectivity that is solely dependent on the catalytic base that is used. Complete branched selectivity is even achieved for ethyl methacrylate, which enables the introduction of a quaternary carbon center. Excellent functional group compatibility is demonstrated for both linear and branched alkylations. The operational simplicity and broad scope of this transformation allow for rapid access to functionalized azines of direct pharmaceutical and agrochemical relevance. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Thermal and catalytic pyrolysis of a mixture of plastics from small waste electrical and electronic equipment (WEEE).

PubMed

Santella, Chiara; Cafiero, Lorenzo; De Angelis, Doina; La Marca, Floriana; Tuffi, Riccardo; Vecchio Ciprioti, Stefano

2016-08-01

Pyrolysis seems a promising route for recycling of heterogeneous, contaminated and additives containing plastics from waste electrical and electronic equipment (WEEE). This study deals with the thermal and catalytic pyrolysis of a synthetic mixture containing real waste plastics, representative of polymers contained in small WEEE. Two zeolite-based catalysts were used at 400°C: HUSY and HZSM-5 with a high silica content, while three different temperatures were adopted for the thermal cracking: 400, 600 and 800°C. The mass balance showed that the oil produced by pyrolysis is always the main product regardless the process conditions selected, with yields ranging from 83% to 93%. A higher yield was obtained when pyrolysis was carried out with HZSM-5 at 400°C and without catalysts, but at 600 and 800°C. Formation of a significant amount of solid residue (about 13%) is observed using HUSY. The oily liquid product of pyrolysis, analysed by GC-MS and GC-FID, as well as by elemental analysis and for energy content, appeared lighter, less viscous and with a higher concentration of monoaromatics under catalytic condition, if compared to the liquid product derived from thermal degradation at the same temperature. HZSM-5 led to the production of a high yield of styrene (17.5%), while HUSY favoured the formation of ethylbenzene (15%). Energy released by combustion of the oil was around 39MJ/kg, thus suggesting the possibility to exploit it as a fuel, if the recovery of chemical compounds could not be realised. Elemental and proximate analysis of char and GC-TCD analysis of the gas were also performed. Finally, it was estimated to what extent these two products, showing a relevant ability to release energy, could fulfil the energy demand requested in pyrolysis. Copyright © 2016 Elsevier Ltd. All rights reserved.

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.

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

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

Lewis, F.A.; Parrish, G.

1984-10-01

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

Effectiveness of secondary prevention and treatment interventions for crack-cocaine abuse: a comprehensive narrative overview of English-language studies.

PubMed

Fischer, Benedikt; Blanken, Peter; Da Silveira, Dartiu; Gallassi, Andrea; Goldner, Elliot M; Rehm, Jürgen; Tyndall, Mark; Wood, Evan

2015-04-01

There are an estimated several million crack-cocaine users globally; use is highest in the Americas. Most crack users are socio-economically marginalized (e.g., homeless), and feature elevated risks for morbidity (e.g., blood-borne viruses), mortality and crime/violence involvement, resulting in extensive burdens. No comprehensive reviews of evidence-based prevention and/or treatment interventions specifically for crack use exist. We conducted a comprehensive narrative overview of English-language studies on the efficacy of secondary prevention and treatment interventions for crack (cocaine) abuse/dependence. Literature searches (1990-2014) using pertinent keywords were conducted in main scientific databases. Titles/abstracts were reviewed for relevance, and full studies were included in the review if involving a primary prevention/treatment intervention study comprising a substantive crack user sample. Intervention outcomes considered included drug use, health risks/status (e.g., HIV or sexual risks) and select social outcome indicators. Targeted (e.g., behavioral/community-based) prevention measures show mixed and short-term effects on crack use/HIV risk outcomes. Material (e.g., safer crack use kit distribution) interventions also document modest efficacy in risk reduction; empirical assessments of environmental (e.g., drug consumption facilities) for crack smokers are not available. Diverse psycho-social treatment (including contingency management) interventions for crack abuse/dependence show some positive but also limited/short-term efficacy, yet likely constitute best currently available treatment options. Ancillary treatments show little effects but are understudied. Despite ample studies, pharmaco-therapeutic/immunotherapy treatment agents have not produced convincing evidence; select agents may hold potential combined with personalized approaches and/or psycho-social strategies. No comprehensively effective 'gold-standard' prevention/treatment interventions for crack abuse exist; concerted research towards improved interventions is urgently needed. Copyright © 2015 Elsevier B.V. All rights reserved.

Fatigue life and crack growth prediction methodology

NASA Technical Reports Server (NTRS)

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

1993-01-01

The capabilities of a plasticity-induced crack-closure model and life-prediction code to predict fatigue crack growth and fatigue lives of metallic materials are reviewed. Crack-tip 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(K(sub eff))) under constant-amplitude loading. Some modifications to the delta(K(sub eff))-rate relations were needed in the near threshold regime to fit small-crack growth rate behavior and endurance limits. The model was then used to calculate small- and large-crack growth rates, and in some cases total fatigue lives, for several aluminum and titanium alloys under constant-amplitude, variable-amplitude, and spectrum loading. Fatigue lives were calculated using the crack growth relations and microstructural features like those that initiated cracks. Results from the tests and analyses agreed well.

Evolution of catalytic RNA in the laboratory

NASA Technical Reports Server (NTRS)

Joyce, Gerald F.

1992-01-01

We are interested in the biochemistry of existing RNA enzymes and in the development of RNA enzymes with novel catalytic function. The focal point of our research program has been the design and operation of a laboratory system for the controlled evolution of catalytic RNA. This system serves as working model of RNA-based life and can be used to explore the catalytic potential of RNA. Evolution requires the integration of three chemical processes: amplification, mutation, and selection. Amplification results in additional copies of the genetic material. Mutation operates at the level of genotype to introduce variability, this variability in turn being expressed as a range of phenotypes. Selection operates at the level of phenotype to reduce variability by excluding those individuals that do not conform to the prevailing fitness criteria. These three processes must be linked so that only the selected individuals are amplified, subject to mutational error, to produce a progeny distribution of mutant individuals. We devised techniques for the amplification, mutation, and selection of catalytic RNA, all of which can be performed rapidly in vitro within a single reaction vessel. We integrated these techniques in such a way that they can be performed iteratively and routinely. This allowed us to conduct evolution experiments in response to artificially-imposed selection constraints. Our objective was to develop novel RNA enzymes by altering the selection constraints in a controlled manner. In this way we were able to expand the catalytic repertoire of RNA. Our long-range objective is to develop an RNA enzyme with RNA replicase activity. If such an enzyme had the ability to produce additional copies of itself, then RNA evolution would operate autonomously and the origin of life will have been realized in the laboratory.

Method For Manufacturing Articles For High Temperature Use, And Articles Made Therewith

DOEpatents

Wang, Hongyu; Mitchell, David Joseph; Lau, Yuk-Chiu; Henry, Arnold Thomas

2006-02-28

A method for manufacturing an article for use in a high-temperature environment, and an article for use in such an environment, are presented. The method comprises providing a substrate; selecting a desired vertical crack density for a protective coating to be deposited on the substrate; providing a powder, wherein the powder has a size range selected to provide a coating having the desired vertical crack density; and applying a thermal-sprayed coating to the substrate, the coating having the desired vertical crack density, wherein the powder is used as a raw material for the coating.

Method For Manufacturing Articles For High Temperature Use, And Articles Made Therewith

DOEpatents

Wang, Hongyu; Mitchell, David Joseph; Lau, Yuk-Chiu; Henry, Arnold Thomas

2005-03-15

A method for manufacturing an article for use in a high-temperature environment, and an article for use in such an environment, are presented. The method comprises providing a substrate; selecting a desired vertical crack density for a protective coating to be deposited on the substrate; providing a powder, wherein the powder has a size range selected to provide a coating having the desired vertical crack density; and applying a thermal-sprayed coating to the substrate, the coating having the desired vertical crack density, wherein the powder is used as a raw material for the coating.

Characteristics of volatile organic compounds (VOCs) emitted from a petroleum refinery in Beijing, China

NASA Astrophysics Data System (ADS)

Wei, Wei; Cheng, Shuiyuan; Li, Guohao; Wang, Gang; Wang, Haiyan

2014-06-01

This study made a field VOCs (volatile organic compounds) measurement for a petroleum refinery in Beijing by determining 56 PAMS VOCs, which are demanded for photochemical assessment in US, and obtained the characteristics of VOCs emitted from the whole refinery and from its inner main devices. During the monitoring period, this refinery brought about an average increase of 61 ppbv in the ambient TVOCs (sum of the PAMS VOCs) at the refinery surrounding area, while the background of TVOCs there was only 10-30 ppbv. In chemical profile, the VOCs emitted from the whole refinery was characteristic by isobutane (8.7%), n-butane (7.9%), isopentane (6.3%), n-pentane (4.9%%), n-hexane (7.6%), C6 branched alkanes (6.0%), propene (12.7%), 1-butene (4.1%), benzene (7.8%), and toluene (5.9%). On the other hand, the measurement for the inner 5 devices, catalytic cracking units (CCU2 and CCU3), catalytic reforming unit (CRU), tank farm (TF), and wastewater treatment(WT), revealed the higher level of VOCs pollutions (about several hundred ppbv of TVOCs), and the individual differences in VOCs chemical profiles. Based on the measured speciated VOCs data at the surrounding downwind area, PMF receptor model was applied to identify the VOCs sources in the refinery. Then, coupling with the VOCs chemical profiles measured at the device areas, we concluded that CCU1/3 contributes to 25.9% of the TVOCs at the surrounding downwind area by volume, followed by CCU2 (24.7%), CRU (18.9%), TF (18.3%) and WT (12.0%), which was accordant with the research of US EPA (2008). Finally, ozone formation potentials of the 5 devices were also calculated by MIR technique, which showed that catalytic cracking units, accounting for about 55.6% to photochemical ozone formation, should be given the consideration of VOCs control firstly.

COST OF SELECTIVE CATALYTIC REDUCTION (SCR) APPLICATION FOR NOX CONTROL ON COAL-FIRED BOILERS

EPA Science Inventory

The report provides a methodology for estimating budgetary costs associated with retrofit applications of selective catalytic reduction (SCR) technology on coal-fired boilers. SCR is a postcombustion nitrogen oxides (NOx) control technology capable of providing NOx reductions >90...

HYBRID SNCR-SCR TECHNOLOGIES FOR NOX CONTROL: MODELING AND EXPERIMENT

EPA Science Inventory

The hybrid process of homogeneous gas-phase selective non-catalytic reduction (SNCR) followed by selective catalytic reduction (SCR) of nitric oxide (NO) was investigated through experimentation and modeling. Measurements, using NO-doped flue gas from a gas-fired 29 kW test combu...

Comparing the floquet stability of open and breathing fatigue cracks in an overhung rotordynamic system

NASA Astrophysics Data System (ADS)

Varney, Philip; Green, Itzhak

2017-11-01

Rotor cracks represent an uncommon but serious threat to rotating machines and must be detected early to avoid catastrophic machine failure. An important aspect of analyzing rotor cracks is understanding their influence on the rotor stability. It is well-known that the extent of rotor instability versus shaft speed is exacerbated by deeper cracks. Consequently, crack propagation can eventually result in an unstable response even if the shaft speed remains constant. Most previous investigations of crack-induced rotor instability concern simple Jeffcott rotors. This work advances the state-of-the-art by (a) providing a novel inertial-frame model of an overhung rotor, and (b) assessing the stability of the cracked overhung rotor using Floquet stability analysis. The rotor Floquet stability analysis is performed for both an open crack and a breathing crack, and conclusions are drawn regarding the importance of appropriately selecting the crack model. The rotor stability is analyzed versus crack depth, external viscous damping ratio, and rotor inertia. In general, this work concludes that the onset of instability occurs at lower shaft speeds for thick rotors, lower viscous damping ratios, and deeper cracks. In addition, when comparing commensurate cracks, the breathing crack is shown to induce more regions of instability than the open crack, though the open crack generally predicts an unstable response for shallower cracks than the breathing crack. Keywords: rotordynamics, stability, rotor cracks.

Enabling Catalytic Strategies for Biomass Conversion

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

Waymouth, Robert

This research program employed a mix of fundamental investigations of catalytic reactivity with targeted approaches for the catalytic synthesis of monomers and renewable polymers. We investigated the mechanisms of selective aerobic oxidation of polyols and carbohydrates with Pd catalysts with a special focus on the role of hydrogen peroxide and peroxy intermediates in an effort to increase catalyst lifetime. We also extended our studies on the selective oxidation of sugars to ketoses and the oxidative lactonization of 1,5-diols to generate new families of lactone monomers.

Catalytic conversion reactions in nanoporous systems with concentration-dependent selectivity: Statistical mechanical modeling

DOE PAGES

Garcia, Andres; Wang, Jing; Windus, Theresa L.; ...

2016-05-20

Statistical mechanical modeling is developed to describe a catalytic conversion reaction A → B c or B t with concentration-dependent selectivity of the products, B c or B t, where reaction occurs inside catalytic particles traversed by narrow linear nanopores. The associated restricted diffusive transport, which in the extreme case is described by single-file diffusion, naturally induces strong concentration gradients. Hence, by comparing kinetic Monte Carlo simulation results with analytic treatments, selectivity is shown to be impacted by strong spatial correlations induced by restricted diffusivity in the presence of reaction and also by a subtle clustering of reactants, A.

EFFECT OF SELECTIVE CATALYTIC REDUCTION ON MERCURY, 2002 FIELD STUDIES UPDATE

EPA Science Inventory

The report documents the 2002 "Selective Catalytic Reduction Mercury Field Sampling Project." An overall evaluation of the results from both 2001 and 2002 testing is also provided. The project was sponsored by the Electric Power Research Institute (EPRI), the U.S. Department of...

COST OF SELECTIVE CATALYTIC REDUCTION (SCR) APPLICATION FOR NOX CONTROL ON COAL-FIRED BOILERS

EPA Science Inventory

The report provides a methodology for estimating budgetary costs associ-ated with retrofit applications of selec-tive catalytic reduction (SCR) technology on coal-fired boilers. SCR is a post-combustion nitrogen oxides (NOX) con-trol technology capable of providing NOX reductions...

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.

Slow crack growth in glass in combined mode I and mode II loading

NASA Technical Reports Server (NTRS)

Shetty, D. K.; Rosenfield, A. R.

1991-01-01

Slow crack growth in soda-lime glass under combined mode I and mode II loading was investigated in precracked disk specimens in which pure mode I, pure mode II, and various combinations of mode I and mode II were achieved by loading in diametral compression at selected angles with respect to symmetric radial cracks. It is shown that slow crack growth under these conditions can be described by a simple exponential relationship with elastic strain energy release rate as the effective crack-driving force parameter. It is possible to interpret this equation in terms of theoretical models that treat subcritical crack growth as a thermally activated bond-rupture process with an activation energy dependent on the environment, and the elastic energy release rate as the crack-driving force parameter.

Controlling stress corrosion cracking in mechanism components of ground support equipment

NASA Technical Reports Server (NTRS)

Majid, W. A.

1988-01-01

The selection of materials for mechanism components used in ground support equipment so that failures resulting from stress corrosion cracking will be prevented is described. A general criteria to be used in designing for resistance to stress corrosion cracking is also provided. Stress corrosion can be defined as combined action of sustained tensile stress and corrosion to cause premature failure of materials. Various aluminum, steels, nickel, titanium and copper alloys, and tempers and corrosive environment are evaluated for stress corrosion cracking.

Exploiting basic principles to control the selectivity of the vapor phase catalytic oxidative cross-coupling of primary alcohols over nanoporous gold catalysts

DOE PAGES

Wang, Lu-Cun; Stowers, Kara J.; Zugic, Branko; ...

2015-05-20

It is important to achieve high selectivity for high volume chemical synthesis in order to lower energy consumption through reduction in waste. Here, we report the selective synthesis of methyl esters—methyl acetate and methyl butyrate—through catalytic O 2-assisted cross-coupling of methanol with ethanol or 1-butanol using activated, support-free nanoporous gold (npAu). Both well-controlled studies on ingots in UHV and experiments under ambient pressure catalytic conditions on both ingots and microspherical hollow shell catalysts reveal guiding principles for controlling selectivity. Under UHV conditions, the ester products of the cross-coupling of methanol with both ethanol and 1-butanol evolve near room temperature inmore » temperature-programmed reaction studies, indicating that the reactions occur facilely. Furthermore, under steady-state catalytic operation, high stable activity was observed for cross-coupling in flowing gaseous reactant mixtures at atmospheric pressure and 423 K with negligible combustion. Optimum selectivity for cross-coupling is obtained in methanol-rich mixtures due to a combination of two factors: (1) the relative coverage of the respective alkoxys and (2) the relative facility of their β-H elimination. The relative coverage of the alkoxys is governed by van der Waal’s interactions between the alkyl groups and the surface; here, we demonstrate the importance of these weak interactions in a steady-state catalytic process.« less

Wastes as Aggregates, Binders or Additions in Mortars: Selecting Their Role Based on Characterization.

PubMed

Farinha, Catarina Brazão; de Brito, Jorge; Veiga, Rosário; Fernández, J M; Jiménez, J R; Esquinas, A R

2018-03-20

The production of waste has increased over the years and, lacking a recycle or recovery solution, it is forwarded to landfill. The incorporation of wastes in cement-based materials is a solution to reduce waste deposition. In this regard, some researchers have been studying the incorporation of wastes with different functions: aggregate, binder and addition. The incorporation of wastes should take advantage of their characteristics. It requires a judicious analysis of their particles. This research involves the analysis of seven industrial wastes: biomass ashes, glass fibre, reinforced polymer dust, sanitary ware, fluid catalytic cracking, acrylic fibre, textile fibre and glass fibre. The main characteristics and advantages of each waste are enunciated and the best type of introduction in mortars is discussed. The characterization of the wastes as particles is necessary to identify the most suitable incorporation in mortars. In this research, some wastes are studied with a view to their re-use or recycling in mortars. Thus, this research focuses on the chemical, physical and mechanical characterization of industrial wastes and identification of the potentially most advantageous type of incorporation.

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

Motor fuels and chemicals from coal via the Sasol Synthol route

NASA Astrophysics Data System (ADS)

Hoogendoorn, J. C.

1981-03-01

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

Wastes as Aggregates, Binders or Additions in Mortars: Selecting Their Role Based on Characterization

PubMed Central

de Brito, Jorge; Veiga, Rosário

2018-01-01

The production of waste has increased over the years and, lacking a recycle or recovery solution, it is forwarded to landfill. The incorporation of wastes in cement-based materials is a solution to reduce waste deposition. In this regard, some researchers have been studying the incorporation of wastes with different functions: aggregate, binder and addition. The incorporation of wastes should take advantage of their characteristics. It requires a judicious analysis of their particles. This research involves the analysis of seven industrial wastes: biomass ashes, glass fibre, reinforced polymer dust, sanitary ware, fluid catalytic cracking, acrylic fibre, textile fibre and glass fibre. The main characteristics and advantages of each waste are enunciated and the best type of introduction in mortars is discussed. The characterization of the wastes as particles is necessary to identify the most suitable incorporation in mortars. In this research, some wastes are studied with a view to their re-use or recycling in mortars. Thus, this research focuses on the chemical, physical and mechanical characterization of industrial wastes and identification of the potentially most advantageous type of incorporation. PMID:29558418

Fatigue crack growth and life prediction under mixed-mode loading

NASA Astrophysics Data System (ADS)

Sajith, S.; Murthy, K. S. R. K.; Robi, P. S.

2018-04-01

Fatigue crack growth life as a function of crack length is essential for the prevention of catastrophic failures from damage tolerance perspective. In damage tolerance design approach, principles of fracture mechanics are usually applied to predict the fatigue life of structural components. Numerical prediction of crack growth versus number of cycles is essential in damage tolerance design. For cracks under mixed mode I/II loading, modified Paris law (d/a d N =C (ΔKe q ) m ) along with different equivalent stress intensity factor (ΔKeq) model is used for fatigue crack growth rate prediction. There are a large number of ΔKeq models available for the mixed mode I/II loading, the selection of proper ΔKeq model has significant impact on fatigue life prediction. In the present investigation, the performance of ΔKeq models in fatigue life prediction is compared with respect to the experimental findings as there are no guidelines/suggestions available on the selection of these models for accurate and/or conservative predictions of fatigue life. Within the limitations of availability of experimental data and currently available numerical simulation techniques, the results of present study attempt to outline models that would provide accurate and conservative life predictions. Such a study aid the numerical analysts or engineers in the proper selection of the model for numerical simulation of the fatigue life. Moreover, the present investigation also suggests a procedure to enhance the accuracy of life prediction using Paris law.

Examination of the catalytic fitness of the hammerhead ribozyme by in vitro selection.

PubMed Central

Tang, J; Breaker, R R

1997-01-01

We have designed a self-cleaving ribozyme construct that is rendered inactive during preparative in vitro transcription by allosteric interactions with ATP. This allosteric ribozyme was constructed by joining a hammerhead domain to an ATP-binding RNA aptamer, thereby creating a ribozyme whose catalytic rate can be controlled by ATP. Upon purification by PAGE, the engineered ribozyme undergoes rapid self-cleavage when incubated in the absence of ATP. This strategy of "allosteric delay" was used to prepare intact hammerhead ribozymes that would otherwise self-destruct during transcription. Using a similar strategy, we have prepared a combinatorial pool of RNA in order to assess the catalytic fitness of ribozymes that carry the natural consensus sequence for the hammerhead. Using in vitro selection, this comprehensive RNA pool was screened for sequence variants of the hammerhead ribozyme that also display catalytic activity. We find that sequences that comprise the core of naturally occurring hammerhead dominate the population of selected RNAs, indicating that the natural consensus sequence of this ribozyme is optimal for catalytic function. PMID:9257650

Coupling catalytic hydrolysis and oxidation of HCN over HZSM-5 modified by metal (Fe,Cu) oxides

NASA Astrophysics Data System (ADS)

Hu, Yanan; Liu, Jiangping; Cheng, Jinhuan; Wang, Langlang; Tao, Lei; Wang, Qi; Wang, Xueqian; Ning, Ping

2018-01-01

In this work, a series of metal oxides (Fe,Cu) modified HZSM-5 catalysts were synthesized by incipient-wetness impregnation method and then characterized by XRD, N2 adsorption-desorption, H2-TPR, NH3-TPD, UV-vis, FT-IR and XPS measurements. The catalytic hydrolysis and oxidation behaviors toward HCN were investigated. The results indicated that the Fe-Cu/HZSM-5 catalysts exhibited more excellent performence on coupling catalytic hydrolysis and oxidation of HCN than HZSM-5, Fe/HZSM-5, Cu/HZSM-5, and both nearly 100% HCN conversion and 80% N2 selectivity were obtained at about 250 °C. The improved catalytic performance could be ascribed to the creation of highly dispersed iron and copper composites on the surface of the HZSM-5 support, the excellent redox and regulated acid properties of the active ingredients. Moreover, the highly N2 selectivity could be attributed to the good interaction between the Fe and Cu nanocomposites which was facilitated to the NH3-SCR (selective catalytic reduction of NO by NH3) reaction.

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

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

Oyama, Ted; Agblevor, Foster; Battaglia, Francine

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

Study of Silicidation Process of Tungsten Catalyzer during Silicon Film Deposition in Catalytic Chemical Vapor Deposition

NASA Astrophysics Data System (ADS)

Honda, Kazuhiro; Ohdaira, Keisuke; Matsumura, Hideki

2008-05-01

In catalytic chemical vapor deposition (Cat-CVD), often called hot-wire CVD, source gases are decomposed by catalytic cracking reactions with heated catalyzing metal wires. In the case of silicon (Si) film deposition, such metal wires are often converted to silicide, which shortens the lifetime of catalyzing wires. As a catalyzer, tungsten (W) is widely used. Thus, the process of silicidation of a W catalyzer at temperatures over 1650 °C, which is the temperature used in Cat-CVD for Si film deposition, was studied extensively in various experiments. It is found that two phases of tungsten-silicide, WSi2 and W5Si3, are formed at this temperature, and that the radiation emissivity of WSi2 is 1.2 to 1.7 times higher than that of W5Si3 and pure W. The increase of surface emissivity due to the formation of WSi2 decreases the catalyzer surface temperature which induces further growth of the tungsten-silicide layer. It is also found that the suppression of WSi2 formation by elevating catalyzer temperatures over 1750 °C is a key to extending the lifetime of the W catalyzer in Cat-CVD.

Fracture processes and mechanisms of crack growth resistance in human enamel

NASA Astrophysics Data System (ADS)

Bajaj, Devendra; Park, Saejin; Quinn, George D.; Arola, Dwayne

2010-07-01

Human enamel has a complex micro-structure that varies with distance from the tooth’s outer surface. But contributions from the microstructure to the fracture toughness and the mechanisms of crack growth resistance have not been explored in detail. In this investigation the apparent fracture toughness of human enamel and the mechanisms of crack growth resistance were evaluated using the indentation fracture approach and an incremental crack growth technique. Indentation cracks were introduced on polished surfaces of enamel at selected distances from the occlusal surface. In addition, an incremental crack growth approach using compact tension specimens was used to quantify the crack growth resistance as a Junction of distance from the occlusal surface. There were significant differences in the apparent toughness estimated using the two approaches, which was attributed to the active crack length and corresponding scale of the toughening mechanisms.

MERCURY OXIDATION PROMOTED BY A SELECTIVE CATALYTIC REDUCTION CATALYST UNDER SIMULATED POWDER RIVER BASIN COAL COMBUSTION CONDITIONS

EPA Science Inventory

A bench-scale reactor consisting of a natural gas burner and an electrically heated reactor housing a selective catalytic reduction (SCR) catalyst was constructed for studying elemental mercury oxidation under SCR conditions. A low sulfur Power River Basin (PRB) coal combustion ...

GENERIC VERIFICATION PROTOCOL FOR DETERMINATION OF EMISSIONS REDUCTIONS FROM SELECTIVE CATALYTIC REDUCTIONS CONTROL TECHNOLOGIES FOR HIGHWAY, NONROAD, AND STATIONARY USE DIESEL ENGINES

EPA Science Inventory

The protocol describes the Environmental Technology Verification (ETV) Program's considerations and requirements for verification of emissions reduction provided by selective catalytic reduction (SCR) technologies. The basis of the ETV will be comparison of the emissions and perf...

INVESTIGATION OF SELECTIVE CATALYTIC REDUCTION IMPACT ON MERCURY SPECIATION UNDER SIMULATED NOX EMISSION CONTROL CONDITIONS

EPA Science Inventory

Selective catalytic reduction (SCR) technology is being increasingly applied for controlling emissions of nitrogen oxides (NOx) from coal-fired boilers. Some recent field and pilot studies suggest that the operation of SCR could affect the chemical form of mercury in the coal com...

ATLAS 60’ Fording Study

DTIC Science & Technology

1992-03-03

crack. Carbon steel stress cracks in the presence of sodium hydroxide (" caustic embrittlement"), whereas austenitic stainless steels stress crack in...transmission life. - Outboard planetary axle design reduces stresses on differential, drive shafts and axle shaft U-joints. . Enclosed oil disc brakes on... Stress Corrosion Crevice Pitting Erosion Corrosion Uniform Corrosion Intergranular Selective Leaching Page 19 Caterpflar Inc. ATLAS Fording Study Q The

Hydrogen adsorption and diffusion, and subcritical-crack growth in high strength steels and nickel base alloys

NASA Technical Reports Server (NTRS)

Wei, R. P.; Klier, K.; Simmons, G. W.; Chornet, E.

1973-01-01

Embrittlement, or the enhancement of crack growth by gaseous hydrogen in high strength alloys, is of primary interest in selecting alloys for various components in the space shuttle. Embrittlement is known to occur at hydrogen gas pressures ranging from fractions to several hundred atmospheres, and is most severe in the case of martensitic high strength steels. Kinetic information on subcritical crack growth in gaseous hydrogen is sparse at this time. Corroborative information on hydrogen adsorption and diffusion is inadequate to permit a clear determination of the rate controlling process and possible mechanism in hydrogen enhanced crack growth, and for estimating behavior over a range of temperatures and pressures. Therefore, coordinated studies of the kinetics of crack growth, and adsorption and diffusion of hydrogen, using identical materials, have been initiated. Comparable conditions of temperature and pressure will be used in the chemical and mechanical experiments. Inconel 718 alloy and 18Ni(200) maraging steel have been selected for these studies. Results from these studies are expected to provide not only a better understanding of the gaseous hydrogen embrittlement phenomenon itself, but also fundamental information on hydrogen adsorption and diffusion, and crack growth information that can be used directly for design.

Selective Transformation of Various Nitrogen-Containing Exhaust Gases toward N2 over Zeolite Catalysts.

PubMed

Zhang, Runduo; Liu, Ning; Lei, Zhigang; Chen, Biaohua

2016-03-23

In this review we focus on the catalytic removal of a series of N-containing exhaust gases with various valences, including nitriles (HCN, CH3CN, and C2H3CN), ammonia (NH3), nitrous oxide (N2O), and nitric oxides (NO(x)), which can cause some serious environmental problems, such as acid rain, haze weather, global warming, and even death. The zeolite catalysts with high internal surface areas, uniform pore systems, considerable ion-exchange capabilities, and satisfactory thermal stabilities are herein addressed for the corresponding depollution processes. The sources and toxicities of these pollutants are introduced. The important physicochemical properties of zeolite catalysts, including shape selectivity, surface area, acidity, and redox ability, are described in detail. The catalytic combustion of nitriles and ammonia, the direct catalytic decomposition of N2O, and the selective catalytic reduction and direct catalytic decomposition of NO are systematically discussed, involving the catalytic behaviors as well as mechanism studies based on spectroscopic and kinetic approaches and molecular simulations. Finally, concluding remarks and perspectives are given. In the present work, emphasis is placed on the structure-performance relationship with an aim to design an ideal zeolite-based catalyst for the effective elimination of harmful N-containing compounds.

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

High resolution electron microscopy of a small crack at the superficial layer of enamel.

PubMed

Hayashi, Y

1994-12-01

A small enamel crack was investigated using a high resolution electron microscope. The inside of the crack was filled with aggregates of irregularly oriented plate-like crystals. Amorphous mineral deposits were observed among these aggregates at a low magnification. Selected area electron diffractions indicated that the plate-like crystals consisted of hydroxyapatite (OH-AP), and that the amorphous mineral deposits were a mixture of OH-AP and whitlockite. These findings indicate that this crack may have been formed by occlusal and/or masticatory stress, and that a natural occlusion might occur through mineral deposition at the small crack such as in this case.

A probabilistic fatigue analysis of multiple site damage

NASA Technical Reports Server (NTRS)

Rohrbaugh, S. M.; Ruff, D.; Hillberry, B. M.; Mccabe, G.; Grandt, A. F., Jr.

1994-01-01

The variability in initial crack size and fatigue crack growth is incorporated in a probabilistic model that is used to predict the fatigue lives for unstiffened aluminum alloy panels containing multiple site damage (MSD). The uncertainty of the damage in the MSD panel is represented by a distribution of fatigue crack lengths that are analytically derived from equivalent initial flaw sizes. The variability in fatigue crack growth rate is characterized by stochastic descriptions of crack growth parameters for a modified Paris crack growth law. A Monte-Carlo simulation explicitly describes the MSD panel by randomly selecting values from the stochastic variables and then grows the MSD cracks with a deterministic fatigue model until the panel fails. Different simulations investigate the influences of the fatigue variability on the distributions of remaining fatigue lives. Six cases that consider fixed and variable conditions of initial crack size and fatigue crack growth rate are examined. The crack size distribution exhibited a dominant effect on the remaining fatigue life distribution, and the variable crack growth rate exhibited a lesser effect on the distribution. In addition, the probabilistic model predicted that only a small percentage of the life remains after a lead crack develops in the MSD panel.

Nonlinear ultrasonic imaging method for closed cracks using subtraction of responses at different external loads.

PubMed

Ohara, Yoshikazu; Horinouchi, Satoshi; Hashimoto, Makoto; Shintaku, Yohei; Yamanaka, Kazushi

2011-08-01

To improve the selectivity of closed cracks for objects other than cracks in ultrasonic imaging, we propose an extension of a novel imaging method, namely, subharmonic phased array for crack evaluation (SPACE) as well as another approach using the subtraction of responses at different external loads. By applying external static or dynamic loads to closed cracks, the contact state in the cracks varies, resulting in an intensity change of responses at cracks. In contrast, objects other than cracks are independent of external load. Therefore, only cracks can be extracted by subtracting responses at different loads. In this study, we performed fundamental experiments on a closed fatigue crack formed in an aluminum alloy compact tension (CT) specimen using the proposed method. We examined the static load dependence of SPACE images and the dynamic load dependence of linear phased array (PA) images by simulating the external loads with a servohydraulic fatigue testing machine. By subtracting the images at different external loads, we show that this method is useful in extracting only the intensity change of responses related to closed cracks, while canceling the responses of objects other than cracks. Copyright © 2010 Elsevier B.V. All rights reserved.

Atomically Precise Metal Nanoclusters for Catalytic Application

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

Jin, Rongchao

2016-11-18

The central goal of this project is to explore the catalytic application of atomically precise gold nanoclusters. By solving the total structures of ligand-protected nanoclusters, we aim to correlate the catalytic properties of metal nanoclusters with their atomic/electronic structures. Such correlation unravel some fundamental aspects of nanocatalysis, such as the nature of particle size effect, origin of catalytic selectivity, particle-support interactions, the identification of catalytically active centers, etc. The well-defined nanocluster catalysts mediate the knowledge gap between single crystal model catalysts and real-world conventional nanocatalysts. These nanoclusters also hold great promise in catalyzing certain types of reactions with extraordinarily highmore » selectivity. These aims are in line with the overall goals of the catalytic science and technology of DOE and advance the BES mission “to support fundamental research to understand, predict, and ultimately control matter and energy at the level of electrons, atoms, and molecules”. Our group has successfully prepared different sized, robust gold nanoclusters protected by thiolates, such as Au 25(SR) 18, Au 28(SR) 20, Au 38(SR) 24, Au 99(SR) 42, Au 144(SR) 60, etc. Some of these nanoclusters have been crystallographically characterized through X-ray crystallography. These ultrasmall nanoclusters (< 2 nm diameter) exhibit discrete electronic structures due to quantum size effect, as opposed to quasicontinuous band structure of conventional metal nanoparticles or bulk metals. The available atomic structures (metal core plus surface ligands) of nanoclusters serve as the basis for structure-property correlations. We have investigated the unique catalytic properties of nanoclusters (i.e. not observed in conventional nanogold catalysts) and revealed the structure-selectivity relationships. Highlights of our works include: i) Effects of ligand, cluster charge state, and size on the catalytic reactivity in CO oxidation, semihydrogenation of alkynes; ii) Size-controlled synthesis of Au-n clusters and structural elucidation; iii) Catalytic mechanisms and correlation with structures of cluster catalyst; iv) Catalytic properties of Au nanorods in chemoselective hydrogenation of nitrobenzaldehyde and visible light driven photocatalytic reactions.« less

History and utility of zeolite framework-type discovery from a data-science perspective

DOE PAGES

Zimmermann, Nils E. R.; Haranczyk, Maciej

2016-05-02

Mature applications such as fluid catalytic cracking and hydrocracking rely critically on early zeolite structures. With a data-driven approach, we find that the discovery of exceptional zeolite framework types around the new millennium was spurred by exciting new utilization routes. The promising processes have yet not been successfully implemented (“valley of death” effect), mainly because of the lack of thermal stability of the crystals. As a result, this foreshadows limited deployability of recent zeolite discoveries that were achieved by novel crystal synthesis routes.

Evaluation of Catalytic and Thermal Cracking in a JP-8 Fueled Pulsed Detonation Engine (Postprint)

DTIC Science & Technology

2007-09-01

this research. Each 0.91-m-long heat exchanger was fabricated with a 50.8-mm-dia, inconel - 625 , Schedule-10 inner tube and a 63.5-mm-dia, inconel -600...detonation tube had an inconel heat exchanger (described later). The PDE cycle consisted of three equally timed phases--fill, fire, and purge, as shown in...prevent phase change. The fuel was pressure fed to the inlet of the fuel heating system (FHS). The FHS consisted of two inconel heat exchangers, a

Study of the Effect of Swelling on Irradiation Assisted Stress Corrosion Cracking

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

Teysseyre, Sebastien Paul

2016-09-01

This report describes the methodology used to study the effect of swelling on the crack growth rate of an irradiation-assisted stress corrosion crack that is propagating in highly irradiated stainless steel 304 material irradiated to 33 dpa in the Experimental Breeder Reactor-II. The material selection, specimens design, experimental apparatus and processes are described. The results of the current test are presented.

Adaptive Model Predictive Control of Diesel Engine Selective Catalytic Reduction (SCR) Systems

ERIC Educational Resources Information Center

McKinley, Thomas L.

2009-01-01

Selective catalytic reduction or SCR is coming into worldwide use for diesel engine emissions reduction for on- and off-highway vehicles. These applications are characterized by broad operating range as well as rapid and unpredictable changes in operating conditions. Significant nonlinearity, input and output constraints, and stringent performance…

COMPARISON OF WEST GERMAN AND U.S. FLUE GAS DESULFURIZATION AND SELECTIVE CATALYTIC REDUCTION COSTS

EPA Science Inventory

The report documents a comparison of the actual cost retrofitting flue gas desulfurization (FGD) and selective catalytic reduction (SCR) on Federal Republic of German (FRG) boilers to cost estimating procedures used in the U.S. to estimate the retrofit of these controls on U.S. b...

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.

Integrated Biomass Gasification with Catalytic Partial Oxidation for Selective Tar Conversion

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

Zhang, Lingzhi; Wei, Wei; Manke, Jeff

Biomass gasification is a flexible and efficient way of utilizing widely available domestic renewable resources. Syngas from biomass has the potential for biofuels production, which will enhance energy security and environmental benefits. Additionally, with the successful development of low Btu fuel engines (e.g. GE Jenbacher engines), syngas from biomass can be efficiently used for power/heat co-generation. However, biomass gasification has not been widely commercialized because of a number of technical/economic issues related to gasifier design and syngas cleanup. Biomass gasification, due to its scale limitation, cannot afford to use pure oxygen as the gasification agent that used in coal gasification.more » Because, it uses air instead of oxygen, the biomass gasification temperature is much lower than well-understood coal gasification. The low temperature leads to a lot of tar formation and the tar can gum up the downstream equipment. Thus, the biomass gasification tar removal is a critical technology challenge for all types of biomass gasifiers. This USDA/DOE funded program (award number: DE-FG36-O8GO18085) aims to develop an advanced catalytic tar conversion system that can economically and efficiently convert tar into useful light gases (such as syngas) for downstream fuel synthesis or power generation. This program has been executed by GE Global Research in Irvine, CA, in collaboration with Professor Lanny Schmidt's group at the University of Minnesota (UoMn). Biomass gasification produces a raw syngas stream containing H2, CO, CO2, H2O, CH4 and other hydrocarbons, tars, char, and ash. Tars are defined as organic compounds that are condensable at room temperature and are assumed to be largely aromatic. Downstream units in biomass gasification such as gas engine, turbine or fuel synthesis reactors require stringent control in syngas quality, especially tar content to avoid plugging (gum) of downstream equipment. Tar- and ash-free syngas streams are a critical requirement for commercial deployment of biomass-based power/heat co-generation and biofuels production. There are several commonly used syngas clean-up technologies: (1) Syngas cooling and water scrubbing has been commercially proven but efficiency is low and it is only effective at small scales. This route is accompanied with troublesome wastewater treatment. (2) The tar filtration method requires frequent filter replacement and solid residue treatment, leading to high operation and capital costs. (3) Thermal destruction typically operates at temperatures higher than 1000oC. It has slow kinetics and potential soot formation issues. The system is expensive and materials are not reliable at high temperatures. (4) In-bed cracking catalysts show rapid deactivation, with durability to be demonstrated. (5) External catalytic cracking or steam reforming has low thermal efficiency and is faced with problematic catalyst coking. Under this program, catalytic partial oxidation (CPO) is being evaluated for syngas tar clean-up in biomass gasification. The CPO reaction is exothermic, implying that no external heat is needed and the system is of high thermal efficiency. CPO is capable of processing large gas volume, indicating a very compact catalyst bed and a low reactor cost. Instead of traditional physical removal of tar, the CPO concept converts tar into useful light gases (eg. CO, H2, CH4). This eliminates waste treatment and disposal requirements. All those advantages make the CPO catalytic tar conversion system a viable solution for biomass gasification downstream gas clean-up. This program was conducted from October 1 2008 to February 28 2011 and divided into five major tasks. - Task A: Perform conceptual design and conduct preliminary system and economic analysis (Q1 2009 ~ Q2 2009) - Task B: Biomass gasification tests, product characterization, and CPO tar conversion catalyst preparation. This task will be conducted after completing process design and system economics analysis. Major milestones include identification of syngas cleaning requirements for proposed system design, identification and selection of tar compounds and 2 mixtures for use in CPO tests, and preparation of CPO catalysts for validation. (Q3 2009 ~ Q4 2009) - Task C: Test CPO with biomass gasification product gas. Optimize CPO performance with selected tar compounds. Optimize CPO performance with multi-component mixtures. Milestones include optimizing CPO catalysts design, collecting CPO experimental data for next stage kinetic modeling and understanding the effect of relative reactivities on ultimate tar conversion and syngas yields. (Q1 2010 ~ Q3 2010) - Task D: Develop tar CPO kinetic model with CPO kinetic model and modeling results as deliverables. (Q3 2010 ~ Q2 2011) - Task E: Project management and reporting. Milestone: Quarterly reports and presentations, final report, work presented at national technical conferences (Q1 2009 ~ Q2 2011) At the beginning of the program, IP landscaping was conducted to understand the operation of various types of biomass gasifiers, their unique syngas/tar compositions and potential tar mitigation options using the catalytic partial oxidation technology. A process simulation model was developed to quantify the system performance and economics impact of CPO tar removal technology. Biomass gasification product compositions used for performance evaluation tests were identified after literature review and system modeling. A reaction system for tar conversion tests was designed, constructed, with each individual component shaken-down in 2009. In parallel, University of Minnesota built a lab-scale unit and evaluated the tar removal performance using catalytic reforming. Benzene was used as the surrogate compound. The biomass gasification raw syngas composition was provided by GE through system studies. In 2010, GE selected different tar compounds and evaluated the tar removal effectiveness of the CPO catalyst. The catalytic performance was evaluated under different operating conditions, including catalyst geometry, S/C ratio, O/C ratio, GHSV, and N2 dilution. An understanding of how to optimize catalytic tar removal efficiency by varying operating conditions has been developed. GE collaborated with UoMn in examining inorganic impurities effects. Catalysts were pre-impregnated with inorganic impurities commonly present in biomass gasification syngas, including Si, Ca, Mg, Na, K, P and S. UoMn performed catalyst characterization and has acquired fundamental understandings of impurities effect on catalytic tar removal. Based on experimental data and the proposed reaction pathway, GE constructed a model to predict kinetic performance for biomass gasification tar cleanup process. Experimental data (eg. tar conversion, reactor inlet and outlet temperatures, product distribution) at different operating conditions were used to validate the model. A good fit between model predictions and experimental data was found. This model will be a valuable tool in designing the tar removal reactor and identifying appropriate operating conditions. We attended the 2011 DOE Biomass Program Thermochemical Platform Review held in Denver, CO from February 16 to 18 and received very positive comments from the review panel. Further, syngas utility and biomass to power/fuel companies expressed strong interest in our tar removal technology.« less

Influence of bitumen type on cracking resistance of asphalt mixtures used in pavement overlays

NASA Astrophysics Data System (ADS)

Jaskula, P.; Szydlowski, C.; Stienss, M.

2018-05-01

Cracking is one of the predominant distresses occurring in flexible pavements, especially in old pavements that were rehabilitated with an asphalt overlay. In such cases asphalt mixtures should be designed to ensure high resistance to reflective cracking because new asphalt layers are exposed to existing cracks of the old pavement. The nature of these cracks can be various (transverse, longitudinal as well as crazy cracking). One factor that minimizes this type of distress is the proper mix design process, which should involve selection of specific bitumen binder and mineral mix gradation. However, still there is no universally adopted laboratory test method that would allow to clearly assess resistance of asphalt mixtures to reflective cracking. This paper describes the usage of one of the devices developed to test asphalt mixtures in terms of such distress – Texas Overlay Tester. For this test, samples prepared in laboratory conditions (i.e. compacted with the use of Superpave Gyratory Compactor) as well as obtained in the field (by core drilling) can be used. The results are obtained not only quickly and easily, but also with sufficient repeatability. The described method characterizes both crack initiation and crack propagation properties of asphalt mixtures. In this work one type of mineral mixture was tested with 4 different types of bitumen (one neat bitumen, two ordinary polymer-modified and one polymer-modified with high polymer content). For selected cases extra additives (rubber and loose fibres) were also tested. In total, six asphalt mixtures were tested. A ranking of the used binders was created on the basis of the results in order to conclude which bitumen would ensure the best performance characteristics in terms of reflective cracking. The results have clearly shown that deliberate choice of the binder used in the asphalt mixture for the overlay will significantly improve its reflective cracking resistance or even fatigue resistance.

Fatigue disbonding analysis of wide composite panels by means of Lamb waves

NASA Astrophysics Data System (ADS)

Michalcová, Lenka; Rechcígel, Lukáš; Bělský, Petr; Kucharský, Pavel

2018-03-01

Guided wave-based monitoring of composite structures plays an important role in the area of structural health monitoring (SHM) of aerospace structures. Adhesively bonded joints have not yet fulfilled current airworthiness requirements; hence, assemblies of carbon fibre-reinforced parts still require mechanical fasteners, and a verified SHM method with reliable disbonding/delamination detection and propagation assessment is needed. This study investigated the disbonding/delamination propagation in adhesively bonded panels using Lamb waves during fatigue tests. Analyses focused on the proper frequency and mode selection, sensor placement and selection of parameter sensitive to the growth of disbonding areas. Piezoelectric transducers placed across the bonded area were used as actuators and sensors. Lamb wave propagation was investigated considering the actual shape of the crack front and the mode of the crack propagation. The actual cracked area was determined by ultrasonic A-scans. A correlation between the crack propagation rate and the A0 mode velocity was found.

Subcritical crack growth in soda-lime glass in combined mode I and mode II loading

NASA Technical Reports Server (NTRS)

Singh, Dileep; Shetty, Dinesh K.

1990-01-01

Subcritical crack growth under mixed-mode loading was studied in soda-lime glass. Pure mode I, combined mode I and mode II, and pure mode II loadings were achieved in precracked disk specimens by loading in diametral compression at selected angles with respect to the symmetric radial crack. Crack growth was monitored by measuring the resistance changes in a microcircuit grid consisting of parallel, electrically conducting grid lines deposited on the surface of the disk specimens by photolithography. Subcritical crack growth rates in pure mode I, pure mode II, and combined mode I and mode II loading could be described by an exponential relationship between crack growth rate and an effective crack driving force derived from a mode I-mode II fracture toughness envelope. The effective crack driving force was based on an empirical representation of the noncoplanar strain energy release rate. Stress intensities for kinked cracks were assessed using the method of caustics and an initial decrease and a subsequent increase in the subcritical crack growth rates of kinked cracks were shown to correlate with the variations of the mode I and the mode II stress intensities.

Grain boundary selective oxidation and intergranular stress corrosion crack growth of high-purity nickel binary alloys in high-temperature hydrogenated water

DOE PAGES

Bruemmer, S. M.; Olszta, M. J.; Toloczko, M. B.; ...

2017-11-26

The effects of alloying elements in Ni-5at%X binary alloys on intergranular (IG) corrosion and stress corrosion cracking (SCC) have been assessed in 300–360 °C hydrogenated water at the Ni/NiO stability line. Alloys with Cr or Al additions exhibited grain boundary oxidation and IGSCC, while localized degradation was not observed for pure Ni, Ni-Cu or Ni-Fe alloys. Environment-enhanced crack growth was determined by comparing the response in water and N 2 gas. Lastly, results demonstrate that selective grain boundary oxidation of Cr and Al promoted IGSCC of these Ni alloys in hydrogenated water.

Grain boundary selective oxidation and intergranular stress corrosion crack growth of high-purity nickel binary alloys in high-temperature hydrogenated water

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

Bruemmer, S. M.; Olszta, M. J.; Toloczko, M. B.

The effects of alloying elements in Ni-5at%X binary alloys on intergranular (IG) corrosion and stress corrosion cracking (SCC) have been assessed in 300–360 °C hydrogenated water at the Ni/NiO stability line. Alloys with Cr or Al additions exhibited grain boundary oxidation and IGSCC, while localized degradation was not observed for pure Ni, Ni-Cu or Ni-Fe alloys. Environment-enhanced crack growth was determined by comparing the response in water and N 2 gas. Lastly, results demonstrate that selective grain boundary oxidation of Cr and Al promoted IGSCC of these Ni alloys in hydrogenated water.

Grain boundary selective oxidation and intergranular stress corrosion crack growth of high-purity nickel binary alloys in high-temperature hydrogenated water

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

Bruemmer, S. M.; Olszta, M. J.; Toloczko, M. B.

The effects of alloying elements in Ni-5at%X binary alloys on intergranular (IG) corrosion and stress corrosion cracking (SCC) have been assessed in 300-360°C hydrogenated water at the Ni/NiO stability line. Alloys with Cr or Al additions exhibited grain boundary oxidation and IGSCC, while localized degradation was not observed for pure Ni, Ni-Cu or Ni-Fe alloys. Environment-enhanced crack growth was determined by comparing the response in water and N2 gas. Results demonstrate that selective grain boundary oxidation of Cr and Al promoted IGSCC of these Ni alloys in hydrogenated water.

Study on optimization method of test conditions for fatigue crack detection using lock-in vibrothermography

NASA Astrophysics Data System (ADS)

Min, Qing-xu; Zhu, Jun-zhen; Feng, Fu-zhou; Xu, Chao; Sun, Ji-wei

2017-06-01

In this paper, the lock-in vibrothermography (LVT) is utilized for defect detection. Specifically, for a metal plate with an artificial fatigue crack, the temperature rise of the defective area is used for analyzing the influence of different test conditions, i.e. engagement force, excitation intensity, and modulated frequency. The multivariate nonlinear and logistic regression models are employed to estimate the POD (probability of detection) and POA (probability of alarm) of fatigue crack, respectively. The resulting optimal selection of test conditions is presented. The study aims to provide an optimized selection method of the test conditions in the vibrothermography system with the enhanced detection ability.

In vitro selection of catalytic RNAs

NASA Technical Reports Server (NTRS)

Chapman, K. B.; Szostak, J. W.

1994-01-01

In vitro selection techniques are poised to allow a rapid expansion of the study of catalysis by RNA enzymes (ribozymes). This truly molecular version of genetics has already been applied to the study of the structures of known ribozymes and to the tailoring of their catalytic activity to meet specific requirements of substrate specificity or reaction conditions. During the past year, in vitro selection has been successfully used to isolate novel RNA catalysts from random sequence pools.

A recyclable Au(I) catalyst for selective homocoupling of arylboronic acids: significant enhancement of nano-surface binding for stability and catalytic activity.

PubMed

Zhang, Xin; Zhao, Haitao; Wang, Jianhui

2010-08-01

Au nanoparticles stabilized by polystyrene-co-polymethacrylic acid microspheres (PS-co-PMAA) were prepared and characterized via X-ray diffraction (XRD), and transmission electron microscope (TEM). The Au nanoparticles supported on the microspheres showed highly selective catalytic activity for homo-coupling reactions of arylboronic acids in a system of aryl-halides and arylboronic acids. X-ray photoelectron spectroscopy (XPS) spectra of the catalyst shows large amounts of Au(I) complexes band to the surface of the Au nanoparticles, which contributes to the selective homocoupling of the arylboronic acids. More importantly, this supported Au complex is a highly recyclable catalyst. The supported Au catalyst can be recycled and reused at least 6 times for a phenylboronic acid reactant, whereas the parent complex shows very low catalytic activity for this compound. The high catalytic activity of this material is attributed to: (1) the high surface to volume ratio which leads to more active sites being exposed to reactants; (2) the strong surface binding of the Au nanoparticle to the Au(I) complexes, which enhances both the stability and the catalytic activity of these complexes.

Heterogeneous Catalysis: A Central Science for a Sustainable Future.

PubMed

Friend, Cynthia M; Xu, Bingjun

2017-03-21

Developing active, selective, and energy efficient heterogeneous catalytic processes is key to a sustainable future because heterogeneous catalysis is at the center of the chemicals and energy industries. The design, testing, and implementation of robust and selective heterogeneous catalytic processes based on insights from fundamental studies could have a tremendous positive impact on the world.

Environmental Technology Verification: Test Report of Mobile Source Selective Catalytic Reduction--Nett Technologies, Inc., BlueMAX 100 version A urea-based selective catalytic reduction technology

EPA Science Inventory

Nett Technologies’ BlueMAX 100 version A Urea-Based SCR System utilizes a zeolite catalyst coating on a cordierite honeycomb substrate for heavy-duty diesel nonroad engines for use with commercial ultra-low–sulfur diesel fuel. This environmental technology verification (ETV) repo...

PILOT-SCALE STUDY OF THE EFFECT OF SELECTIVE CATALYTIC REDUCTION CATALYST ON MERCURY SPECIATION IN ILLINOIS AND POWDER RIVER BASIN COAL COMBUSTION FLUE GASES

EPA Science Inventory

A study was conducted to investigate the effect of selective catalytic reduction (SCR) catalyst on mercury (Hg) speciation in bituminous and subbituminous coal combustion flue gases. Three different Illinois Basin bituminous coals (from high to low sulfur and chlorine) and one Po...

In-situ upgrading of biomass pyrolysis vapors: catalyst screening on a fixed bed reactor.

PubMed

Stefanidis, S D; Kalogiannis, K G; Iliopoulou, E F; Lappas, A A; Pilavachi, P A

2011-09-01

In-situ catalytic upgrading of biomass fast pyrolysis vapors was performed in a fixed bed bench-scale reactor at 500°C, for catalyst screening purposes. The catalytic materials tested include a commercial equilibrium FCC catalyst (E-cat), various commercial ZSM-5 formulations, magnesium oxide and alumina materials with varying specific surface areas, nickel monoxide, zirconia/titania, tetragonal zirconia, titania and silica alumina. The bio-oil was characterized measuring its water content, the carbon-hydrogen-oxygen (by difference) content and the chemical composition of its organic fraction. Each catalytic material displayed different catalytic effects. High surface area alumina catalysts displayed the highest selectivity towards hydrocarbons, yielding however low organic liquid products. Zirconia/titania exhibited good selectivity towards desired compounds, yielding higher organic liquid product than the alumina catalysts. The ZSM-5 formulation with the highest surface area displayed the most balanced performance having a moderate selectivity towards hydrocarbons, reducing undesirable compounds and producing organic liquid products at acceptable yields. Copyright © 2011 Elsevier Ltd. All rights reserved.

Catalytic nanoporous membranes

DOEpatents

Pellin, Michael J [Naperville, IL; Hryn, John N [Naperville, IL; Elam, Jeffrey W [Elmhurst, IL

2009-12-01

A nanoporous catalytic membrane which displays several unique features including pores which can go through the entire thickness of the membrane. The membrane has a higher catalytic and product selectivity than conventional catalysts. Anodic aluminum oxide (AAO) membranes serve as the catalyst substrate. This substrate is then subjected to Atomic Layer Deposition (ALD), which allows the controlled narrowing of the pores from 40 nm to 10 nm in the substrate by deposition of a preparatory material. Subsequent deposition of a catalytic layer on the inner surfaces of the pores reduces pore sizes to less than 10 nm and allows for a higher degree of reaction selectivity. The small pore sizes allow control over which molecules enter the pores, and the flow-through feature can allow for partial oxidation of reactant species as opposed to complete oxidation. A nanoporous separation membrane, produced by ALD is also provided for use in gaseous and liquid separations. The membrane has a high flow rate of material with 100% selectivity.

Low-temperature gas from marine shales: wet gas to dry gas over experimental time.

PubMed

Mango, Frank D; Jarvie, Daniel M

2009-11-09

Marine shales exhibit unusual behavior at low temperatures under anoxic gas flow. They generate catalytic gas 300 degrees below thermal cracking temperatures, discontinuously in aperiodic episodes, and lose these properties on exposure to trace amounts of oxygen. Here we report a surprising reversal in hydrocarbon generation. Heavy hydrocarbons are formed before light hydrocarbons resulting in wet gas at the onset of generation grading to dryer gas over time. The effect is moderate under gas flow and substantial in closed reactions. In sequential closed reactions at 100 degrees C, gas from a Cretaceous Mowry shale progresses from predominately heavy hydrocarbons (66% C5, 2% C1) to predominantly light hydrocarbons (56% C1, 8% C5), the opposite of that expected from desorption of preexisting hydrocarbons. Differences in catalyst substrate composition explain these dynamics. Gas flow should carry heavier hydrocarbons to catalytic sites, in contrast to static conditions where catalytic sites are limited to in-place hydrocarbons. In-place hydrocarbons and their products should become lighter with conversion thus generating lighter hydrocarbon over time, consistent with our experimental results. We recognize the similarities between low-temperature gas generation reported here and the natural progression of wet gas to dry gas over geologic time. There is now substantial evidence for natural catalytic activity in source rocks. Natural gas at thermodynamic equilibrium and the results reported here add to that evidence. Natural catalysis provides a plausible and unique explanation for the origin and evolution of gas in sedimentary basins.

Life cycle assessment of hydrogenated biodiesel production from waste cooking oil using the catalytic cracking and hydrogenation method.

PubMed

Yano, Junya; Aoki, Tatsuki; Nakamura, Kazuo; Yamada, Kazuo; Sakai, Shin-ichi

2015-04-01

There is a worldwide trend towards stricter control of diesel exhaust emissions, however presently, there are technical impediments to the use of FAME (fatty acid methyl esters)-type biodiesel fuel (BDF). Although hydrogenated biodiesel (HBD) is anticipated as a new diesel fuel, the environmental performance of HBD and its utilization system have not been adequately clarified. Especially when waste cooking oil is used as feedstock, not only biofuel production but also the treatment of waste cooking oil is an important function for society. A life cycle assessment (LCA), including uncertainty analysis, was conducted to determine the environmental benefits (global warming, fossil fuel consumption, urban air pollution, and acidification) of HBD produced from waste cooking oil via catalytic cracking and hydrogenation, compared with fossil-derived diesel fuel or FAME-type BDF. Combined functional unit including "treatment of waste cooking oil" and "running diesel vehicle for household waste collection" was established in the context of Kyoto city, Japan. The calculation utilized characterization, damage, and integration factors identified by LIME2, which was based on an endpoint modeling method. The results show that if diesel vehicles that comply with the new Japanese long-term emissions gas standard are commonly used in the future, the benefit of FAME-type BDF will be relatively limited. Furthermore, the scenario that introduced HBD was most effective in reducing total environmental impact, meaning that a shift from FAME-type BDF to HBD would be more beneficial. Copyright © 2015 Elsevier Ltd. All rights reserved.

Fatigue-Life Prediction Methodology Using Small-Crack Theory

NASA Technical Reports Server (NTRS)

Newmann, James C., Jr.; Phillips, Edward P.; Swain, M. H.

1997-01-01

This paper reviews the capabilities of a plasticity-induced crack-closure model to predict fatigue lives of metallic materials using 'small-crack theory' for various materials and loading conditions. Crack-tip constraint factors, to account for three-dimensional state-of-stress effects, were selected to correlate large-crack growth rate data as a function of the effective-stress-intensity factor range (delta K(eff)) under constant-amplitude loading. Some modifications to the delta k(eff)-rate relations were needed in the near-threshold regime to fit measured small-crack growth rate behavior and fatigue endurance limits. 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 made of two aluminum alloys and a steel under constant-amplitude and spectrum loading. Fatigue lives were calculated using the crack-growth relations and microstructural features like those that initiated cracks for the aluminum alloys and steel for edge-notched specimens. An equivalent-initial-flaw-size concept was used to calculate fatigue lives in other cases. Results from the tests and analyses agreed well.

Chemiluminescence analyzer of NOx as a high-throughput screening tool in selective catalytic reduction of NO

PubMed Central

Oh, Kwang Seok; Woo, Seong Ihl

2011-01-01

A chemiluminescence-based analyzer of NOx gas species has been applied for high-throughput screening of a library of catalytic materials. The applicability of the commercial NOx analyzer as a rapid screening tool was evaluated using selective catalytic reduction of NO gas. A library of 60 binary alloys composed of Pt and Co, Zr, La, Ce, Fe or W on Al2O3 substrate was tested for the efficiency of NOx removal using a home-built 64-channel parallel and sequential tubular reactor. The NOx concentrations measured by the NOx analyzer agreed well with the results obtained using micro gas chromatography for a reference catalyst consisting of 1 wt% Pt on γ-Al2O3. Most alloys showed high efficiency at 275 °C, which is typical of Pt-based catalysts for selective catalytic reduction of NO. The screening with NOx analyzer allowed to select Pt-Ce(X) (X=1–3) and Pt–Fe(2) as the optimal catalysts for NOx removal: 73% NOx conversion was achieved with the Pt–Fe(2) alloy, which was much better than the results for the reference catalyst and the other library alloys. This study demonstrates a sequential high-throughput method of practical evaluation of catalysts for the selective reduction of NO. PMID:27877438

Gas Selectivity Control in Co3O4 Sensor via Concurrent Tuning of Gas Reforming and Gas Filtering using Nanoscale Hetero-Overlayer of Catalytic Oxides.

PubMed

Jeong, Hyun-Mook; Jeong, Seong-Yong; Kim, Jae-Hyeok; Kim, Bo-Young; Kim, Jun-Sik; Abdel-Hady, Faissal; Wazzan, Abdulaziz A; Al-Turaif, Hamad Ali; Jang, Ho Won; Lee, Jong-Heun

2017-11-29

Co 3 O 4 sensors with a nanoscale TiO 2 or SnO 2 catalytic overlayer were prepared by screen-printing of Co 3 O 4 yolk-shell spheres and subsequent e-beam evaporation of TiO 2 and SnO 2 . The Co 3 O 4 sensors with 5 nm thick TiO 2 and SnO 2 overlayers showed high responses (resistance ratios) to 5 ppm xylene (14.5 and 28.8) and toluene (11.7 and 16.2) at 250 °C with negligible responses to interference gases such as ethanol, HCHO, CO, and benzene. In contrast, the pure Co 3 O 4 sensor did not show remarkable selectivity toward any specific gas. The response and selectivity to methylbenzenes and ethanol could be systematically controlled by selecting the catalytic overlayer material, varying the overlayer thickness, and tuning the sensing temperature. The significant enhancement of the selectivity for xylene and toluene was attributed to the reforming of less reactive methylbenzenes into more reactive and smaller species and oxidative filtering of other interference gases, including ubiquitous ethanol. The concurrent control of the gas reforming and oxidative filtering processes using a nanoscale overlayer of catalytic oxides provides a new, general, and powerful tool for designing highly selective and sensitive oxide semiconductor gas sensors.

Field investigation of low-temperature cracking and stiffness moduli on selected roads with conventional and high modulus asphalt concrete

NASA Astrophysics Data System (ADS)

Judycki, Józef; Jaczewski, Mariusz; Ryś, Dawid; Pszczoła, Marek; Jaskuła, Piotr; Glinicki, Adam

2017-09-01

High Modulus Asphalt Concrete (HMAC) was introduced in Poland as a one of the solutions to the problem of rutting, type of deterioration common in the 1990s. After first encouraging trials in 2002 HMAC was widely used for heavily loaded national roads and motorways. However some concerns were raised about low-temperature cracking of HMAC. This was the main reason of the studies presented in this article were started. The article presents the comparison of performance of pavements constructed in typical contract conditions with the road bases made of HMAC and conventional asphalt concrete (AC). The field investigation was focused on the number of low-temperature cracks, bearing capacity (based on FWD test) of road sections localized in coldest region of Poland. Also load transfer efficiency of selected low-temperature cracks was assessed. FWD test confirmed lower deflections of pavements with HMAC and two times higher stiffness modulus of asphalt courses in comparison to pavements constructed with conventional AC mixtures. Relation of stiffness of asphalt layers and amount of low-temperature cracks showed that the higher stiffness modulus of asphalt layers could lead to increase of the number of low-temperature cracks. FWD test results showed that the load transfer efficiency of low-temperature cracks on pavements with HMAC presents very low values, very close to lack of load transfer. It was surprising as section with HMAC road base were aged from 2 to 5 years and presented very good bearing capacity.

Analyses of Fatigue and Fatigue-Crack Growth under Constant- and Variable-Amplitude Loading

NASA Technical Reports Server (NTRS)

Newman, J. C., 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 K(sub eff)) under constant-amplitude loading. Modifications to the delta K(sub eff)-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.

Nano-cracks in a synthetic graphite composite for nuclear applications

NASA Astrophysics Data System (ADS)

Liu, Dong; Cherns, David

2018-05-01

Mrozowski nano-cracks in nuclear graphite were studied by transmission electron microscopy and selected area diffraction. The material consisted of single crystal platelets typically 1-2 nm thick and stacked with large relative rotations around the c-axis; individual platelets had both hexagonal and cubic stacking order. The lattice spacing of the (0002) planes was about 3% larger at the platelet boundaries which were the source of a high fraction of the nano-cracks. Tilting experiments demonstrated that these cracks were empty, and not, as often suggested, filled by amorphous material. In addition to conventional Mrozowski cracks, a new type of nano-crack is reported, which originates from the termination of a graphite platelet due to crystallographic requirements. Both types are crucial to understanding the evolution of macro-scale graphite properties with neutron irradiation.

Using advanced tomography techniques to investigate the development of White Etching Cracks in a prematurely failed field bearing

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

Gould, Benjamin; Greco, Aaron; Stadler, Kenred

Crack surrounded by areas of microstructural alteration deemed "White etching cracks" (WECs) lead to premature failures within a multitude applications. While the exact cause of these failures remains unknown, a large number of hypotheses exist as to how and why these cracks form. The aim of the current work is to study newly initiated WEC networks using X-ray tomography followed by selective sectioning, in an attempt to elucidate the formation mechanisms of these cracks. The results obtained show that, for the presented bearing, WECs form preferentially around multi-phase inclusions containing aluminum, manganese, and sulfur. Additionally the results support the ideamore » that the microstructural alterations form secondary to any cracking, suggesting that the alterations are simply a symptom of a preexisting failure.« less

Enhanced treatment selection for reflective joint cracking in composite pavements : final report.

DOT National Transportation Integrated Search

2015-09-01

This research developed a decisionmaking process that can be used by INDOT to enhance identification of the condition of the : underlying concrete joints or cracks by looking at the surface distresses of the asphalt overlay in composite pavements....

Evaluation of deck durability on continuous beam highway bridges.

DOT National Transportation Integrated Search

1985-01-01

In an effort to determine the extent of deck cracking on continuous steel beam bridges and the effect of the cracking on deck durability, 137 structures were visually inspected and 5 of these were selected for detailed evaluation. The general survey ...

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

Air breathing lithium power cells

DOEpatents

Farmer, Joseph C.

2014-07-15

A cell suitable for use in a battery according to one embodiment includes a catalytic oxygen cathode; a stabilized zirconia electrolyte for selective oxygen anion transport; a molten salt electrolyte; and a lithium-based anode. A cell suitable for use in a battery according to another embodiment includes a catalytic oxygen cathode; an electrolyte; a membrane selective to molecular oxygen; and a lithium-based anode.

Iron-catalysed fluoroaromatic coupling reactions under catalytic modulation with 1,2-bis(diphenylphosphino)benzene.

PubMed

Hatakeyama, Takuji; Kondo, Yoshiyuki; Fujiwara, Yu-Ichi; Takaya, Hikaru; Ito, Shingo; Nakamura, Eiichi; Nakamura, Masaharu

2009-03-14

A catalytic amount of 1,2-bis(diphenylphosphino)benzene (DPPBz) achieves selective cleavage of sp(3)-carbon-halogen bond in the iron-catalysed cross-coupling between polyfluorinated arylzinc reagents and alkyl halides, which was unachievable with a stoichiometric modifier such as TMEDA; the selective iron-catalysed fluoroaromatic coupling provides easy and practical access to polyfluorinated aromatic compounds.

Tuning selectivity in catalysis by controlling particle shape

NASA Astrophysics Data System (ADS)

Lee, Ilkeun; Delbecq, Françoise; Morales, Ricardo; Albiter, Manuel A.; Zaera, Francisco

2009-02-01

A catalytic process for the selective formation of cis olefins would help minimize the production of unhealthy trans fats during the partial hydrogenation of edible oils. Here we report on the design of such a process on the basis of studies with model systems. Temperature programmed desorption data on single crystals showed that the isomerization of trans olefins to their cis counterparts is promoted by (111) facets of platinum, and that such selectivity is reversed on more open surfaces. Quantum mechanics calculations suggested that the extra stability of cis olefins seen on hydrogen-saturated Pt(111) surfaces may be due to a lesser degree of surface reconstruction, a factor found to be significant in the adsorption on close-packed platinum surfaces. Kinetic data using catalysts made out of dispersed tetrahedral Pt nanoparticles corroborated the selective promotion of the trans-to-cis isomerization on the (111) facets of the metal. Our work provides an example for how catalytic selectivity may be controlled by controlling the shape of the catalytic particles.

Self-Replicating Cracks: A Collaborative Fracture Mode in Thin Films

NASA Astrophysics Data System (ADS)

Marthelot, Joël; Roman, Benoît; Bico, José; Teisseire, Jérémie; Dalmas, Davy; Melo, Francisco

2014-08-01

Straight cracks are observed in thin coatings under residual tensile stress, resulting into the classical network pattern observed in china crockery, old paintings, or dry mud. Here, we present a novel fracture mechanism where delamination and propagation occur simultaneously, leading to the spontaneous self-replication of an initial template. Surprisingly, this mechanism is active below the standard critical tensile load for channel cracks and selects a robust interaction length scale on the order of 30 times the film thickness. Depending on triggering mechanisms, crescent alleys, spirals, or long bands are generated over a wide range of experimental parameters. We describe with a simple physical model, the selection of the fracture path and provide a configuration diagram displaying the different failure modes.

Study of gas tungsten arc welding procedures for tantalum alloy T-111 (Ta-8 W-2Hf) plate

NASA Technical Reports Server (NTRS)

Gold, R. E.; Kesterson, R. L.

1973-01-01

Methods of eliminating or reducing underbread cracking in multipass GTA welds in thick T-111 plate were studied. Single V butt welds prepared using experimental filler metal compositions and standard weld procedures resulted in only moderate success in reducing underbread cracking. Subsequent procedural changes incorporating manual welding, slower weld speeds, and three or fewer fill passes resulted in crack-free single V welds only when the filler metal was free of hafnium. The double V joint design with successive fill passes on opposite sides of the joint produced excellent welds. The quality of each weld was determined metallographically since the cracking, when present, was very slight and undetectable using standard NDT techniques. Tensile and bend tests were performed on selected weldments. The inherent filler metal strength and the joint geometry determined the strength of the weldment. Hardness and electron beam microprobe traverses were made on selected specimens with the result that significant filler metal-base metal dilution as well as hafnium segregation was detected. A tentative explanation of T-111 plate underbread cracking is presented based on the intrinsic effects of hafnium in the weldment.

DOE-GO-14154-1 OHIO FINAL report Velocys 30Sept08

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

Terry J. Mazanec

2008-09-30

The overall goal of the OHIO project was to develop a commercially viable high intensity process to produce ethylene by controlled catalytic reaction of ethane with oxygen in a microchannel reactor. Microchannel technology provides a breakthrough solution to the challenges identified in earlier development work on catalytic ethane oxidation. Heat and mass transfer limitations at the catalyst surface create destructively high temperatures that are responsible for increased production of waste products (CO, CO2, and CH4). The OHIO project focused on microscale energy and mass transfer management, designed to alleviate these transport limitations, thereby improving catalyst selectivity and saving energy-rich feedstock.more » The OHIO project evaluated ethane oxidation in small scale microchannel laboratory reactors including catalyst test units, and full commercial length single- and multi-channel reactors. Small scale catalyst and single channel results met target values for ethylene yields, demonstrating that the microchannel concept improves mass and heat transport compared to conventional reactors and results in improved ethylene yield. Earlier economic sensitivity studies of ethane oxidation processes suggested that only modest improvements were necessary to provide a system that provides significant feedstock, energy, and capital benefits compared to conventional steam ethane cracking. The key benefit derived from the OHIO process is energy savings. Ethylene production consumes more energy than any other U.S. chemical process.1 The OHIO process offers improved feedstock utilization and substantial energy savings due to a novel reaction pathway and the unique abilities of microchannel process technology to control the reaction temperature and other critical process parameters. Based on projected economic benefits of the process, the potential energy savings could reach 150 trillion Btu/yr by the year 2020, which is the equivalent of over 25 million barrels of oil.« less

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

DOE PAGES

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

2018-01-02

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

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

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

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

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

Tuning the Selectivity of Single-Site Supported Metal Catalysts with Ionic Liquids

DOE PAGES

Babucci, Melike; Fang, Chia -Yu; Hoffman, Adam S.; ...

2017-09-11

1,3-Dialkylimidazolium ionic liquid coatings act as electron donors, increasing the selectivity for partial hydrogenation of 1,3-butadiene catalyzed by iridium complexes supported on high-surface-area γ-Al 2O 3. High-energy-resolution fluorescence detection X-ray absorption near-edge structure (HERFD XANES) measurements quantify the electron donation and are correlated with the catalytic activity and selectivity. Furthermore, the results demonstrate broad opportunities to tune electronic environments and catalytic properties of atomically dispersed supported metal catalysts.

A sinter-resistant catalytic system fabricated by maneuvering the selectivity of SiO2 deposition onto the TiO2 surface versus the Pt nanoparticle surface.

PubMed

Lu, Ping; Campbell, Charles T; Xia, Younan

2013-10-09

A triphasic catalytic system (Pt/TiO2-SiO2) with an "islands in the sea" configuration was fabricated by controlling the selectivity of SiO2 deposition onto the surface of TiO2 versus the surface of Pt nanoparticles. The Pt surface was exposed, while the nanoparticles were supported on TiO2 and isolated from each other by SiO2 to achieve both significantly improved sinter resistance up to 700 °C and outstanding activity after high-temperature calcination. This work not only demonstrates the feasibility of using a new triphasic system with uncovered catalyst to maximize the thermal stability and catalytic activity but also offers a general approach to the synthesis of high-performance catalytic systems with tunable compositions.

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.

Genetic analysis of biodegradation of tetralin by a Sphingomonas strain

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

Hernaez, M.J.; Santero, E.; Reineke, W.

Tetralin (1,2,3,4-tetrahydronaphthalene) is produced for industrial purposes from naphthalene by catalytic hydrogenation or from anthracene by cracking. A strain designated TFA which very efficiently utilizes tetralin has been isolated from the Rhine river. The strain has been identified as Sphingomonas macrogoltabidus, based on 16S rDNA sequence similarity. Genetic analysis of tetralin biodegradation has been performed by insertion mutagenesis and by physical analysis and analysis of complementation between the mutants. The genes involved in tetralin utilization are clustered in a region of 9 kb, comprising at least five genes grouped in two divergently transcribed operons.

A Review of Australian Investigations on Aeronautical Fatigue During the Period April 1983 to March 1985.

DTIC Science & Technology

1985-03-01

surface crack 6 mm deep . The unpatched specimens sustained on average approximately 25,000 cycles at 5 + 5 ksi whilst the patched specimen survived...directly a relationship between crack growth and selected AE parameters. However, crack growth information available from NDI and fractography has been...It was found that maintaining a good quality component data tracking base is not a straight-forward operation and the lessons learned have been

Mix design of asphalt mixture used for the waterproof and anti-cracking layer in the rainy area of South China.

PubMed

Liu, Fuming; Dong, Aixia; Liu, Chaoqun; Wu, Wenqing

2018-01-01

In this study, the asphalt mixture (porosity <2%) was tested for use between the upper and middle layers of the asphalt pavement to improve its interlayer structure and to enhance its related waterproof and anti-cracking ability. Considering the weather characteristics and traffic conditions in Jiangxi Province, appropriate raw materials were selected. Based on the technical indexes of the raw materials, expected porosity (<2%), and AC-5 standard for the asphalt mixture, experiments were conducted to determine the best gradation range of the waterproof and anti-cracking layer, and to obtain the optimum amount of the asphalt and fiber used based on Marshall tests. The high-temperature rutting test, low-temperature cracking test, and water stability test were conducted to evaluate the pavement performance of the waterproof and anti-cracking layer. A waterproof and anti-cracking layer was added between the upper and middle layers of the asphalt pavement, which has excellent performance for avoiding cracks and water damage.

Selective catalytic reduction system and process for control of NO.sub.x emissions in a sulfur-containing gas stream

DOEpatents

Sobolevskiy, Anatoly

2015-08-11

An exhaust gas treatment process, apparatus, and system for reducing the concentration of NOx, CO and hydrocarbons in a gas stream, such as an exhaust stream (29), via selective catalytic reduction with ammonia is provided. The process, apparatus and system include a catalytic bed (32) having a reducing only catalyst portion (34) and a downstream reducing-plus-oxidizing portion (36). Each portion (34, 36) includes an amount of tungsten. The reducing-plus-oxidizing catalyst portion (36) advantageously includes a greater amount of tungsten than the reducing catalyst portion (36) to markedly limit ammonia salt formation.

Stress-corrosion cracking in metals

NASA Technical Reports Server (NTRS)

1971-01-01

Criteria and recommended practices for preventing stress-corrosion cracking from impairing the structural integrity and flightworthiness of space vehicles are presented. The important variables affecting stress-corrosion cracking are considered to be the environment, including time and temperature; metal composition, and structure; and sustained tensile stress. For designing spacecraft structures that are free of stress-corrosion cracking for the service life of the vehicle the following rules apply: (1) identification and control of the environments to which the structure will be exposed during construction, storage, transportation, and use; (2) selection of alloy compositions and tempers which are resistant to stress-corrosion cracking in the identified environment; (3) control of fabrication and other processes which may introduce residual tensile stresses or damage the material; (4) limitation of the combined residual and applied tensile stresses to below the threshold stress level for the onset of cracking throughout the service life of the vehicle; and (5) establishment of a thorough inspection program.

Methods and apparatuses for preparing a surface to have catalytic activity

DOEpatents

Cooks, Robert G [West Lafayette, IN; Peng, Wen-Ping [West Lafayette, IN; Ouyang, Zheng [West Lafayette, IN; Goodwin, Michael P [West Lafayette, IN

2011-03-22

The invention provides methods and apparatuses that utilize mass spectrometry for preparation of a surface to have catalytic activity through molecular soft-landing of mass selected ions. Mass spectrometry is used to generate combinations of atoms in a particular geometrical arrangement, and ion soft-landing selects this molecular entity or combination of entities and gently deposits the entity or combination intact onto a surface.

Stereodivergent catalytic doubly diastereoselective nitroaldol reactions using heterobimetallic complexes.

PubMed

Sohtome, Yoshihiro; Kato, Yuko; Handa, Shinya; Aoyama, Naohiro; Nagawa, Keita; Matsunaga, Shigeki; Shibasaki, Masakatsu

2008-06-05

Stereodivergent construction of three contiguous stereocenters in catalytic doubly diastereoselective nitroaldol reactions of alpha-chiral aldehydes with nitroacetaldehyde dimethyl acetal using two types of heterobimetallic catalysts is described. A La-Li-BINOL (LLB) catalyst afforded anti,syn-nitroaldol products in >20:1-14:1 selectivity, and a Pd/La/Schiff base catalyst afforded complimentary syn,syn-nitroaldol products in 10:1-5:1 selectivity.

Environmental Technology Verification Test Report of Mobile Source Selective Catalytic Reduction, Johnson Matthey SCCRT, Version 1, Selective Catalytic Reduction Technology with a Catalyzed Continuously Regenerating Trap

EPA Science Inventory

The Johnson Matthey SCCRT, v.1 technology is a urea-based SCR system combined with a CCRT filter designed for on-highway light, medium, and heavy heavy-duty diesel, urban and non-urban, bus exhaust gas recirculation (EGR)-or non-EGR-equipped engines for use with commercial ultra-...

Chemoselective catalytic conversion of glycerol as a biorenewable source to valuable commodity chemicals.

PubMed

Zhou, Chun-Hui Clayton; Beltramini, Jorge N; Fan, Yong-Xian; Lu, G Q Max

2008-03-01

New opportunities for the conversion of glycerol into value-added chemicals have emerged in recent years as a result of glycerol's unique structure, properties, bioavailability, and renewability. Glycerol is currently produced in large amounts during the transesterification of fatty acids into biodiesel and as such represents a useful by-product. This paper provides a comprehensive review and critical analysis on the different reaction pathways for catalytic conversion of glycerol into commodity chemicals, including selective oxidation, selective hydrogenolysis, selective dehydration, pyrolysis and gasification, steam reforming, thermal reduction into syngas, selective transesterification, selective etherification, oligomerization and polymerization, and conversion of glycerol into glycerol carbonate.

Morphological effects on the selectivity of intramolecular versus intermolecular catalytic reaction on Au nanoparticles.

PubMed

Wang, Dan; Sun, Yuanmiao; Sun, Yinghui; Huang, Jing; Liang, Zhiqiang; Li, Shuzhou; Jiang, Lin

2017-06-14

It is hard for metal nanoparticle catalysts to control the selectivity of a catalytic reaction in a simple process. In this work, we obtain active Au nanoparticle catalysts with high selectivity for the hydrogenation reaction of aromatic nitro compounds, by simply employing spine-like Au nanoparticles. The density functional theory (DFT) calculations further elucidate that the morphological effect on thermal selectivity control is an internal key parameter to modulate the nitro hydrogenation process on the surface of Au spines. These results show that controlled morphological effects may play an important role in catalysis reactions of noble metal NPs with high selectivity.

An Iron Reservoir to the Catalytic Metal

PubMed Central

Liu, Fange; Geng, Jiafeng; Gumpper, Ryan H.; Barman, Arghya; Davis, Ian; Ozarowski, Andrew; Hamelberg, Donald; Liu, Aimin

2015-01-01

The rubredoxin motif is present in over 74,000 protein sequences and 2,000 structures, but few have known functions. A secondary, non-catalytic, rubredoxin-like iron site is conserved in 3-hydroxyanthranilate 3,4-dioxygenase (HAO), from single cellular sources but not multicellular sources. Through the population of the two metal binding sites with various metals in bacterial HAO, the structural and functional relationship of the rubredoxin-like site was investigated using kinetic, spectroscopic, crystallographic, and computational approaches. It is shown that the first metal presented preferentially binds to the catalytic site rather than the rubredoxin-like site, which selectively binds iron when the catalytic site is occupied. Furthermore, an iron ion bound to the rubredoxin-like site is readily delivered to an empty catalytic site of metal-free HAO via an intermolecular transfer mechanism. Through the use of metal analysis and catalytic activity measurements, we show that a downstream metabolic intermediate can selectively remove the catalytic iron. As the prokaryotic HAO is often crucial for cell survival, there is a need for ensuring its activity. These results suggest that the rubredoxin-like site is a possible auxiliary iron source to the catalytic center when it is lost during catalysis in a pathway with metabolic intermediates of metal-chelating properties. A spare tire concept is proposed based on this biochemical study, and this concept opens up a potentially new functional paradigm for iron-sulfur centers in iron-dependent enzymes as transient iron binding and shuttling sites to ensure full metal loading of the catalytic site. PMID:25918158

Quality management of cracking distress survey in flexible pavements using LTRC digital highway data vehicle : research project capsule.

DOT National Transportation Integrated Search

2016-04-01

The primary objectives of this research are to compare and validate cracking survey : results on selected fl exible pavements obtained from the LTRC data collection system : and from the Louisiana current contracted application; to investigate the fe...

Analysis of a hybrid, unidirectional buffer strip laminate

NASA Technical Reports Server (NTRS)

Dharani, L. R.; Goree, J. G.

1983-01-01

A method of analysis capable of predicting accurately the fracture behavior of a unidirectional composite laminate containing symmetrically placed buffer strips is presented. As an example, for a damaged graphite/epoxy laminate, the results demonstrate the manner in which to select the most efficient combination of buffer strip properties necessary to inhibit crack growth. Ultimate failure of the laminate after crack arrest can occur under increasing load either by continued crack extension through the buffer strips or the crack can jump the buffer strips. For some typical hybrid materials it is found that a buffer strip spacing-to-width ratio of about four to one is the most efficient.

Some advances/results in monitoring road cracks from 2D pavement images within the scope of the collaborative FP7 TRIMM project

NASA Astrophysics Data System (ADS)

Baltazart, Vincent; Moliard, Jean-Marc; Amhaz, Rabih; Wright, Dean; Jethwa, Manish

2015-04-01

Monitoring road surface conditions is an important issue in many countries. Several projects have looked into this issue in recent years, including TRIMM 2011-2014. The objective of such projects has been to detect surface distresses, like cracking, raveling and water ponding, in order to plan effective road maintenance and to afford a better sustainability of the pavement. The monitoring of cracking conventionally focuses on open cracks on the surface of the pavement, as opposed to reflexive cracks embedded in the pavement materials. For monitoring surface condition, in situ human visual inspection has been gradually replaced by automatic image data collection at traffic speed. Off-line image processing techniques have been developed for monitoring surface condition in support of human visual control. Full automation of crack monitoring has been approached with caution, and depends on a proper manual assessment of the performance. This work firstly presents some aspects of the current state of monitoring that have been reported so far in the literature and in previous projects: imaging technology and image processing techniques. Then, the work presents the two image processing techniques that have been developed within the scope of the TRIMM project to automatically detect pavement cracking from images. The first technique is a heuristic approach (HA) based on the search for gradient within the image. It was originally developed to process pavement images from the French imaging device, Aigle-RN. The second technique, the Minimal Path Selection (MPS) method, has been developed within an ongoing PhD work at IFSTTAR. The proposed new technique provides a fine and accurate segmentation of the crack pattern along with the estimation of the crack width. HA has been assessed against the field data collection provided by Yotta and TRL with the imaging device Tempest 2. The performance assessment has been threefold: first it was performed against the reference data set including 130 km of pavement images over UK roads, second over a few selected short sections of contiguous pavement images, and finally over a few sample images as a case study. The performance of MPS has been assessed against an older image data base. Pixel-based PGT was available to provide the most sensitive performance assessment. MPS has shown its ability to provide a very accurate cracking pattern without reducing the image resolution on the segmented images. Thus, it allows measurement of the crack width; it is found to behave more robustly against the image texture and better matched for dealing with low contrast pavement images. The benchmarking of seven automatic segmentation techniques has been provided at both the pixel and the grid levels. The performance assessment includes three minimal path selection algorithms, namely MPS, Free Form Anisotropy (FFA), one geodesic contour with automatic selection of points of interests (GC-POI), HA, and two Markov-based methods. Among others, MPS approach reached the best performance at the pixel level while it is matched to the FFA approach at the grid level. Finally, the project has emphasized the need for a reliable ground truth data collection. Owing to its accuracy, MPS may serve as a reference benchmark for other methods to provide the automatic segmentation of pavement images at the pixel level and beyond. As a counterpart, MPS requires a reduction in the computing time. Keywords: cracking, automatic segmentation, image processing, pavement, surface distress, monitoring, DICE, performance

The Crack Cocaine Crisis. Joint Hearing before the Select Committee on Narcotics Abuse and Control, House of Representatives and the Select Committee on Children, Youth, and Families. House of Representatives, Ninety-Ninth Congress, Second Session (July 15, 1986).

ERIC Educational Resources Information Center

Congress of the U.S., Washington, DC. House Select Committee on Children, Youth, and Families.

This document contains witness testimonies and prepared statements from the Congressional hearing called to examine what the federal government as well as local and state governments are doing and can do to respond to the growing problem of crack cocaine, and what prevention and treatment approaches are effective. Opening statements and/or…

Elevated temperature crack growth

NASA Technical Reports Server (NTRS)

Kim, K. S.; Yau, J. F.; Vanstone, R. H.; Laflen, J. H.

1984-01-01

Critical gas turbine engine hot section components such as blades, vanes, and combustor liners tend to develop minute cracks during early stages of operations. The ability of currently available path-independent (P-I) integrals to correlate fatigue crack propagation under conditions that simulate the turbojet engine combustor liner environment was determined. To date, an appropriate specimen design and a crack displacement measurement method were determined. Alloy 718 was selected as the analog material based on its ability to simulate high temperature behavior at lower temperatures in order to facilitate experimental measurements. Available P-I integrals were reviewed and the best approaches are being programmed into a finite element post processor for eventual comparison with experimental data. The experimental data will include cyclic crack growth tests under thermomechanical conditions, and, additionally, thermal gradients.

Cost-effectiveness and performance of overlay systems in Illinois, volume 2 : guidelines for interlayer system selection decision when used in HMA overlays.

DOT National Transportation Integrated Search

2009-05-01

In an effort to control reflective cracking in hot-mix asphalt (HMA) overlays placed over Portland Cement : Concrete (PCC) pavements, several reflective crack control (RCC) systems, including interlayer systems, : have been used. However, the cost-ef...

Development of a high-temperature durable catalyst for use in catalytic combustors for advanced automotive gas turbine engines

NASA Astrophysics Data System (ADS)

Tong, H.; Snow, G. C.; Chu, E. K.; Chang, R. L. S.; Angwin, M. J.; Pessagno, S. L.

1981-09-01

Durable catalytic reactors for advanced gas turbine engines were developed. Objectives were: to evaluate furnace aging as a cost effective catalytic reactor screening test, measure reactor degradation as a function of furnace aging, demonstrate 1,000 hours of combustion durability, and define a catalytic reactor system with a high probability of successful integration into an automotive gas turbine engine. Fourteen different catalytic reactor concepts were evaluated, leading to the selection of one for a durability combustion test with diesel fuel for combustion conditions. Eight additional catalytic reactors were evaluated and one of these was successfully combustion tested on propane fuel. This durability reactor used graded cell honeycombs and a combination of noble metal and metal oxide catalysts. The reactor was catalytically active and structurally sound at the end of the durability test.

Development of a high-temperature durable catalyst for use in catalytic combustors for advanced automotive gas turbine engines

NASA Technical Reports Server (NTRS)

Tong, H.; Snow, G. C.; Chu, E. K.; Chang, R. L. S.; Angwin, M. J.; Pessagno, S. L.

1981-01-01

Durable catalytic reactors for advanced gas turbine engines were developed. Objectives were: to evaluate furnace aging as a cost effective catalytic reactor screening test, measure reactor degradation as a function of furnace aging, demonstrate 1,000 hours of combustion durability, and define a catalytic reactor system with a high probability of successful integration into an automotive gas turbine engine. Fourteen different catalytic reactor concepts were evaluated, leading to the selection of one for a durability combustion test with diesel fuel for combustion conditions. Eight additional catalytic reactors were evaluated and one of these was successfully combustion tested on propane fuel. This durability reactor used graded cell honeycombs and a combination of noble metal and metal oxide catalysts. The reactor was catalytically active and structurally sound at the end of the durability test.

Crystal structures and catalytic performance of three new methoxy substituted salen type nickel(II) Schiff base complexes derived from meso-1,2-diphenyl-1,2-ethylenediamine

NASA Astrophysics Data System (ADS)

Ghaffari, Abolfazl; Behzad, Mahdi; Pooyan, Mahsa; Amiri Rudbari, Hadi; Bruno, Giuseppe

2014-04-01

Three new nickel(II) complexes of a series of methoxy substituted salen type Schiff base ligands were synthesized and characterized by IR, UV-Vis and 1H NMR spectroscopy and elemental analysis. The ligands were synthesized from the condensation of meso-1,2-diphenyl-1,2-ethylenediamine with n-methoxysalicylaldehyde (n = 3, 4 and 5). Crystal structures of these complexes were determined. Electrochemical behavior of the complexes was studied by means of cyclic voltammetry in DMSO solutions. Catalytic performance of the complexes was studied in the epoxidation of cyclooctene using tert-butylhydroperoxide (TBHP) as oxidant under various conditions to find the optimum operating parameters. Low catalytic activity with moderate epoxide selectivity was observed in in-solvent conditions but in the solvent-free conditions, enhanced catalytic activity with high epoxide selectivity was achieved.

Stress corrosion cracking properties of 15-5PH steel

NASA Technical Reports Server (NTRS)

Rosa, Ferdinand

1993-01-01

Unexpected occurrence of failures, due to stress corrosion cracking (SCC) of structural components, indicate a need for improved characterization of materials and more advanced analytical procedures for reliably predicting structures performance. Accordingly, the purpose of this study was to determine the stress corrosion susceptibility of 15-5PH steel over a wide range of applied strain rates in a highly corrosive environment. The selected environment for this investigation was a highly acidified sodium chloride (NaCl) aqueous solution. The selected alloy for the study was a 15-5PH steel in the H900 condition. The slow strain rate technique was selected to test the metals specimens.

K-nearest neighbors based methods for identification of different gear crack levels under different motor speeds and loads: Revisited

NASA Astrophysics Data System (ADS)

Wang, Dong

2016-03-01

Gears are the most commonly used components in mechanical transmission systems. Their failures may cause transmission system breakdown and result in economic loss. Identification of different gear crack levels is important to prevent any unexpected gear failure because gear cracks lead to gear tooth breakage. Signal processing based methods mainly require expertize to explain gear fault signatures which is usually not easy to be achieved by ordinary users. In order to automatically identify different gear crack levels, intelligent gear crack identification methods should be developed. The previous case studies experimentally proved that K-nearest neighbors based methods exhibit high prediction accuracies for identification of 3 different gear crack levels under different motor speeds and loads. In this short communication, to further enhance prediction accuracies of existing K-nearest neighbors based methods and extend identification of 3 different gear crack levels to identification of 5 different gear crack levels, redundant statistical features are constructed by using Daubechies 44 (db44) binary wavelet packet transform at different wavelet decomposition levels, prior to the use of a K-nearest neighbors method. The dimensionality of redundant statistical features is 620, which provides richer gear fault signatures. Since many of these statistical features are redundant and highly correlated with each other, dimensionality reduction of redundant statistical features is conducted to obtain new significant statistical features. At last, the K-nearest neighbors method is used to identify 5 different gear crack levels under different motor speeds and loads. A case study including 3 experiments is investigated to demonstrate that the developed method provides higher prediction accuracies than the existing K-nearest neighbors based methods for recognizing different gear crack levels under different motor speeds and loads. Based on the new significant statistical features, some other popular statistical models including linear discriminant analysis, quadratic discriminant analysis, classification and regression tree and naive Bayes classifier, are compared with the developed method. The results show that the developed method has the highest prediction accuracies among these statistical models. Additionally, selection of the number of new significant features and parameter selection of K-nearest neighbors are thoroughly investigated.

Comparison of Two Preparation Methods on Catalytic Activity and Selectivity of Ru-Mo/HZSM5 for Methane Dehydroaromatization

DOE PAGES

Petkovic, Lucia M.; Ginosar, Daniel M.

2014-01-01

Catalytic performance of Mo/HZSM5 and Ru-Mo/HZSM5 catalysts prepared by vaporization-deposition of molybdenum trioxide and impregnation with ammonium heptamolybdate was analyzed in terms of catalyst activity and selectivity, nitrogen physisorption analyses, temperature-programmed oxidation of carbonaceous residues, and temperature-programmed reduction. Vaporization-deposition rendered the catalyst more selective to ethylene and coke than the catalyst prepared by impregnation. This result was assigned to lower interaction of molybdenum carbide with the zeolite acidic sites.

Metal Catalysts for Heterogeneous Catalysis: From Single Atoms to Nanoclusters and Nanoparticles.

PubMed

Liu, Lichen; Corma, Avelino

2018-05-23

Metal species with different size (single atoms, nanoclusters, and nanoparticles) show different catalytic behavior for various heterogeneous catalytic reactions. It has been shown in the literature that many factors including the particle size, shape, chemical composition, metal-support interaction, and metal-reactant/solvent interaction can have significant influences on the catalytic properties of metal catalysts. The recent developments of well-controlled synthesis methodologies and advanced characterization tools allow one to correlate the relationships at the molecular level. In this Review, the electronic and geometric structures of single atoms, nanoclusters, and nanoparticles will be discussed. Furthermore, we will summarize the catalytic applications of single atoms, nanoclusters, and nanoparticles for different types of reactions, including CO oxidation, selective oxidation, selective hydrogenation, organic reactions, electrocatalytic, and photocatalytic reactions. We will compare the results obtained from different systems and try to give a picture on how different types of metal species work in different reactions and give perspectives on the future directions toward better understanding of the catalytic behavior of different metal entities (single atoms, nanoclusters, and nanoparticles) in a unifying manner.

Z-Selective Catalytic Olefin Cross-Metathesis

PubMed Central

Meek, Simon J.; O’Brien, Robert V.; Llaveria, Josep; Schrock, Richard R.; Hoveyda, Amir H.

2011-01-01

Alkenes are found in a great number of biologically active molecules and are employed in numerous transformations in organic chemistry. Many olefins exist as E or higher energy Z isomers. Catalytic procedures for stereoselective formation of alkenes are therefore valuable; nonetheless, methods for synthesis of 1,2-disubstituted Z olefins are scarce. Here we report catalytic Z-selective cross-metathesis reactions of terminal enol ethers, which have not been reported previously, and allylic amides, employed thus far only in E-selective processes; the corresponding disubstituted alkenes are formed in up to >98% Z selectivity and 97% yield. Transformations, promoted by catalysts that contain the highly abundant and inexpensive molybdenum, are amenable to gram scale operations. Use of reduced pressure is introduced as a simple and effective strategy for achieving high stereoselectivity. Utility is demonstrated by syntheses of anti-oxidant C18 (plasm)-16:0 (PC), found in electrically active tissues and implicated in Alzheimer’s disease, and the potent immunostimulant KRN7000. PMID:21430774

Selective catalytic reduction manages ships' emissions

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

McMahon, K.R.

1994-10-01

Ships employed by USS-Posco Industries are the first seagoing vessels that use selective catalytic reduction in marine diesel engine design, resulting in a 90 percent reduction of nitrogen oxide emissions. The vessels, which deliver semifinished steel coils, or hot bands'', to the company's terminal in the San Francisco Bay area, were commissioned for $120 million by Pohang Iron and Steel Co. Ltd., one of UPI's parent companies. Installing the catalytic reduction equipment cost $12 million. As anticipated, NOx concentrations were reduced between 90 percent and 95 percent. However, achieving high mass NOx reduction proved more difficult, because exhaust gas hadmore » to be maintained within the desired temperature range.« less

Technical intelligence and culture: Nut cracking in humans and chimpanzees.

PubMed

Boesch, Christophe; Bombjaková, Daša; Boyette, Adam; Meier, Amelia

2017-06-01

According to the technical intelligence hypothesis, humans are superior to all other animal species in understanding and using tools. However, the vast majority of comparative studies between humans and chimpanzees, both proficient tool users, have not controlled for the effects of age, prior knowledge, past experience, rearing conditions, or differences in experimental procedures. We tested whether humans are superior to chimpanzees in selecting better tools, using them more dexteriously, achieving higher performance and gaining access to more resource as predicted under the technical intelligence hypothesis. Aka and Mbendjele hunter-gatherers in the rainforest of Central African Republic and the Republic of Congo, respectively, and Taï chimpanzees in the rainforest of Côte d'Ivoire were observed cracking hard Panda oleosa nuts with different tools, as well as the soft Coula edulis and Elaeis guinensis nuts. The nut-cracking techniques, hammer material selection and two efficiency measures were compared. As predicted, the Aka and the Mbendjele were able to exploit more species of hard nuts in the forest than chimpanzees. However, the chimpanzees were sometimes more efficient than the humans. Social roles differed between the two species, with the Aka and especially the Mbendjele exhibiting cooperation between nut-crackers whereas the chimpanzees were mainly individualistic. Observations of nut-cracking by humans and chimpanzees only partially supported the technical intelligence hypothesis as higher degrees of flexibility in tool selection seen in chimpanzees compensated for use of less efficient tool material than in humans. Nut cracking was a stronger social undertaking in humans than in chimpanzees. © 2017 Wiley Periodicals, Inc.

Selective Internal Oxidation as a Mechanism for Intergranular Stress Corrosion Cracking of Ni-Cr-Fe Alloys

NASA Astrophysics Data System (ADS)

Capell, Brent M.; Was, Gary S.

2007-06-01

The mechanism of selective internal oxidation (SIO) for intergranular stress corrosion cracking (IGSCC) of nickel-base alloys has been investigated through a series of experiments using high-purity alloys and a steam environment to control the formation of NiO on the surface. Five alloys (Ni-9Fe, Ni-5Cr, Ni-5Cr-9Fe, Ni-16Cr-9Fe, and Ni-30Cr-9Fe) were used to investigate oxidation and intergranular cracking behavior for hydrogen-to-water vapor partial pressure ratios (PPRs) between 0.001 and 0.9. The Ni-9Fe, Ni-5Cr, and Ni-5Cr-9Fe alloys formed a uniform Ni(OH)2 film at PPRs less than 0.09, and the higher chromium alloys formed chromium-rich oxide films over the entire PPR range studied. Corrosion coupon results show that grain boundary oxides extended for significant depths (>150 nm) below the sample surface for all but the highest Cr containing alloy. Constant extension rate tensile (CERT) test results showed that intergranular cracking varied with PPR and cracking was more pronounced at a PPR value where nonprotective Ni(OH)2 was able to form and a link between the nonprotective Ni(OH)2 film and the formation of grain boundary oxides is suggested. The observation of grain boundary oxides in stressed and unstressed samples as well as the influence of alloy content on IG cracking and oxidation support SIO as a mechanism for IGSCC.

Effect of crack on natural frequency for beam type of structures

NASA Astrophysics Data System (ADS)

Sawant, Saurabh U.; Chauhan, Santosh J.; Deshmukh, Nilaj N.

2017-07-01

Detection of damage in early stages reduces chances of sudden failure of that structure which is important from safety and economic point of view. Crack or damage affects dynamic behavior of structure. In last few decades many researchers have been developing different approaches to detect the damage based on its dynamic behavior. This paper focuses on effect on natural frequency of cantilever beam due to the presence of crack at different locations and with different depths. Cantilever beam is selected for analysis because these beams are most common structures used in many industrial applications. In the present study, modeling of healthy and damaged cantilever beam is done using ANSYSsoftware. Crack at 38 different locations with 1 mm, 2 mm and 3 mm crack depth were created for each of these locations. The effect of these cracks on natural frequency were analyzed over the healthy beam for the first four mode shapes. It is found that the presence of crack decreases the natural frequency of the beam and at some particular locations, the natural frequency of the cracked beam is found to be almost the same as that of the healthy beam.

Microstructural examination of fatigue crack tip in high strength steel

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

Fukuoka, C.; Yoshizawa, H.; Nakagawa, Y.G.

1993-10-01

Fatigue tests were performed to examine how microstructural conditioning influences crack initiation and propagation in SA508 class 3 low-carbon steel. A 3-mm-long crack was introduced in compact tension (CT) fatigue test specimens under four different loads in order to obtain crack tip plastic zones at different stress intensity factor ranges, [Delta]K = 18, 36, 54, and 72 MPa[radical]m. The microstructure of the plastic zones around the crack tip were examined by transmission electron microscopy (TEM) and selected area electron diffraction (SAD). Micro-orientation of the dislocation cells in the plastic zones of all of the CT samples increased to 4 degmore » from the level of an as-received sample. Four-point bending fatigue tests were performed for plate shape samples with a large cyclic strain range. The SAD value of the bending samples was also 4 deg in the damaged area where cracks already initiated at an early stage of the fatigue process. These test results indicate that the microstructural conditioning is a prerequisite for the fatigue crack initiation and propagation in SA508. These observations may lead to better understanding of how fatigue initiation processes transit to cracks.« less

Crack detection using resonant ultrasound spectroscopy

DOEpatents

Migliori, A.; Bell, T.M.; Rhodes, G.W.

1994-10-04

Method and apparatus are provided for detecting crack-like flaws in components. A plurality of exciting frequencies are generated and applied to a component in a dry condition to obtain a first ultrasonic spectrum of the component. The component is then wet with a selected liquid to penetrate any crack-like flaws in the component. The plurality of exciting frequencies are again applied to the component and a second ultrasonic spectrum of the component is obtained. The wet and dry ultrasonic spectra are then analyzed to determine the second harmonic components in each of the ultrasonic resonance spectra and the second harmonic components are compared to ascertain the presence of crack-like flaws in the component. 5 figs.

Stochastic model for fatigue crack size and cost effective design decisions. [for aerospace structures

NASA Technical Reports Server (NTRS)

Hanagud, S.; Uppaluri, B.

1975-01-01

This paper describes a methodology for making cost effective fatigue design decisions. The methodology is based on a probabilistic model for the stochastic process of fatigue crack growth with time. The development of a particular model for the stochastic process is also discussed in the paper. The model is based on the assumption of continuous time and discrete space of crack lengths. Statistical decision theory and the developed probabilistic model are used to develop the procedure for making fatigue design decisions on the basis of minimum expected cost or risk function and reliability bounds. Selections of initial flaw size distribution, NDT, repair threshold crack lengths, and inspection intervals are discussed.

Crack detection using resonant ultrasound spectroscopy

DOEpatents

Migliori, Albert; Bell, Thomas M.; Rhodes, George W.

1994-01-01

Method and apparatus are provided for detecting crack-like flaws in components. A plurality of exciting frequencies are generated and applied to a component in a dry condition to obtain a first ultrasonic spectrum of the component. The component is then wet with a selected liquid to penetrate any crack-like flaws in the component. The plurality of exciting frequencies are again applied to the component and a second ultrasonic spectrum of the component is obtained. The wet and dry ultrasonic spectra are then analyzed to determine the second harmonic components in each of the ultrasonic resonance spectra and the second harmonic components are compared to ascertain the presence of crack-like flaws in the component.

Analysis of damaging process and crack propagation

NASA Astrophysics Data System (ADS)

Semenski, D.; Wolf, H.; Božić, Ž.

2010-06-01

Supervising and health monitoring of structures can assess the actual state of existing structures after initial loading or in the state of operation. Structural life management requires the integration of design and analysis, materials behavior and structural testing, as given for several examples. Procedure of survey of structural elements and criteria for their selection must be strongly defined as it is for the offshore gas platforms. Numerical analysis of dynamic loading is shown for the Aeolian vibrations of overhead transmission line conductors. Since the damper’s efficiency strongly depends on its position, the procedure of determining the optimum position of the damper is described. The optical method of caustics is established in isotropic materials for determination of the stress intensity factors (SIFs) of the cracks in deformed structures and is advantageously improved for the application to fiberreinforced composites. A procedure for simulation of crack propagation for multiple cracks was introduced and SIFs have been calculated by using finite element method. Crack growth of a single crack or a periodical array of cracks initiated at the stiffeners in a stiffened panel has been investigated.

Assessment of crack opening area for leak rates

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

Sharples, J.K.; Bouchard, P.J.

1997-04-01

This paper outlines the background to recommended crack opening area solutions given in a proposed revision to leak before break guidance for the R6 procedure. Comparisons with experimental and analytical results are given for some selected cases of circumferential cracks in cylinders. It is shown that elastic models can provide satisfactory estimations of crack opening displacement (and area) but they become increasingly conservative for values of L{sub r} greater than approximately 0.4. The Dugdale small scale yielding model gives conservative estimates of crack opening displacement with increasing enhancement for L{sub r} values greater than 0.4. Further validation of the elastic-plasticmore » reference stress method for up to L{sub r} values of about 1.0 is presented by experimental and analytical comparisons. Although a more detailed method, its application gives a best estimate of crack opening displacement which may be substantially greater than small scale plasticity models. It is also shown that the local boundary conditions in pipework need to be carefully considered when evaluating crack opening area for through-wall bending stresses resulting from welding residual stresses or geometry discontinuities.« less

Salivary buffer capacity, pH, and stimulated flow rate of crack cocaine users.

PubMed

Woyceichoski, Iverson Ernani Cogo; Costa, Carlos Henrique; de Araújo, Cristiano Miranda; Brancher, João Armando; Resende, Luciane Grochocki; Vieira, Iran; de Lima, Antonio Adilson Soares

2013-08-01

Crack cocaine is the freebase form of cocaine that can be smoked. The use of this drug has been considered a public health problem in many countries. The aim of this study was to assess the stimulated salivary flow rate (SSFR), pH, and the buffer capacity of saliva in crack cocaine users. Stimulated whole saliva was collected from 54 selected crack cocaine users and 40 non-users. All samples were analyzed for SSFR, pH, and buffer capacity. SSFR was analyzed by gravimetric method. The buffer capacity and pH were determined using a digital pH meter. The crack cocaine users demonstrated higher buffer capacity than the control group (P > 0.05). Salivary pH was lower in crack cocaine users (P < 0.05). Mean values of the SSFR for the experimental and control groups were 1.1 and 1.3 mL/min, respectively (P > 0.05). Crack cocaine users might exhibit a significant decrease in salivary pH, but not in salivary flow rate or buffer capacity. © 2012 Blackwell Publishing Asia Pty Ltd.

Microstructural examination of

NASA Astrophysics Data System (ADS)

Fukuoka, C.; Yoshizawa, H.; Nakagawa, Y. G.; Lapides, M. E.

1993-10-01

Fatigue tests were performed to examine how microstructural conditioning influences crack initiation and propagation in SA508 class 3 low-carbon steel. A 3-mm-long crack was introduced in compact tension (CT) fatigue test specimens under four different loads in order to obtain crack tip plastic zones at different stress intensity factor ranges, ΔK = 18, 36, 54, and 72 MPa√m. The microstructure of the plastic zones around the crack tip were examined by trans- mission electron microscopy (TEM) and selected area electron diffraction (SAD). Micro- orientation of the dislocation cells in the plastic zones of all of the CT samples increased to 4 deg from the level of an as-received sample. Four-point bending fatigue tests were performed for plate shape samples with a large cyclic strain range. The SAD value of the bending samples was also 4 deg in the damaged area where cracks already initiated at an early stage of the fatigue process. These test results indicate that the microstructural conditioning is a prerequisite for the fatigue crack initiation and propagation in SA508. These observations may lead to better under- standing of how fatigue initiation processes transit to cracks.

A Comparison of Single-Cycle Versus Multiple-Cycle Proof Testing Strategies

NASA Technical Reports Server (NTRS)

McClung, R. C.; Chell, G. G.; Millwater, H. R.; Russell, D. A.; Millwater, H. R.

1999-01-01

Single-cycle and multiple-cycle proof testing (SCPT and MCPT) strategies for reusable aerospace propulsion system components are critically evaluated and compared from a rigorous elastic-plastic fracture mechanics perspective. Earlier MCPT studies are briefly reviewed. New J-integral estimation methods for semielliptical surface cracks and cracks at notches are derived and validated. Engineering methods are developed to characterize crack growth rates during elastic-plastic fatigue crack growth (FCG) and the tear-fatigue interaction near instability. Surface crack growth experiments are conducted with Inconel 718 to characterize tearing resistance, FCG under small-scale yielding and elastic-plastic conditions, and crack growth during simulated MCPT. Fractography and acoustic emission studies provide additional insight. The relative merits of SCPT and MCPT are directly compared using a probabilistic analysis linked with an elastic-plastic crack growth computer code. The conditional probability of failure in service is computed for a population of components that have survived a previous proof test, based on an assumed distribution of initial crack depths. Parameter studies investigate the influence of proof factor, tearing resistance, crack shape, initial crack depth distribution, and notches on the MCPT versus SCPT comparison. The parameter studies provide a rational basis to formulate conclusions about the relative advantages and disadvantages of SCPT and MCPT. Practical engineering guidelines are proposed to help select the optimum proof test protocol in a given application.

A Comparison of Single-Cycle Versus Multiple-Cycle Proof Testing Strategies

NASA Technical Reports Server (NTRS)

McClung, R. C.; Chell, G. G.; Millwater, H. R.; Russell, D. A.; Orient, G. E.

1996-01-01

Single-cycle and multiple-cycle proof testing (SCPT and MCPT) strategies for reusable aerospace propulsion system components are critically evaluated and compared from a rigorous elastic-plastic fracture mechanics perspective. Earlier MCPT studies are briefly reviewed. New J-integral estimation methods for semi-elliptical surface cracks and cracks at notches are derived and validated. Engineering methods are developed to characterize crack growth rates during elastic-plastic fatigue crack growth (FCG) and the tear-fatigue interaction near instability. Surface crack growth experiments are conducted with Inconel 718 to characterize tearing resistance, FCG under small-scale yielding and elastic-plastic conditions, and crack growth during simulated MCPT. Fractography and acoustic emission studies provide additional insight. The relative merits of SCPT and MCPT are directly compared using a probabilistic analysis linked with an elastic-plastic crack growth computer code. The conditional probability of failure in service is computed for a population of components that have survived a previous proof test, based on an assumed distribution of initial crack depths. Parameter studies investigate the influence of proof factor, tearing resistance, crack shape, initial crack depth distribution, and notches on the MCPT vs. SCPT comparison. The parameter studies provide a rational basis to formulate conclusions about the relative advantages and disadvantages of SCPT and MCPT. Practical engineering guidelines are proposed to help select the optimum proof test protocol in a given application.

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

Babucci, Melike; Fang, Chia -Yu; Hoffman, Adam S.

1,3-Dialkylimidazolium ionic liquid coatings act as electron donors, increasing the selectivity for partial hydrogenation of 1,3-butadiene catalyzed by iridium complexes supported on high-surface-area γ-Al 2O 3. High-energy-resolution fluorescence detection X-ray absorption near-edge structure (HERFD XANES) measurements quantify the electron donation and are correlated with the catalytic activity and selectivity. Furthermore, the results demonstrate broad opportunities to tune electronic environments and catalytic properties of atomically dispersed supported metal catalysts.

Distinguishing molecular environments in supported Pt catalysts and their influences on activity and selectivity

NASA Astrophysics Data System (ADS)

Jones, Louis Chin

This thesis entails the synthesis, automated catalytic testing, and in situ molecular characterization of supported Pt and Pt-alloy nanoparticle (NP) catalysts, with emphasis on how to assess the molecular distributions of Pt environments that are affecting overall catalytic activity and selectivity. We have taken the approach of (a) manipulating nucleation and growth of NPs using oxide supports, surfactants, and inorganic complexes to create Pt NPs with uniform size, shape, and composition, (b) automating batch and continuous flow catalytic reaction tests, and (c) characterizing the molecular environments of Pt surfaces using in situ infrared (IR) spectroscopy and solid-state 195Pt NMR. The following will highlight the synthesis and characterization of Ag-doped Pt NPs and their influence on C 2H2 hydrogenation selectivity, and the implementation of advanced solid-state 195Pt NMR techniques to distinguish how distributions of molecular Pt environments vary with nanoparticle size, support, and surface composition.

Directional synthesis of ethylbenzene through catalytic transformation of lignin.

PubMed

Fan, Minghui; Jiang, Peiwen; Bi, Peiyan; Deng, Shumei; Yan, Lifeng; Zhai, Qi; Wang, Tiejun; Li, Quanxin

2013-09-01

Transformation of lignin to ethylbenzene can provide an important bulk raw material for the petrochemical industry. This work explored the production of ethylbenzene from lignin through the directional catalytic depolymerization of lignin into the aromatic monomers followed by the selective alkylation of the aromatic monomers. For the first step, the aromatics selectivity of benzene derived from the catalytic depolymerization of lignin reached about 90.2 C-mol% over the composite catalyst of Re-Y/HZSM-5 (25). For the alkylation of the aromatic monomers in the second step, the highest selectivity of ethylbenzene was about 72.3 C-mol% over the HZSM-5 (25) catalyst. The reaction pathway for the transformation of lignin to ethylbenzene was also addressed. Present transformation potentially provides a useful approach for the production of the basic petrochemical material and development of high-end chemicals utilizing lignin as the abundant natural aromatic resource. Copyright © 2013 Elsevier Ltd. All rights reserved.

Catalysis by clusters with precise numbers of atoms

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

Tyo, Eric C.; Vajda, Stefan

2015-07-03

Clusters that contain only a small number of atoms can exhibit unique and often unexpected properties. The clusters are of particular interest in catalysis because they can act as individual active sites, and minor changes in size and composition – such as the addition or removal of a single atom – can have a substantial influence on the activity and selectivity of a reaction. Here we review recent progress in the synthesis, characterization and catalysis of well-defined sub-nanometre clusters. We examine work on size-selected supported clusters in ultra-high vacuum environments and under realistic reaction conditions, and explore the use ofmore » computational methods to provide a mechanistic understanding of their catalytic properties. We also highlight the potential of size-selected clusters to provide insights into important catalytic processes and their use in the development of novel catalytic systems.« less

Assessing edge cracking resistance in AHSS automotive parts by the Essential Work of Fracture methodology

NASA Astrophysics Data System (ADS)

Frómeta, D.; Tedesco, M.; Calvo, J.; Lara, A.; Molas, S.; Casellas, D.

2017-09-01

Lightweight designs and demanding safety requirements in automotive industry are increasingly promoting the use of Advanced High Strength Steel (AHSS) sheets. Such steels present higher strength (above 800 MPa) but lower ductility than conventional steels. Their great properties allow the reduction of the thickness of automobile structural components without compromising the safety, but also introduce new challenges to parts manufacturers. The fabrication of most cold formed components starts from shear cut blanks and, due to the lower ductility of AHSS, edge cracking problems can appear during forming operations, forcing the stop of the production and slowing down the industrial process. Forming Limit Diagrams (FLD) and FEM simulations are very useful tools to predict fracture problems in zones with high localized strain, but they are not able to predict edge cracking. It has been observed that the fracture toughness, measured through the Essential Work of Fracture (EWF) methodology, is a good indicator of the stretch flangeability in AHSS and can help to foresee this type of fractures. In this work, a serial production automotive component has been studied. The component showed cracks in some flanged edges when using a dual phase steel. It is shown that the conventional approach to explain formability, based on tensile tests and FLD, fails in the prediction of edge cracking. A new approach, based on fracture mechanics, help to solve the problem by selecting steel grades with higher fracture toughness, measured by means of EWF. Results confirmed that fracture toughness, in terms of EWF, can be readily used as a material parameter to rationalize cracking related problems and select AHSS with improved edge cracking resistance.

Thermoregulatory value of cracking-clay soil shelters for small vertebrates during extreme desert conditions.

PubMed

Waudby, Helen P; Petit, Sophie

2017-05-01

Deserts exhibit extreme climatic conditions. Small desert-dwelling vertebrates have physiological and behavioral adaptations to cope with these conditions, including the ability to seek shelter. We investigated the temperature (T) and relative humidity (RH) regulating properties of the soil cracks that characterize the extensive cracking-clay landscapes of arid Australia, and the extent of their use by 2 small marsupial species: fat-tailed and stripe-faced dunnarts (Sminthopsis crassicaudata and Sminthopsis macroura). We measured hourly (over 24-h periods) the T and RH of randomly-selected soil cracks compared to outside conditions, during 2 summers and 2 winters. We tracked 17 dunnarts (8 Sminthopsis crassicaudata and 9 Sminthopsis macroura) to quantify their use of cracks. Cracks consistently moderated microclimate, providing more stable conditions than available from non-crack points, which often displayed comparatively dramatic fluctuations in T and RH. Both dunnart species used crack shelters extensively. Cracks constitute important shelter for small animals during extreme conditions by providing a stable microclimate, which is typically cooler than outside conditions in summer and warmer in winter. Cracks likely play a fundamental sheltering role by sustaining the physiological needs of small mammal populations. Globally, cracking-clay areas are dominated by agricultural land uses, including livestock grazing. Management of these systems should focus not only on vegetation condition, but also on soil integrity, to maintain shelter resources for ground-dwelling fauna. © 2016 International Society of Zoological Sciences, Institute of Zoology/Chinese Academy of Sciences and John Wiley & Sons Australia, Ltd.

Comparative evaluation of dentinal crack formation after root canal preparation using ProTaper Next, OneShape, and Hyflex EDM

PubMed Central

Das, Sanjib; Pradhan, Prasanti Kumari; Lata, S.; Sinha, Sachidananda Prasad

2018-01-01

Introduction: The purpose of this study was to compare the incidence of dentinal crack formation after root canal preparation using ProTaper Next, OneShape, and Hyflex electrodischarge machining (HEDM). Materials and Methods: A total of 75 extracted mandibular premolars were selected. The root canals were instrumented using ProTaper Next, OneShape, and HEDM rotary files. All roots were horizontally sectioned at 3, 6, and 9 mm from apex with slow-speed saw under water cooling. The sections were observed under a stereomicroscope at ×25 to determine the absence or presence of crack. Data were analyzed using post hoc test and one-way ANOVA. Results: ProTaper Next and HEDM produced significantly less cracks than OneShape. Conclusion: Within the limitation of this in vitro study, it can be concluded that nickel–titanium instruments may cause cracks on the root surface. ProTaper Next and HEDM tend to produce less number of cracks as compared to OneShape. PMID:29674816

Heterobimetallic transition metal/rare earth metal bifunctional catalysis: a Cu/Sm/Schiff base complex for syn-selective catalytic asymmetric nitro-Mannich reaction.

PubMed

Handa, Shinya; Gnanadesikan, Vijay; Matsunaga, Shigeki; Shibasaki, Masakatsu

2010-04-07

The full details of a catalytic asymmetric syn-selective nitro-Mannich reaction promoted by heterobimetallic Cu/Sm/dinucleating Schiff base complexes are described, demonstrating the effectiveness of the heterobimetallic transition metal/rare earth metal bifunctional catalysis. The first-generation system prepared from Cu(OAc)(2)/Sm(O-iPr)(3)/Schiff base 1a = 1:1:1 with an achiral phenol additive was partially successful for achieving the syn-selective catalytic asymmetric nitro-Mannich reaction. The substrate scope and limitations of the first-generation system remained problematic. After mechanistic studies on the catalyst prepared from Sm(O-iPr)(3), we reoptimized the catalyst preparation method, and a catalyst derived from Sm(5)O(O-iPr)(13) showed broader substrate generality as well as higher reactivity and stereoselectivity compared to Sm(O-iPr)(3). The optimal system with Sm(5)O(O-iPr)(13) was applicable to various aromatic, heteroaromatic, and isomerizable aliphatic N-Boc imines, giving products in 66-99% ee and syn/anti = >20:1-13:1. Catalytic asymmetric synthesis of nemonapride is also demonstrated using the catalyst derived from Sm(5)O(O-iPr)(13).

Understanding activity and selectivity of metal-nitrogen-doped carbon catalysts for electrochemical reduction of CO2.

PubMed

Ju, Wen; Bagger, Alexander; Hao, Guang-Ping; Varela, Ana Sofia; Sinev, Ilya; Bon, Volodymyr; Roldan Cuenya, Beatriz; Kaskel, Stefan; Rossmeisl, Jan; Strasser, Peter

2017-10-16

Direct electrochemical reduction of CO 2 to fuels and chemicals using renewable electricity has attracted significant attention partly due to the fundamental challenges related to reactivity and selectivity, and partly due to its importance for industrial CO 2 -consuming gas diffusion cathodes. Here, we present advances in the understanding of trends in the CO 2 to CO electrocatalysis of metal- and nitrogen-doped porous carbons containing catalytically active M-N x moieties (M = Mn, Fe, Co, Ni, Cu). We investigate their intrinsic catalytic reactivity, CO turnover frequencies, CO faradaic efficiencies and demonstrate that Fe-N-C and especially Ni-N-C catalysts rival Au- and Ag-based catalysts. We model the catalytically active M-N x moieties using density functional theory and correlate the theoretical binding energies with the experiments to give reactivity-selectivity descriptors. This gives an atomic-scale mechanistic understanding of potential-dependent CO and hydrocarbon selectivity from the M-N x moieties and it provides predictive guidelines for the rational design of selective carbon-based CO 2 reduction catalysts.Inexpensive and selective electrocatalysts for CO 2 reduction hold promise for sustainable fuel production. Here, the authors report N-coordinated, non-noble metal-doped porous carbons as efficient and selective electrocatalysts for CO 2 to CO conversion.

Epi-cleaning of Ge/GeSn heterostructures

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

Di Gaspare, L.; Sabbagh, D.; De Seta, M.

2015-01-28

We demonstrate a very-low temperature cleaning technique based on atomic hydrogen irradiation for highly (1%) tensile strained Ge epilayers grown on metastable, partially strain relaxed GeSn buffer layers. Atomic hydrogen is obtained by catalytic cracking of hydrogen gas on a hot tungsten filament in an ultra-high vacuum chamber. X-ray photoemission spectroscopy, reflection high energy electron spectroscopy, atomic force microscopy, secondary ion mass spectroscopy, and micro-Raman showed that an O- and C-free Ge surface was achieved, while maintaining the same roughness and strain condition of the as-deposited sample and without any Sn segregation, at a process temperature in the 100–300 °C range.

Epi-cleaning of Ge/GeSn heterostructures

NASA Astrophysics Data System (ADS)

Di Gaspare, L.; Sabbagh, D.; De Seta, M.; Sodo, A.; Wirths, S.; Buca, D.; Zaumseil, P.; Schroeder, T.; Capellini, G.

2015-01-01

We demonstrate a very-low temperature cleaning technique based on atomic hydrogen irradiation for highly (1%) tensile strained Ge epilayers grown on metastable, partially strain relaxed GeSn buffer layers. Atomic hydrogen is obtained by catalytic cracking of hydrogen gas on a hot tungsten filament in an ultra-high vacuum chamber. X-ray photoemission spectroscopy, reflection high energy electron spectroscopy, atomic force microscopy, secondary ion mass spectroscopy, and micro-Raman showed that an O- and C-free Ge surface was achieved, while maintaining the same roughness and strain condition of the as-deposited sample and without any Sn segregation, at a process temperature in the 100-300 °C range.

Nanoscale Chemical Imaging of an Individual Catalyst Particle with Soft X-ray Ptychography

DOE PAGES

Wise, Anna M.; Weker, Johanna Nelson; Kalirai, Sam; ...

2016-02-26

Understanding Fe deposition in fluid catalytic cracking (FCC) catalysis is critical for the mitigation of catalyst degradation. We employ soft X-ray ptychography to determine at the nanoscale the distribution and chemical state of Fe in an aged FCC catalyst particle. We also show that both particle swelling due to colloidal Fe deposition and Fe penetration into the matrix as a result of precracking of large organic molecules occur. Furthermore, the application of ptychography allowed us to provide direct visual evidence for these two distinct Fe-based deactivation mechanisms, which have so far been proposed only on the basis of indirect evidence.

Magnetic cobaltic nanoparticle-anchored carbon nanocomposite derived from cobalt-dipicolinic acid coordination polymer: An enhanced catalyst for environmental oxidative and reductive reactions.

PubMed

Wu, Chang-Hsun; Lin, Jyun-Ting; Lin, Kun-Yi Andrew

2018-05-01

Direct carbonization of cobalt complexes represents as a convenient approach to prepare magnetic carbon/cobalt nanocomposites (MCCNs) as heterogeneous environmental catalysts. However, most of MCCNs derived from consist of sheet-like carbon matrices with very sparse cobaltic nanoparticles (NPs), making them exhibit relatively low catalytic activities, porosity and magnetism. In this study, dipicolinic acid (DPA) is selected to prepare a 3-dimensional cobalt coordination polymer (CoDPA). MCCN derived from CoDPA can consist of a porous carbon matrix embedded with highly-dense Co 0 and Co 3 O 4 NPs. This magnetic Co 0 /Co 3 O 4 NP-anchored carbon composite (MCNC) appears as a promising heterogeneous catalyst for oxidative and reductive environmental catalytic reactions. As peroxymonosulfate (PMS) activation is selected as a model catalytic oxidative reaction, MCNC exhibits a much higher catalytic activity than Co 3 O 4 , a benchmark catalyst for PMS activation. The reductive catalytic activity of MCNC is demonstrated through 4-nitrophenol (4-NP) reduction in the presence of NaBH 4 . MCNC could rapidly react with NaBH 4 to generate H 2 for hydrogenation of 4-NP to 4-aminophenol (4-AP). In comparison with other precious metallic catalysts, MCNC also shows a relatively high catalytic activity. These results indicate that MCNC is a conveniently prepared and highly effective and stable carbon-supported cobaltic heterogeneous catalyst for versatile environmental catalytic applications. Copyright © 2018 Elsevier Inc. All rights reserved.

Catalytic Amination of Alcohols, Aldehydes, and Ketones

NASA Astrophysics Data System (ADS)

Klyuev, M. V.; Khidekel', M. L.

1980-01-01

Data on the catalytic amination of alcohols and carbonyl compounds are examined, the catalysts for these processes are described, and the problems of their effectiveness, selectivity, and stability are discussed. The possible mechanisms of the reactions indicated are presented. The bibliography includes 266 references.

Ce-Sn binary oxide catalyst for the selective catalytic reduction of NOx by NH3

NASA Astrophysics Data System (ADS)

Liu, Zhiming; Feng, Xu; Zhou, Zizheng; Feng, Yongjun; Li, Junhua

2018-01-01

Ce-Sn binary oxide catalysts prepared by the hydrothermal method have been investigated for the selective catalytic reduction (SCR) of NOx with NH3. Compared with pure CeO2 and SnO2, Ce-Sn binary oxide catalyst showed significantly higher NH3-SCR activity. Moreover, Ce-Sn catalyst showed high resistance against H2O and SO2. The high catalytic performance of Ce-Sn binary oxide is attributed to the synergetic effect between Ce and Sn species, which not only enhances the redox property of the catalyst but also increases the Lewis acidity, thus promoting the adsorption and activation of NH3 species, which contributes to improving the NH3-SCR performance.

Turning Biodiesel Waste Glycerol into 1,3-Propanediol: Catalytic Performance of Sulphuric acid-Activated Montmorillonite Supported Platinum Catalysts in Glycerol Hydrogenolysis.

PubMed

Samudrala, Shanthi Priya; Kandasamy, Shalini; Bhattacharya, Sankar

2018-05-10

Direct C-O hydrogenolysis of bioglycerine to produce 1,3-propanediol selectively is a vital technology that can expand the scope of biodiesel industry and green chemical production from biomass. Herein we report sulphuric acid-activated montmorillonite clay supported platinum nanoparticles as highly effective solid acid catalysts for the selective production of 1,3-propanediol from glycerol. The catalytic performances of the catalysts were investigated in the hydrogenolysis of glycerol with a fixed bed reactor under ambient pressure. The results were found promising and showed that the activation of montmorillonite by sulphuric acid incorporated Brønsted acidity in the catalyst and significantly improved the selectivity to 1,3-propanediol. The catalytic performance of different platinum loaded catalysts was examined and 2 wt% Pt/S-MMT catalyst presented superior activity among others validating 62% 1,3-propanediol selectivity at 94% glycerol conversion. The catalytic activity of 2Pt/S-MMT was systematically investigated under varying reaction parameters including reaction temperature, hydrogen flow rate, glycerol concentration, weight hourly space velocity, and contact time to derive the optimum conditions for the reaction. The catalyst stability, reusability and structure-activity correlation were also elucidated. The high performance of the catalyst could be ascribed to well disperse Pt nanoparticles immobilized on acid-activated montmorillonite, wider pore-structure and appropriate acid sites of the catalyst.

Synthesis, structural characterization and selectively catalytic properties of metal-organic frameworks with nano-sized channels: A modular design strategy

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

Qiu Lingguang; Gu Lina; Hu Gang

2009-03-15

Modular design method for designing and synthesizing microporous metal-organic frameworks (MOFs) with selective catalytical activity was described. MOFs with both nano-sized channels and potential catalytic activities could be obtained through self-assembly of a framework unit and a catalyst unit. By selecting hexaaquo metal complexes and the ligand BTC (BTC=1,3,5-benzenetricarboxylate) as framework-building blocks and using the metal complex [M(phen){sub 2}(H{sub 2}O){sub 2}]{sup 2+} (phen=1,10-phenanthroline) as a catalyst unit, a series of supramolecular MOFs 1-7 with three-dimensional nano-sized channels, i.e. [M{sup 1}(H{sub 2}O){sub 6}].[M{sup 2}(phen){sub 2}(H{sub 2}O){sub 2}]{sub 2}.2(BTC).xH{sub 2}O (M{sup 1}, M{sup 2}=Co(II), Ni(II), Cu(II), Zn(II), or Mn(II), phen=1,10-phenanthroline, BTC=1,3,5-benzenetricarboxylate, x=22-24),more » were synthesized through self-assembly, and their structures were characterized by IR, elemental analysis, and single-crystal X-ray diffraction. These supramolecular microporous MOFs showed significant size and shape selectivity in the catalyzed oxidation of phenols, which is due to catalytic reactions taking place in the channels of the framework. Design strategy, synthesis, and self-assembly mechanism for the construction of these porous MOFs were discussed. - Grapical abstract: A modular design strategy has been developed to synthesize microporous metal-organic frameworks with potential catalytic activity by self-assembly of the framework-building blocks and the catalyst unit.« less

Reactibodies generated by kinetic selection couple chemical reactivity with favorable protein dynamics

PubMed Central

Smirnov, Ivan; Carletti, Eugénie; Kurkova, Inna; Nachon, Florian; Nicolet, Yvain; Mitkevich, Vladimir A.; Débat, Hélène; Avalle, Bérangère; Belogurov, Alexey A.; Kuznetsov, Nikita; Reshetnyak, Andrey; Masson, Patrick; Tonevitsky, Alexander G.; Ponomarenko, Natalia; Makarov, Alexander A.; Friboulet, Alain; Tramontano, Alfonso; Gabibov, Alexander

2011-01-01

Igs offer a versatile template for combinatorial and rational design approaches to the de novo creation of catalytically active proteins. We have used a covalent capture selection strategy to identify biocatalysts from within a human semisynthetic antibody variable fragment library that uses a nucleophilic mechanism. Specific phosphonylation at a single tyrosine within the variable light-chain framework was confirmed in a recombinant IgG construct. High-resolution crystallographic structures of unmodified and phosphonylated Fabs display a 15-Å-deep two-chamber cavity at the interface of variable light (VL) and variable heavy (VH) fragments having a nucleophilic tyrosine at the base of the site. The depth and structure of the pocket are atypical of antibodies in general but can be compared qualitatively with the catalytic site of cholinesterases. A structurally disordered heavy chain complementary determining region 3 loop, constituting a wall of the cleft, is stabilized after covalent modification by hydrogen bonding to the phosphonate tropinol moiety. These features and presteady state kinetics analysis indicate that an induced fit mechanism operates in this reaction. Mutations of residues located in this stabilized loop do not interfere with direct contacts to the organophosphate ligand but can interrogate second shell interactions, because the H3 loop has a conformation adjusted for binding. Kinetic and thermodynamic parameters along with computational docking support the active site model, including plasticity and simple catalytic components. Although relatively uncomplicated, this catalytic machinery displays both stereo- and chemical selectivity. The organophosphate pesticide paraoxon is hydrolyzed by covalent catalysis with rate-limiting dephosphorylation. This reactibody is, therefore, a kinetically selected protein template that has enzyme-like catalytic attributes. PMID:21896761

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

Thi, Trinh Cham, E-mail: s1240009@jaist.ac.jp; Koyama, Koichi; Ohdaira, Keisuke

We improve the passivation property of n-type crystalline silicon (c-Si) surface passivated with a catalytic chemical vapor deposited (Cat-CVD) Si nitride (SiN{sub x}) film by inserting a phosphorous (P)-doped layer formed by exposing c-Si surface to P radicals generated by the catalytic cracking of PH{sub 3} molecules (Cat-doping). An extremely low surface recombination velocity (SRV) of 2 cm/s can be achieved for 2.5 Ω cm n-type (100) floating-zone Si wafers passivated with SiN{sub x}/P Cat-doped layers, both prepared in Cat-CVD systems. Compared with the case of only SiN{sub x} passivated layers, SRV decreases from 5 cm/s to 2 cm/s. The decrease in SRVmore » is the result of field effect created by activated P atoms (donors) in a shallow P Cat-doped layer. Annealing process plays an important role in improving the passivation quality of SiN{sub x} films. The outstanding results obtained imply that SiN{sub x}/P Cat-doped layers can be used as promising passivation layers in high-efficiency n-type c-Si solar cells.« less

Treatment of power utilities exhaust

DOEpatents

Koermer, Gerald [Basking Ridge, NJ

2012-05-15

Provided is a process for treating nitrogen oxide-containing exhaust produced by a stationary combustion source by the catalytic reduction of nitrogen oxide in the presence of a reductant comprising hydrogen, followed by ammonia selective catalytic reduction to further reduce the nitrogen oxide level in the exhaust.

Nanofibrous electrocatalysts

DOEpatents

Liu, Di Jia; Shui, Jianglan; Chen, Chen

2016-05-24

A nanofibrous catalyst and method of manufacture. A precursor solution of a transition metal based material is formed into a plurality of interconnected nanofibers by electro-spinning the precursor solution with the nanofibers converted to a catalytically active material by a heat treatment. Selected subsequent treatments can enhance catalytic activity.

Structure and Dynamics of Zr6O8 Metal-Organic Framework Node Surfaces Probed with Ethanol Dehydration as a Catalytic Test Reaction.

PubMed

Yang, Dong; Ortuño, Manuel A; Bernales, Varinia; Cramer, Christopher J; Gagliardi, Laura; Gates, Bruce C

2018-03-14

Some metal-organic frameworks (MOFs) incorporate nodes that are metal oxide clusters such as Zr 6 O 8 . Vacancies on the node surfaces, accidental or by design, act as catalytic sites. Here, we report elucidation of the chemistry of Zr 6 O 8 nodes in the MOFs UiO-66 and UiO-67 having used infrared and nuclear magnetic resonance spectroscopies to determine the ligands on the node surfaces originating from the solvents and modifiers used in the syntheses and having elucidated the catalytic properties of the nodes for ethanol dehydration, which takes place selectively to make diethyl ether but not ethylene at 473-523 K. Density functional theory calculations show that the key to the selective catalysis is the breaking of node-linker bonds (or the accidental adjacency of open/defect sites) that allows catalytically fruitful bonding of the reactant ethanol to neighboring sites on the nodes, facilitating the bimolecular ether formation through an S N 2 mechanism.

Catalytic conversion of methane to methanol using Cu-zeolites.

PubMed

Alayon, Evalyn Mae C; Nachtegaal, Maarten; Ranocchiari, Marco; van Bokhoven, Jeroen A

2012-01-01

The conversion of methane to value-added liquid chemicals is a promising answer to the imminent demand for fuels and chemical synthesis materials in the advent of a dwindling petroleum supply. Current technology requires high energy input for the synthesis gas production, and is characterized by low overall selectivity, which calls for alternative reaction routes. The limitation to achieve high selectivity is the high C-H bond strength of methane. High-temperature reaction systems favor gas-phase radical reactions and total oxidation. This suggests that the catalysts for methane activation should be active at low temperatures. The enzymatic-inspired metal-exchanged zeolite systems apparently fulfill this need, however, methanol yield is low and a catalytic process cannot yet be established. Homogeneous and heterogeneous catalytic systems have been described which stabilize the intermediate formed after the first C-H activation. The understanding of the reaction mechanism and the determination of the active metal sites are important for formulating strategies for the upgrade of methane conversion catalytic technologies.

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.

Perspective: Size selected clusters for catalysis and electrochemistry

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

Halder, Avik; Curtiss, Larry A.; Fortunelli, Alessandro

We report that size-selected clusters containing a handful of atoms may possess noble catalytic properties different from nano-sized or bulk catalysts. Size- and composition-selected clusters can also serve as models of the catalytic active site, where an addition or removal of a single atom can have a dramatic effect on their activity and selectivity. In this Perspective, we provide an overview of studies performed under both ultra-high vacuum and realistic reaction conditions aimed at the interrogation, characterization and understanding of the performance of supported size-selected clusters in heterogeneous and electrochemical reactions, which address the effects of cluster size, cluster composition,more » cluster-support interactions and reaction conditions, the key parameters for the understanding and control of catalyst functionality. Computational modelling based on density functional theory sampling of local minima and energy barriers or ab initio Molecular Dynamics simulations is an integral part of this research by providing fundamental understanding of the catalytic processes at the atomic level, as well as by predicting new materials compositions which can be validated in experiments. Lastly, we discuss approaches which aim at the scale up of the production of well-defined clusters for use in real world applications.« less

Perspective: Size selected clusters for catalysis and electrochemistry

DOE PAGES

Halder, Avik; Curtiss, Larry A.; Fortunelli, Alessandro; ...

2018-03-15

We report that size-selected clusters containing a handful of atoms may possess noble catalytic properties different from nano-sized or bulk catalysts. Size- and composition-selected clusters can also serve as models of the catalytic active site, where an addition or removal of a single atom can have a dramatic effect on their activity and selectivity. In this Perspective, we provide an overview of studies performed under both ultra-high vacuum and realistic reaction conditions aimed at the interrogation, characterization and understanding of the performance of supported size-selected clusters in heterogeneous and electrochemical reactions, which address the effects of cluster size, cluster composition,more » cluster-support interactions and reaction conditions, the key parameters for the understanding and control of catalyst functionality. Computational modelling based on density functional theory sampling of local minima and energy barriers or ab initio Molecular Dynamics simulations is an integral part of this research by providing fundamental understanding of the catalytic processes at the atomic level, as well as by predicting new materials compositions which can be validated in experiments. Lastly, we discuss approaches which aim at the scale up of the production of well-defined clusters for use in real world applications.« less

Perspective: Size selected clusters for catalysis and electrochemistry

NASA Astrophysics Data System (ADS)

Halder, Avik; Curtiss, Larry A.; Fortunelli, Alessandro; Vajda, Stefan

2018-03-01

Size-selected clusters containing a handful of atoms may possess noble catalytic properties different from nano-sized or bulk catalysts. Size- and composition-selected clusters can also serve as models of the catalytic active site, where an addition or removal of a single atom can have a dramatic effect on their activity and selectivity. In this perspective, we provide an overview of studies performed under both ultra-high vacuum and realistic reaction conditions aimed at the interrogation, characterization, and understanding of the performance of supported size-selected clusters in heterogeneous and electrochemical reactions, which address the effects of cluster size, cluster composition, cluster-support interactions, and reaction conditions, the key parameters for the understanding and control of catalyst functionality. Computational modeling based on density functional theory sampling of local minima and energy barriers or ab initio molecular dynamics simulations is an integral part of this research by providing fundamental understanding of the catalytic processes at the atomic level, as well as by predicting new materials compositions which can be validated in experiments. Finally, we discuss approaches which aim at the scale up of the production of well-defined clusters for use in real world applications.

Catalytic generation of methane at 60-100 °C and 0.1-300 MPa from source rocks containing kerogen Types I, II, and III

NASA Astrophysics Data System (ADS)

Wei, Lin; Schimmelmann, Arndt; Mastalerz, Maria; Lahann, Richard W.; Sauer, Peter E.; Drobniak, Agnieszka; Strąpoć, Dariusz; Mango, Frank D.

2018-06-01

Low temperature (60 and 100 °C) and long-term (6 months to 5 years) heating of pre-evacuated and sterilized shales and coals containing kerogen Types I (Mahogany Shale), II (Mowry Shale and New Albany Shale), and III (Springfield Coal and Wilcox Lignite) with low initial maturities (vitrinite reflectance Ro 0.39-0.62%) demonstrates that catalytically generated hydrocarbons may explain the occurrence of some non-biogenic natural gas accumulations where insufficient thermal maturity contradicts the conventional thermal cracking paradigm. Extrapolation of the observed rate of catalytic methanogenesis in the laboratory suggests that significant amounts of sedimentary organic carbon can be converted to relatively dry natural gas over tens of thousands of years in sedimentary basins at temperatures as low as 60 °C. Our laboratory experiments utilized source rock (shale and coal) chips sealed in gold and Pyrex® glass tubes in the presence of hydrogen-isotopically contrasting waters. Parallel heating experiments applied hydrostatic pressures from 0.1 to 300 MPa. Control experiments constrained the influence of pre-existing and residual methane in closed pores of rock chips that was unrelated to newly generated methane. This study's experimental methane yields at 60 and 100 °C are 5-11 orders of magnitude higher than the theoretically predicted yields from kinetic models of thermogenic methane generation, which strongly suggests a contribution of catalytic methanogenesis. Higher temperature, longer heating time, and lower hydrostatic pressure enhanced catalytic methanogenesis. No clear relationships were observed between kerogen type or total organic carbon content and methane yields via catalysis. Catalytic methanogenesis was strongest in Mowry Shale where methane yields at 60 °C amounted to ∼2.5 μmol per gram of organic carbon after one year of hydrous heating at ambient pressure. In stark contrast to the earlier findings of hydrogen isotopic exchange between water and thermogenic methane in hydrous pyrolysis experiments above 300 °C, the hydrogen isotopic composition of added water exerted limited influence on the δ2H value of methane generated catalytically at low temperatures. We hypothesize that the catalytic sites responsible for methanogenesis are located in hydrophobic microenvironments with limited access to water. The δ13CCH4 values of methane generated catalytically at 60-100 °C range from ∼-57.6 to -41.4‰ and are thus similar to typical thermogenic methane (δ13CCH4 >-50‰) and microbially generated methane (<-55‰). Future studies need to evaluate the possibility that clumped isotope characteristics of catalytically generated methane can diagnose the low-temperature regime of catalytic methanogenesis. Furthermore, testing of freshly cored anoxic rocks is needed to determine whether the use of archived, oxygen-exposed rocks in geochemical maturation/catalysis studies introduces artifacts in experimental hydrocarbon yields.

Theoretical investigation of the selective dehydration and dehydrogenation of ethanol catalyzed by small molecules.

PubMed

Wang, Yanqun; Tang, Yizhen; Shao, Youxiang

2017-09-01

Catalytic dehydration and dehydrogenation reactions of ethanol have been investigated systematically using the ab initio quantum chemistry methods The catalysts include water, hydrogen peroxide, formic acid, phosphoric acid, hydrogen fluoride, ammonia, and ethanol itself. Moreover, a few clusters of water and ethanol were considered to simulate the catalytic mechanisms in supercritical water and supercritical ethanol. The barriers for both dehydration and dehydrogenation can be reduced significantly in the presence of the catalysts. It is revealed that the selectivity of the catalytic dehydration and dehydrogenation depends on the acidity and basicity of the catalysts and the sizes of the clusters. The acidic catalyst prefers dehydration while the basic catalysts tend to promote dehydrogenation more effectively. The calculated water-dimer catalysis mechanism supports the experimental results of the selective oxidation of ethanol in the supercritical water. It is suggested that the solvent- and catalyst-free self-oxidation of the supercritical ethanol could be an important mechanism for the selective dehydrogenation of ethanol on the theoretical point of view. Copyright © 2017 Elsevier Inc. All rights reserved.

Detection and Analysis of Enamel Cracks by Quantitative Light-induced Fluorescence Technology.

PubMed

Jun, Mi-Kyoung; Ku, Hye-Min; Kim, Euiseong; Kim, Hee-Eun; Kwon, Ho-Keun; Kim, Baek-Il

2016-03-01

The ability to accurately detect tooth cracks and quantify their depth would allow the prediction of crack progression and treatment success. The aim of this in vitro study was to determine the capabilities of quantitative light-induced fluorescence (QLF) technology in the detection of enamel cracks. Ninety-six extracted human teeth were selected for examining naturally existing or suspected cracked teeth surfaces using a photocuring unit. QLF performed with a digital camera (QLF-D) images were used to assess the ability to detect enamel cracks based on the maximum fluorescence loss value (ΔFmax, %), which was then analyzed using the QLF-D software. A histologic evaluation was then performed in which the samples were sectioned and observed with the aid of a polarized light microscope. The relationship between ΔFmax and the histology findings was assessed based on the Spearman rank correlation. The sensitivity and specificity were calculated to evaluate the validity of using QLF-D to analyze enamel inner-half cracks and cracks extending to the dentin-enamel junction. There was a strong correlation between the results of histologic evaluations of enamel cracks and the ΔFmax value, with a correlation coefficient of 0.84. The diagnostic accuracy of QLF-D had a sensitivity of 0.87 and a specificity of 0.98 for enamel inner-half cracks and a sensitivity of 0.90 and a specificity of 1.0 for cracks extending to the dentin-enamel junction. These results indicate that QLF technology would be a useful clinical tool for diagnosing enamel cracks, especially given that this is a nondestructive method. Copyright © 2016 American Association of Endodontists. Published by Elsevier Inc. All rights reserved.

Effect of composition and calcination temperature of ceria-zirconia-alumina mixed oxides on catalytic performances of ethanol conversion

NASA Astrophysics Data System (ADS)

Chuklina, S. G.; Maslenkova, S. A.; Pylinina, A. I.; Podzorova, L. I.; Ilyicheva, A. A.

2017-02-01

In the present study, we investigated the effect of preparation method, phase composition and calcination temperature of the (Ce-TZP) - Al2O3 mixed oxides on their structural features and catalytic performance in ethanol conversion. Ceria-zirconia-alumina mixed oxides with different (Ce+Zr)/Al atomic ratios were prepared via sol-gel method. Catalytic activity and selectivity were investigated for ethanol conversion to acetaldehyde, ethylene and diethyl ether.

Hydrogen adsorption and diffusion, and subcritical-crack growth in high-strength steels and nickel base alloys

NASA Technical Reports Server (NTRS)

Wei, R. P.; Klier, K.; Simmons, G. W.

1974-01-01

Coordinated studies of the kinetics of crack growth and of hydrogen adsorption and diffusion were initiated to develop information that is needed for a clearer determination of the rate controlling process and possible mechanism for hydrogen enhanced crack growth, and for estimating behavior over a range of temperatures and pressures. Inconel 718 alloy and 18Ni(200) maraging steel were selected for these studies. 18Ni(250) maraging steel, 316 stainless steel, and iron single crystal of (111) orientation were also included in the chemistry studies. Crack growth data on 18Ni(250) maraging steel from another program are included for comparison. No sustained-load crack growth was observed for the Inconel 718 alloy in gaseous hydrogen. Gaseous hydrogen assisted crack growth in the 18Ni maraging steels were characterized by K-independent (Stage 2) extension over a wide range of hydrogen pressures (86 to 2000 torr or 12 kN/m2 to 266 kN/m2) and test temperatures (-60 C to +100 C). The higher strength 18Ni(250) maraging steel was more susceptible than the lower strength 200 grade. A transition temperature was observed, above which crack growth rates became diminishingly small.

Effects of Outlets on Cracking Risk and Integral Stability of Super-High Arch Dams

PubMed Central

Hu, Hang

2014-01-01

In this paper, case study on outlet cracking is first conducted for the Goupitan and Xiaowan arch dams. A nonlinear FEM method is then implemented to study effects of the outlets on integral stability of the Xiluodu arch dam under two loading conditions, i.e., normal loading and overloading conditions. On the basis of the case study and the numerical modelling, the outlet cracking mechanism, risk, and corresponding reinforcement measures are discussed. Furthermore, the numerical simulation reveals that (1) under the normal loading conditions, the optimal distribution of the outlets will contribute to the tensile stress release in the local zone of the dam stream surface and decrease the outlet cracking risk during the operation period. (2) Under the overloading conditions, the cracks initiate around the outlets, then propagate along the horizontal direction, and finally coalesce with those in adjacent outlets, where the yield zone of the dam has a shape of butterfly. Throughout this study, a dam outlet cracking risk control and reinforcement principle is proposed to optimize the outlet design, select the appropriate concrete material, strengthen the temperature control during construction period, design reasonable impounding scheme, and repair the cracks according to their classification. PMID:25152907

Probability of brittle failure

NASA Technical Reports Server (NTRS)

Kim, A.; Bosnyak, C. P.; Chudnovsky, A.

1991-01-01

A methodology was developed for collecting statistically representative data for crack initiation and arrest from small number of test specimens. An epoxy (based on bisphenol A diglycidyl ether and polyglycol extended diglycyl ether and cured with diethylene triamine) is selected as a model material. A compact tension specimen with displacement controlled loading is used to observe multiple crack initiation and arrests. The energy release rate at crack initiation is significantly higher than that at a crack arrest, as has been observed elsewhere. The difference between these energy release rates is found to depend on specimen size (scale effect), and is quantitatively related to the fracture surface morphology. The scale effect, similar to that in statistical strength theory, is usually attributed to the statistics of defects which control the fracture process. Triangular shaped ripples (deltoids) are formed on the fracture surface during the slow subcritical crack growth, prior to the smooth mirror-like surface characteristic of fast cracks. The deltoids are complementary on the two crack faces which excludes any inelastic deformation from consideration. Presence of defects is also suggested by the observed scale effect. However, there are no defects at the deltoid apexes detectable down to the 0.1 micron level.

Recent progress in asymmetric bifunctional catalysis using multimetallic systems.

PubMed

Shibasaki, Masakatsu; Kanai, Motomu; Matsunaga, Shigeki; Kumagai, Naoya

2009-08-18

The concept of bifunctional catalysis, wherein both partners of a bimolecular reaction are simultaneously activated, is very powerful for designing efficient asymmetric catalysts. Catalytic asymmetric processes are indispensable for producing enantiomerically enriched compounds in modern organic synthesis, providing more economical and environmentally benign results than methods requiring stoichiometric amounts of chiral reagents. Extensive efforts in this field have produced many asymmetric catalysts, and now a number of reactions can be rendered asymmetric. We have focused on the development of asymmetric catalysts that exhibit high activity, selectivity, and broad substrate generality under mild reaction conditions. Asymmetric catalysts based on the concept of bifunctional catalysis have emerged as a particularly effective class, enabling simultaneous activation of multiple reaction components. Compared with conventional catalysts, bifunctional catalysts generally exhibit enhanced catalytic activity and higher levels of stereodifferentiation under milder reaction conditions, attracting much attention as next-generation catalysts for prospective practical applications. In this Account, we describe recent advances in enantioselective catalysis with bifunctional catalysts. Since our identification of heterobimetallic rare earth-alkali metal-BINOL (REMB) complexes, we have developed various types of bifunctional multimetallic catalysts. The REMB catalytic system is effective for catalytic asymmetric Corey-Chaykovsky epoxidation and cyclopropanation. A dinucleating Schiff base has emerged as a suitable multidentate ligand for bimetallic catalysts, promoting catalytic syn-selective nitro-Mannich, anti-selective nitroaldol, and Mannich-type reactions. The sugar-based ligand GluCAPO provides a suitable platform for polymetallic catalysts; structural elucidation revealed that their higher order polymetallic structures are a determining factor for their function in the catalytic asymmetric Strecker reaction. Rational design identified a related ligand, FujiCAPO, which exhibits superior performance in catalytic asymmetric conjugate addition of cyanide to enones and a catalytic asymmetric Diels-Alder-type reaction. The combination of an amide-based ligand with a rare earth metal constitutes a unique catalytic system: the ligand-metal association is in equilibrium because of structural flexibility. These catalytic systems are effective for asymmetric amination of highly coordinative substrate as well as for Mannich-type reaction of alpha-cyanoketones, in which hydrogen bonding cooperatively contributes to substrate activation and stereodifferentiation. Most of the reactions described here generate stereogenic tetrasubstituted carbons or quaternary carbons, noteworthy accomplishments even with modern synthetic methods. Several reactions have been incorporated into the asymmetric synthesis of therapeutics (or their candidate molecules) such as Tamiflu, AS-3201 (ranirestat), GRL-06579A, and ritodrine, illustrating the usefulness of bifunctional asymmetric catalysis.

Catalytic Organometallic Reactions of Ammonia

PubMed Central

Klinkenberg, Jessica L.

2012-01-01

Until recently, ammonia had rarely succumbed to catalytic transformations with homogeneous catalysts, and the development of such reactions that are selective for the formation of single products under mild conditions has encountered numerous challenges. However, recently developed catalysts have allowed several classes of reactions to create products with nitrogen-containing functional groups from ammonia. These reactions include hydroaminomethylation, reductive amination, alkylation, allylic substitution, hydroamination, and cross-coupling. This Minireview describes examples of these processes and the factors that control catalyst activity and selectivity. PMID:20857466

Selective catalytic reduction system and process using a pre-sulfated zirconia binder

DOEpatents

Sobolevskiy, Anatoly; Rossin, Joseph A.

2010-06-29

A selective catalytic reduction (SCR) process with a palladium catalyst for reducing NOx in a gas, using hydrogen as a reducing agent is provided. The process comprises contacting the gas stream with a catalyst system, the catalyst system comprising (ZrO.sub.2)SO.sub.4, palladium, and a pre-sulfated zirconia binder. The inclusion of a pre-sulfated zirconia binder substantially increases the durability of a Pd-based SCR catalyst system. A system for implementing the disclosed process is further provided.

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

Catalytic Oxidation of Methane into Methanol over Copper-Exchanged Zeolites with Oxygen at Low Temperature

PubMed Central

2016-01-01

The direct catalytic conversion of methane to liquid oxygenated compounds, such as methanol or dimethyl ether, at low temperature using molecular oxygen is a grand challenge in C–H activation that has never been met with synthetic, heterogeneous catalysts. We report the first demonstration of direct, catalytic oxidation of methane into methanol with molecular oxygen over copper-exchanged zeolites at low reaction temperatures (483–498 K). Reaction kinetics studies show sustained catalytic activity and high selectivity for a variety of commercially available zeolite topologies under mild conditions (e.g., 483 K and atmospheric pressure). Transient and steady state measurements with isotopically labeled molecules confirm catalytic turnover. The catalytic rates and apparent activation energies are affected by the zeolite topology, with caged-based zeolites (e.g., Cu-SSZ-13) showing the highest rates. Although the reaction rates are low, the discovery of catalytic sites in copper-exchanged zeolites will accelerate the development of strategies to directly oxidize methane into methanol under mild conditions. PMID:27413787

Clean catalytic combustor program

NASA Technical Reports Server (NTRS)

Ekstedt, E. E.; Lyon, T. F.; Sabla, P. E.; Dodds, W. J.

1983-01-01

A combustor program was conducted to evolve and to identify the technology needed for, and to establish the credibility of, using combustors with catalytic reactors in modern high-pressure-ratio aircraft turbine engines. Two selected catalytic combustor concepts were designed, fabricated, and evaluated. The combustors were sized for use in the NASA/General Electric Energy Efficient Engine (E3). One of the combustor designs was a basic parallel-staged double-annular combustor. The second design was also a parallel-staged combustor but employed reverse flow cannular catalytic reactors. Subcomponent tests of fuel injection systems and of catalytic reactors for use in the combustion system were also conducted. Very low-level pollutant emissions and excellent combustor performance were achieved. However, it was obvious from these tests that extensive development of fuel/air preparation systems and considerable advancement in the steady-state operating temperature capability of catalytic reactor materials will be required prior to the consideration of catalytic combustion systems for use in high-pressure-ratio aircraft turbine engines.

Discovery of a selective catalytic p300/CBP inhibitor that targets lineage-specific tumours

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

Lasko, Loren M.; Jakob, Clarissa G.; Edalji, Rohinton P.

The dynamic and reversible acetylation of proteins, catalysed by histone acetyltransferases (HATs) and histone deacetylases (HDACs), is a major epigenetic regulatory mechanism of gene transcription1 and is associated with multiple diseases. Histone deacetylase inhibitors are currently approved to treat certain cancers, but progress on the development of drug-like histone actyltransferase inhibitors has lagged behind2. The histone acetyltransferase paralogues p300 and CREB-binding protein (CBP) are key transcriptional co-activators that are essential for a multitude of cellular processes, and have also been implicated in human pathological conditions (including cancer3). Current inhibitors of the p300 and CBP histone acetyltransferase domains, including natural products4,more » bi-substrate analogues5 and the widely used small molecule C6466,7, lack potency or selectivity. Here, we describe A-485, a potent, selective and drug-like catalytic inhibitor of p300 and CBP. We present a high resolution (1.95 Å) co-crystal structure of a small molecule bound to the catalytic active site of p300 and demonstrate that A-485 competes with acetyl coenzyme A (acetyl-CoA). A-485 selectively inhibited proliferation in lineage-specific tumour types, including several haematological malignancies and androgen receptor-positive prostate cancer. A-485 inhibited the androgen receptor transcriptional program in both androgen-sensitive and castration-resistant prostate cancer and inhibited tumour growth in a castration-resistant xenograft model. These results demonstrate the feasibility of using small molecule inhibitors to selectively target the catalytic activity of histone acetyltransferases, which may provide effective treatments for transcriptional activator-driven malignancies and diseases.« less

Simplified moment tensor analysis and unified decomposition of acoustic emission source: Application to in situ hydrofracturing test

NASA Astrophysics Data System (ADS)

Ohtsu, Masayasu

1991-04-01

An application of a moment tensor analysis to acoustic emission (AE) is studied to elucidate crack types and orientations of AE sources. In the analysis, simplified treatment is desirable, because hundreds of AE records are obtained from just one experiment and thus sophisticated treatment is realistically cumbersome. Consequently, a moment tensor inversion based on P wave amplitude is employed to determine six independent tensor components. Selecting only P wave portion from the full-space Green's function of homogeneous and isotropic material, a computer code named SiGMA (simplified Green's functions for the moment tensor analysis) is developed for the AE inversion analysis. To classify crack type and to determine crack orientation from moment tensor components, a unified decomposition of eigenvalues into a double-couple (DC) part, a compensated linear vector dipole (CLVD) part, and an isotropic part is proposed. The aim of the decomposition is to determine the proportion of shear contribution (DC) and tensile contribution (CLVD + isotropic) on AE sources and to classify cracks into a crack type of the dominant motion. Crack orientations determined from eigenvectors are presented as crack-opening vectors for tensile cracks and fault motion vectors for shear cracks, instead of stereonets. The SiGMA inversion and the unified decomposition are applied to synthetic data and AE waveforms detected during an in situ hydrofracturing test. To check the accuracy of the procedure, numerical experiments are performed on the synthetic waveforms, including cases with 10% random noise added. Results show reasonable agreement with assumed crack configurations. Although the maximum error is approximately 10% with respect to the ratios, the differences on crack orientations are less than 7°. AE waveforms detected by eight accelerometers deployed during the hydrofracturing test are analyzed. Crack types and orientations determined are in reasonable agreement with a predicted failure plane from borehole TV observation. The results suggest that tensile cracks are generated first at weak seams and then shear cracks follow on the opened joints.

Spontaneous emergence of cataclysmic networks in spatially extended systems

NASA Astrophysics Data System (ADS)

Manrubia, Susanna C.; Poyatos, Juan F.; Pérez-Mercader, Juan

2002-11-01

A system of interacting chemical species able to catalyse each others' production is studied. We consider a two-dimensional surface where single molecules attach, diffuse, catalytically interact, and decay. The population of species molecules and the network of interactions among them are dynamical entities. After a short transient time, robust catalytic cycles emerge and a "stationary" state of high diversity and large population numbers settles down. Population dynamics and physical space select among possible graphs of catalytic interactions. The organization of the system is robust: parasitic invaders are short-lived, their populations are kept at low levels, and are unable to sweep away the emerging catalytic cycles.

Percussive tool use by Taï Western chimpanzees and Fazenda Boa Vista bearded capuchin monkeys: a comparison

PubMed Central

Visalberghi, Elisabetta; Sirianni, Giulia; Fragaszy, Dorothy; Boesch, Christophe

2015-01-01

Percussive tool use holds special interest for scientists concerned with human origins. We summarize the findings from two field sites, Taï and Fazenda Boa Vista, where percussive tool use by chimpanzees and bearded capuchins, respectively, has been extensively investigated. We describe the ecological settings in which nut-cracking occurs and focus on four aspects of nut-cracking that have important cognitive implications, namely selection of tools, tool transport, tool modification and modulation of actions to reach the goal of cracking the nut. We comment on similarities and differences in behaviour and consider whether the observed differences reflect ecological, morphological, social and/or cognitive factors. Both species are sensitive to physical properties of tools, adjust their selection of hammers conditionally to the resistance of the nuts and to transport distance, and modulate the energy of their strikes under some conditions. However, chimpanzees transport hammers more frequently and for longer distances, take into account a higher number of combinations of variables and occasionally intentionally modify tools. A parsimonious interpretation of our findings is that morphological, ecological and social factors account for the observed differences. Confirmation of plausible cognitive differences in nut-cracking requires data not yet available. PMID:26483529

Fatigue and fail-safe design features of the DC-10 airplane

NASA Technical Reports Server (NTRS)

Stone, M. E.

1972-01-01

The philosophy and methods used in the design of the DC-10 aircraft to assure structural reliability against cracks under repeated service loads are described in detail. The approach consists of three complementary parts: (1) the structure is designed to be fatigue resistant for a crack-free life of 60,000 flight hours; (2) inasmuch as small undetected cracks could develop from other sources, such as material flaws and manufacturing preloads, the structure also is designed to arrest and control cracks within a reasonable service-inspection interval; and (3) a meaningful service-inspection program has been defined on the basis of analysis and test experience from the design development program. This service-inspection program closes the loop to assure the structural integrity of the DC-10 airframe. Selected materials, fasteners, and structural arrangements are used to achieve these design features with minimum structural weight and with economy in manufacturing and maintenance. Extensive analyses and testing were performed to develop and verify the design. The basic design considerations for fatigue-resistant structure are illustrated in terms of material selection, design loads spectra, methods for accurate stress and fatigue damage analysis, and proven concepts for efficient detail design.

Research on Crack Formation in Gypsum Partitions with Doorway by Means of FEM and Fracture Mechanics

NASA Astrophysics Data System (ADS)

Kania, Tomasz; Stawiski, Bohdan

2017-10-01

Cracking damage in non-loadbearing internal partition walls is a serious problem that frequently occurs in new buildings within the short term after putting them into service or even before completion of construction. Damage in partition walls is sometimes so great that they cannot be accepted by their occupiers. This problem was illustrated by the example of damage in a gypsum partition wall with doorway attributed to deflection of the slabs beneath and above it. In searching for the deflection which causes damage in masonry walls, fracture mechanics applied to the Finite Element Method (FEM) have been used. For a description of gypsum behaviour, the smeared cracking material model has been selected, where stresses are transferred across the narrowly opened crack until its width reaches the ultimate value. Cracks in the Finite Element models overlapped the real damage observed in the buildings. In order to avoid cracks under the deflection of large floor slabs, the model of a wall with reinforcement in the doorstep zone and a 40 mm thick elastic junction between the partition and ceiling has been analysed.

Fatigue cracking in road pavement

NASA Astrophysics Data System (ADS)

Mackiewicz, P.

2018-05-01

The article presents the problem of modelling fatigue phenomena occurring in the road pavement. The example of two selected pavements shows the changes occurring under the influence of the load in different places of the pavement layers. Attention is paid to various values of longitudinal and transverse strains generated at the moment of passing the wheel on the pavement. It was found that the key element in the crack propagation analysis is the method of transferring the load to the pavement by the tire and the strain distribution in the pavement. During the passage of the wheel in the lower layers of the pavement, a complex stress state arises. Then vertical, horizontal and tangent stresses with various values appear. The numerical analyses carried out with the use of finite element methods allowed to assess the strain and stress changes occurring in the process of cracking road pavement. It has been shown that low-thickness pavements are susceptible to fatigue cracks arising "bottom to top", while pavements thicker are susceptible to "top to bottom" cracks. The analysis of the type of stress allowed to determine the cracking mechanism.

Area-Selective Atomic Layer Deposition of Metal Oxides on Noble Metals through Catalytic Oxygen Activation

PubMed Central

2017-01-01

Area-selective atomic layer deposition (ALD) is envisioned to play a key role in next-generation semiconductor processing and can also provide new opportunities in the field of catalysis. In this work, we developed an approach for the area-selective deposition of metal oxides on noble metals. Using O2 gas as co-reactant, area-selective ALD has been achieved by relying on the catalytic dissociation of the oxygen molecules on the noble metal surface, while no deposition takes place on inert surfaces that do not dissociate oxygen (i.e., SiO2, Al2O3, Au). The process is demonstrated for selective deposition of iron oxide and nickel oxide on platinum and iridium substrates. Characterization by in situ spectroscopic ellipsometry, transmission electron microscopy, scanning Auger electron spectroscopy, and X-ray photoelectron spectroscopy confirms a very high degree of selectivity, with a constant ALD growth rate on the catalytic metal substrates and no deposition on inert substrates, even after 300 ALD cycles. We demonstrate the area-selective ALD approach on planar and patterned substrates and use it to prepare Pt/Fe2O3 core/shell nanoparticles. Finally, the approach is proposed to be extendable beyond the materials presented here, specifically to other metal oxide ALD processes for which the precursor requires a strong oxidizing agent for growth. PMID:29503508

An investigation of reheat cracking in the weld heat affected zone of type 347 stainless steel

NASA Astrophysics Data System (ADS)

Phung-On, Isaratat

2007-12-01

Reheat cracking has been a persistent problem for welding of many alloys such as the stabilized stainless steels: Types 321 and 347 as well as Cr-Mo-V steels. Similar problem occurs in Ni-base superalloys termed "strain-age cracking". Cracking occurs during the post weld heat treatment. The HAZ is the most susceptible area due to metallurgical reactions in solid state during both heating and cooling thermal cycle. Many investigations have been conducted to understand the RHC mechanism. There is still no comprehensive mechanism to explain its underlying mechanism. In this study, there were two proposed cracking mechanisms. The first is the formation of a PFZ resulting in local weakening and strain localization. The second is the creep-like grain boundary sliding that causes microvoid formation at the grain boundaries and the triple point junctions. Cracking occurs due to the coalescence of the microvoids that form. In this study, stabilized grade stainless steel, Type 347, was selected for investigation of reheat cracking mechanism due to the simplicity of its microstructure and understanding of its metallurgical behavior. The Gleeble(TM) 3800 system was employed due to its capability for precise control of both thermal and mechanical simulation. Cylindrical samples were subjected to thermal cycles for the HAZ simulation followed by PWHT as the reheat cracking test. "Susceptibility C-curves" were plotted as a function of PWHT temperatures and time to failure at applied stress levels of 70% and 80% yield strength. These C-curves show the possible relationship of the reheat cracking susceptibility and carbide precipitation behavior. To identify the mechanism, the sample shape was modified containing two flat surfaces at the center section. These flat surfaces were electro-polished and subjected to the HAZ simulation followed by the placement of the micro-indentation arrays. Then, the reheat cracking test was performed. The cracking mechanism was identified by tracing the shifting of the micro-indentations compared to their original locations. At the 80% stress level, the cracking mechanism was identified as the PFZ weakening, while at the 70% stress as the creep-like grain boundary sliding. A design of experiment (DOE) using a D-optimal design was successfully employed in this study to investigate the effects of microstructures on the reheat cracking susceptibility. The microstructures were modified by heat treatment prior to the reheat cracking test. The grain size and cooling rate were found to have moderate effects on cracking susceptibility. The amount (volume fraction) of MC carbide (NbC) had a significant effect on time to failure. The more NbC formed prior to test, the longer time to failure, and the more resistance to reheat cracking. On the other hand, the amount of GB carbide (M23C6) had an insignificant effect. The statistical interaction between MC carbide with other testing parameters also had strong effect. The PWHT temperature also had significant effect as can be predicted from the susceptibility C-curves. The heat treatment schedules, during cooling and during heating schedules, were also investigated. During cooling schedule was the same schedule done earlier in this study. On the other hand, during heating schedule allowed the sample cool to room temperature prior microstructure modification followed by the reheat cracking test. During heating schedule showed an improvement in resistance to reheat cracking. Microstructure of the crack samples showed the intergranular cracking path and wedge shapes along cracking boundaries. There was also the evidence of grain boundary sliding as a result of the creep-like grain boundary sliding cracking mechanism. SEM showed the intergranular cracking and grain separation with precipitates decorated on the fracture surfaces. The precipitates were identified as Nb-rich, MC carbide (NbC). The fracture surfaces showed micro-ductility and microvoid coalescence. The size of microvoid corresponds to the size of precipitate that forms. In addition, there was intragranular cracking in some location indicating that another failure mechanism may also be possible. It was believed that failure may occur along a precipitate free zone. However, the distinct PFZ could not be detected. A SS-DTA technique was also implemented in order to determine precipitation temperatures of the material. The results showed the possible precipitation temperatures in the range of 850°C to 650°C. However, the results were not confidently reliable due to the small amount of carbide formed that affects the sensitivity of the SS-DTA. A simple grain boundary sliding model was generated proposing that the sliding is operated by the shear stress resulting from the formation of precipitate in the grain interior. Then, the sliding results in the microvoid formation and coalescence followed by cracking. In addition, a simple finite element model was generated to provide the illustration of the shear stress built up by the formation of precipitate. The model showed that shear stress can cause the grain boundary movement/sliding. Based on the results from this study, the recommendation for the selection of post weld heat treatment schedule as well as welding procedures can be determined for the prevention of the reheat cracking. A residual stress should be kept below the critical value during welding and post weld heat treating. The testing procedures used in this study can be applied as the guidelines to conduct the reheat cracking susceptibility test for material selection.

Efficient selective catalytic reduction of NO by novel carbon-doped metal catalysts made from electroplating sludge.

PubMed

Zhang, Jia; Zhang, Jingyi; Xu, Yunfeng; Su, Huimin; Li, Xiaoman; Zhou, Ji Zhi; Qian, Guangren; Li, Li; Xu, Zhi Ping

2014-10-07

Electroplating sludges, once regarded as industrial wastes, are precious resources of various transition metals. This research has thus investigated the recycling of an electroplating sludge as a novel carbon-doped metal (Fe, Ni, Mg, Cu, and Zn) catalyst, which was different from a traditional carbon-supported metal catalyst, for effective NO selective catalytic reduction (SCR). This catalyst removed >99.7% NO at a temperature as low as 300 °C. It also removed NO steadily (>99%) with a maximum specific accumulative reduced amount (MSARA) of 3.4 mmol/g. Gas species analyses showed that NO removal was accompanied by evolving N2 and CO2. Moreover, in a wide temperature window, the sludge catalyst showed a higher CO2 selectivity (>99%) than an activated carbon-supported metal catalyst. Structure characterizations revealed that carbon-doped metal was transformed to metal oxide in the sludge catalyst after the catalytic test, with most carbon (2.33 wt %) being consumed. These observations suggest that NO removal over the sludge catalyst is a typical SCR where metals/metal oxides act as the catalytic center and carbon as the reducing reagent. Therefore, our report probably provides an opportunity for high value-added utilizations of heavy-metal wastes in mitigating atmospheric pollutions.

Catalytic epoxidation activity of keplerate polyoxomolybdate nanoball toward aqueous suspension of olefins under mild aerobic conditions.

PubMed

Rezaeifard, Abdolreza; Haddad, Reza; Jafarpour, Maasoumeh; Hakimi, Mohammad

2013-07-10

Catalytic efficiency of a sphere-shaped nanosized polyoxomolybdate {Mo132} in the aerobic epoxidation of olefins in water at ambient temperature and pressure in the absence of reducing agent is exploited which resulted good-to-high yields and desired selectivity.

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

NASA Astrophysics Data System (ADS)

Rueda Velasquez, Rosa Imelda

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

An Evaluation of Apical Cracks in Teeth Undergoing Orthograde Root Canal Instrumentation.

PubMed

Rose, Elizabeth; Svec, Timothy

2015-12-01

Dentinal damage and cracks induced by orthograde preparation methods have been reported in studies using extracted teeth. The purpose of this in situ investigation was to evaluate dentinal cracks in nonextracted teeth after final instrumentation. The null hypothesis is that orthograde root canal instrumentation will have no effect on crack initiation in teeth retained in the natural periodontium. Mandibular first and second premolars of pig jaws were selected. Forty single-rooted canals were divided into 5 groups (n = 8): (1) WaveOne (Dentsply Tulsa Dental Specialties, Tulsa, OK) 25/08; (2) ProTaper rotary S1, S2, F2 (25/08) (Dentsply Tulsa Dental Specialties); (3) crown-down GT hand files 20/12, 20/10, 20/08 (Dentsply Tulsa Dental Specialties); (4) positive control (purposefully cracked); and (5) negative control (uninstrumented teeth). After instrumentation, superficial soft tissue was removed, and bone was carefully peeled away with surgical burs to the level of the root apices. Roots were resected 1 mm coronal to the working length, stained with caries indicator dye, and transilluminated; images were captured and viewed at 30× magnification to determine the presence or absence of dentinal cracks. WaveOne, ProTaper rotary, and GT hand files produced no cracks. All positive controls had cracks; all negative controls had no cracks. Within the limits of this investigation, the presence of natural periodontal structures may prevent cracking or dentinal damage in teeth receiving orthograde root canal instrumentation. Copyright © 2015 American Association of Endodontists. Published by Elsevier Inc. All rights reserved.

Lifetime prediction for the subsurface crack propagation using three-dimensional dynamic FEA model

NASA Astrophysics Data System (ADS)

Yin, Yuan; Chen, Yun-Xia; Liu, Le

2017-03-01

The subsurface crack propagation is one of the major interests for gear system research. The subsurface crack propagation lifetime is the number of cycles remaining for a spall to appear, which can be obtained through either stress intensity factor or accumulated plastic strain analysis. In this paper, the heavy loads are applied to the gear system. When choosing stress intensity factor, the high compressive stress suppresses Mode I stress intensities and severely reduces Mode II stress intensities in the heavily loaded lubricated contacts. Such that, the accumulated plastic strain is selected to calculate the subsurface crack propagation lifetime from the three-dimensional FEA model through ANSYS Workbench transient analysis. The three-dimensional gear FEA dynamic model with the subsurface crack is built through dividing the gears into several small elements. The calculation of the total cycles of the elements is proposed based on the time-varying accumulated plastic strain, which then will be used to calculate the subsurface crack propagation lifetime. During this process, the demonstration from a subsurface crack to a spall can be uncovered. In addition, different sizes of the elements around the subsurface crack are compared in this paper. The influences of the frictional coefficient and external torque on the crack propagation lifetime are also discussed. The results show that the lifetime of crack propagation decreases significantly when the external load T increasing from 100 N m to 150 N m. Given from the distributions of the accumulated plastic strain, the lifetime shares no significant difference when the frictional coefficient f ranging in 0.04-0.06.

Cracking of Beams Strengthened with Externally Bonded SRP Tapes

NASA Astrophysics Data System (ADS)

Krzywoń, Rafał

2017-10-01

Paper discusses strengthening efficiency of relatively new kind of SRP composite based on high strength steel wires. They are made of ultra-high strength steel primarily used in cords of car tires. Through advanced treatment, the mechanical properties of SRP steel are similar to other high carbon cold drawn steels used in construction industry. Strength significantly exceed 2000 MPa, there is no perfect plasticity at yield stress level. Almost linear stress-strain relationship makes SRP steel mechanical properties similar to carbon fibers. Also flexibility and weight ratio of the composite overlay is slightly worse than CFRP strip. Despite these advantages SRP is not as popular as other composites reinforced with fibers of high strength. This is due to the small number of studies of SRP behavior and applicability. Paper shows selected results of the laboratory test of beams strengthened with use of SRP and CFRP externally bonded overlays. Attention has been focused primarily on the phenomenon of cracking. Comparison include the cracking moment, crack width and spacing, coverage of crack zone. Despite the somewhat lower rigidity of SRP tapes, they have a much better adhesion to concrete, so that the crack width is comparable in almost the whole load range. The paper also includes an assessment of the common methods of checking the condition of cracking in relation to the tested SRP strengthening. The paper presents actual calculation procedures to determine the crack spacing and crack width. The discussed formulas are verified with results of provided laboratory tests.

Experimental and Finite Element Modeling of Near-Threshold Fatigue Crack Growth for the K-Decreasing Test Method

NASA Technical Reports Server (NTRS)

Smith, Stephen W.; Seshadri, Banavara R.; Newman, John A.

2015-01-01

The experimental methods to determine near-threshold fatigue crack growth rate data are prescribed in ASTM standard E647. To produce near-threshold data at a constant stress ratio (R), the applied stress-intensity factor (K) is decreased as the crack grows based on a specified K-gradient. Consequently, as the fatigue crack growth rate threshold is approached and the crack tip opening displacement decreases, remote crack wake contact may occur due to the plastically deformed crack wake surfaces and shield the growing crack tip resulting in a reduced crack tip driving force and non-representative crack growth rate data. If such data are used to life a component, the evaluation could yield highly non-conservative predictions. Although this anomalous behavior has been shown to be affected by K-gradient, starting K level, residual stresses, environmental assisted cracking, specimen geometry, and material type, the specifications within the standard to avoid this effect are limited to a maximum fatigue crack growth rate and a suggestion for the K-gradient value. This paper provides parallel experimental and computational simulations for the K-decreasing method for two materials (an aluminum alloy, AA 2024-T3 and a titanium alloy, Ti 6-2-2-2-2) to aid in establishing clear understanding of appropriate testing requirements. These simulations investigate the effect of K-gradient, the maximum value of stress-intensity factor applied, and material type. A material independent term is developed to guide in the selection of appropriate test conditions for most engineering alloys. With the use of such a term, near-threshold fatigue crack growth rate tests can be performed at accelerated rates, near-threshold data can be acquired in days instead of weeks without having to establish testing criteria through trial and error, and these data can be acquired for most engineering materials, even those that are produced in relatively small product forms.

Trends in Selective Hydrogen Peroxide Production on Transition Metal Surfaces from First Principles

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

Rankin, Rees B.; Greeley, Jeffrey P.

2012-10-19

We present a comprehensive, Density Functional Theory-based analysis of the direct synthesis of hydrogen peroxide, H2O2, on twelve transition metal surfaces. We determine the full thermodynamics and selected kinetics of the reaction network on these metals, and we analyze these energetics with simple, microkinetically motivated rate theories to assess the activity and selectivity of hydrogen peroxide production on the surfaces of interest. By further exploiting Brønsted-Evans-Polanyi relationships and scaling relationships between the binding energies of different adsorbates, we express the results in the form of a two dimensional contour volcano plot, with the activity and selectivity being determined as functionsmore » of two independent descriptors, the atomic hydrogen and oxygen adsorption free energies. We identify both a region of maximum predicted catalytic activity, which is near Pt and Pd in descriptor space, and a region of selective hydrogen peroxide production, which includes Au. The optimal catalysts represent a compromise between activity and selectivity and are predicted to fall approximately between Au and Pd in descriptor space, providing a compact explanation for the experimentally known performance of Au-Pd alloys for hydrogen peroxide synthesis, and suggesting a target for future computational screening efforts to identify improved direct hydrogen peroxide synthesis catalysts. Related methods of combining activity and selectivity analysis into a single volcano plot may be applicable to, and useful for, other aqueous phase heterogeneous catalytic reactions where selectivity is a key catalytic criterion.« less

Selection of ribozymes that catalyse multiple-turnover Diels–Alder cycloadditions by using in vitro compartmentalization

PubMed Central

Agresti, Jeremy J.; Kelly, Bernard T.; Jäschke, Andres; Griffiths, Andrew D.

2005-01-01

In vitro compartmentalization (IVC) has previously been used to evolve protein enzymes. Here, we demonstrate how IVC can be applied to select RNA enzymes (ribozymes) for a property that has previously been unselectable: true intermolecular catalysis. Libraries containing 1011 ribozyme genes are compartmentalized in the aqueous droplets of a water-in-oil emulsion, such that most droplets contain no more than one gene, and transcribed in situ. By coencapsulating the gene, RNA, and the substrates/products of the catalyzed reaction, ribozymes can be selected for all enzymatic properties: substrate recognition, product formation, rate acceleration, and turnover. Here we exploit the complementarity of IVC with systematic evolution of ligands by exponential enrichment (SELEX), which allows selection of larger libraries (≥1015) and for very small rate accelerations (kcat/kuncat) but only selects for intramolecular single-turnover reactions. We selected ≈1014 random RNAs for Diels–Alderase activity with five rounds of SELEX, then six to nine rounds with IVC. All selected ribozymes catalyzed the Diels–Alder reaction in a truly bimolecular fashion and with multiple turnover. Nearly all ribozymes selected by using eleven rounds of SELEX alone contain a common catalytic motif. Selecting with SELEX then IVC gave ribozymes with significant sequence variations in this catalytic motif and ribozymes with completely novel motifs. Interestingly, the catalytic properties of all of the selected ribozymes were quite similar. The ribozymes are strongly product inhibited, consistent with the Diels–Alder transition state closely resembling the product. More efficient Diels–Alderases may need to catalyze a second reaction that transforms the product and prevents product inhibition. PMID:16260754

Design of Stratified Functional Nanoporous Materials for CO 2 Capture and Conversion

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

Johnson, J. Karl; Ye, Jingyun

The objective of this project is to develop novel nanoporous materials for CO 2 capture and conversion. The motivation of this work is that capture of CO 2 from flue gas or the atmosphere coupled with catalytic hydrogenation of CO 2 into valuable chemicals and fuels can reduce the net amount of CO 2 in the atmosphere while providing liquid transportation fuels and other commodity chemicals. One approach to increasing the economic viability of carbon capture and conversion is to design a single material that can be used for both the capture and catalytic conversion of CO 2, because suchmore » a material could increase efficiency through process intensification. We have used density functional theory (DFT) methods to design catalytic moieties that can be incorporated into various metal organic framework (MOF) materials. We chose to work with MOFs because they are highly tailorable, can be functionalized, and have been shown to selectively adsorb CO 2 over N 2, which is a requirement for CO 2 capture from flue gas. Moreover, the incorporation of molecular catalytic moieties into MOF, through covalent bonding, produces a heterogeneous catalytic material having activities and selectivities close to those of homogeneous catalysts, but without the draw-backs associated with homogeneous catalysis.« less

Investigation of Cold Expansion of Short Edge Margin Holes with Pre-existing Cracks in 2024-T351 Aluminum Alloy

DTIC Science & Technology

2011-12-01

Fractography ............................................................................................................ 57 5. DISCUSSION...small radial cracks (0.03 to 0.07 inch) can be retarded by deep cold expansion (3.5% interference fit cold expansion). Petrak and Stewart (1974) and...the research done by Carlson, 13 and is shown in Fig. 48. 4.6 Fractography Select images were taken for fractography purposes. It should be

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

Catalytic two-stage coal hydrogenation process using extinction recycle of heavy liquid fraction

DOEpatents

MacArthur, J.B.; Comolli, A.G.; McLean, J.B.

1989-10-17

A process is described for catalytic two-stage hydrogenation and liquefaction of coal with selective extinction recycle of all heavy liquid fractions boiling above a distillation cut point of about 600--750 F to produce increased yields of low-boiling hydrocarbon liquid and gas products. In the process, the particulate coal feed is slurried with a process-derived liquid solvent normally boiling above about 650 F and fed into a first stage catalytic reaction zone operated at conditions which promote controlled rate liquefaction of the coal, while simultaneously hydrogenating the hydrocarbon recycle oils. The first stage reactor is maintained at 710--800 F temperature, 1,000--4,000 psig hydrogen partial pressure, and 10-90 lb/hr per ft[sup 3] catalyst space velocity. Partially hydrogenated material withdrawn from the first stage reaction zone is passed directly to the second stage catalytic reaction zone maintained at 760--860 F temperature for further hydrogenation and hydroconversion reactions. A 600--750 F[sup +] fraction containing 0--20 W % unreacted coal and ash solids is recycled to the coal slurrying step. If desired, the cut point lower boiling fraction can be further catalytically hydrotreated. By this process, the coal feed is successively catalytically hydrogenated and hydroconverted at selected conditions, to provide significantly increased yields of desirable low-boiling hydrocarbon liquid products and minimal production of hydrocarbon gases, and no net production of undesirable heavy oils and residuum materials. 2 figs.

Catalytic two-stage coal hydrogenation process using extinction recycle of heavy liquid fraction

DOEpatents

MacArthur, James B.; Comolli, Alfred G.; McLean, Joseph B.

1989-01-01

A process for catalytic two-stage hydrogenation and liquefaction of coal with selective extinction recycle of all heavy liquid fractions boiling above a distillation cut point of about 600.degree.-750.degree. F. to produce increased yields of low-boiling hydrocarbon liquid and gas products. In the process, the particulate coal feed is slurried with a process-derived liquid solvent normally boiling above about 650.degree. F. and fed into a first stage catalytic reaction zone operated at conditions which promote controlled rate liquefaction of the coal, while simultaneously hydrogenating the hydrocarbon recycle oils. The first stage reactor is maintained at 710.degree.-800.degree. F. temperature, 1000-4000 psig hydrogen partial pressure, and 10-90 lb/hr per ft.sup.3 catalyst space velocity. Partially hydrogenated material withdrawn from the first stage reaction zone is passed directly to the second stage catalytic reaction zone maintained at 760.degree.-860.degree. F. temperature for further hydrogenation and hydroconversion reactions. A 600.degree.-750.degree. F..sup.+ fraction containing 0-20 W % unreacted coal and ash solids is recycled to the coal slurrying step. If desired, the cut point lower boiling fraction can be further catalytically hydrotreated. By this process, the coal feed is successively catalytically hydrogenated and hydroconverted at selected conditions, to provide significantly increased yields of desirable low-boiling hydrocarbon liquid products and minimal production of hydrocarbon gases, and no net production of undesirable heavy oils and residuum materials.

Low-temperature conversion of ammonia to nitrogen in water with ozone over composite metal oxide catalyst.

PubMed

Chen, Yunnen; Wu, Ye; Liu, Chen; Guo, Lin; Nie, Jinxia; Chen, Yu; Qiu, Tingsheng

2018-04-01

As one of the most important water pollutants, ammonia nitrogen emissions have increased year by year, which has attracted people's attention. Catalytic ozonation technology, which involves production of ·OH radical with strong oxidation ability, is widely used in the treatment of organic-containing wastewater. In this work, MgO-Co 3 O 4 composite metal oxide catalysts prepared with different fabrication conditions have been systematically evaluated and compared in the catalytic ozonation of ammonia (50mg/L) in water. In terms of high catalytic activity in ammonia decomposition and high selectivity for gaseous nitrogen, the catalyst with MgO-Co 3 O 4 molar ratio 8:2, calcined at 500°C for 3hr, was the best one among the catalysts we tested, with an ammonia nitrogen removal rate of 85.2% and gaseous nitrogen selectivity of 44.8%. In addition, the reaction mechanism of ozonation oxidative decomposition of ammonia nitrogen in water with the metal oxide catalysts was discussed. Moreover, the effect of coexisting anions on the degradation of ammonia was studied, finding that SO 4 2- and HCO 3 - could inhibit the catalytic activity while CO 3 2- and Br - could promote it. The presence of coexisting cations had very little effect on the catalytic ozonation of ammonia nitrogen. After five successive reuses, the catalyst remained stable in the catalytic ozonation of ammonia. Copyright © 2017. Published by Elsevier B.V.

Catalytic coal liquefaction process

DOEpatents

Garg, D.; Sunder, S.

1986-12-02

An improved process for catalytic solvent refining or hydroliquefaction of non-anthracitic coal at elevated temperatures under hydrogen pressure in a solvent comprises using as catalyst a mixture of a 1,2- or 1,4-quinone and an alkaline compound, selected from ammonium, alkali metal, and alkaline earth metal oxides, hydroxides or salts of weak acids. 1 fig.

Catalytic coal liquefaction process

DOEpatents

Garg, Diwakar; Sunder, Swaminathan

1986-01-01

An improved process for catalytic solvent refining or hydroliquefaction of non-anthracitic coal at elevated temperatures under hydrogen pressure in a solvent comprises using as catalyst a mixture of a 1,2- or 1,4-quinone and an alkaline compound, selected from ammonium, alkali metal, and alkaline earth metal oxides, hydroxides or salts of weak acids.

Dynamic restructuring drives catalytic activity on nanoporous gold–silver alloy catalysts

DOE PAGES

Zugic, Branko; Wang, Lucun; Heine, Christian; ...

2016-12-19

Bimetallic, nanostructured materials hold promise for improving catalyst activity and selectivity, yet little is known about the dynamic compositional and structural changes that these systems undergo during pretreatment that leads to efficient catalyst function. Here we use ozone-activated silver–gold alloys in the form of nanoporous gold as a case study to demonstrate the dynamic behaviour of bimetallic systems during activation to produce a functioning catalyst. We show that it is these dynamic changes that give rise to the observed catalytic activity. Advanced in situ electron microscopy and X-ray photoelectron spectroscopy are used to demonstrate that major restructuring and compositional changesmore » occur along the path to catalytic function for selective alcohol oxidation. Transient kinetic measurements correlate the restructuring to three types of oxygen on the surface. The direct influence of changes in surface silver concentration and restructuring at the nanoscale on oxidation activity is demonstrated. Finally, our results demonstrate that characterization of these dynamic changes is necessary to unlock the full potential of bimetallic catalytic materials.« less

Dynamic restructuring drives catalytic activity on nanoporous gold–silver alloy catalysts

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

Zugic, Branko; Wang, Lucun; Heine, Christian

Bimetallic, nanostructured materials hold promise for improving catalyst activity and selectivity, yet little is known about the dynamic compositional and structural changes that these systems undergo during pretreatment that leads to efficient catalyst function. Here we use ozone-activated silver–gold alloys in the form of nanoporous gold as a case study to demonstrate the dynamic behaviour of bimetallic systems during activation to produce a functioning catalyst. We show that it is these dynamic changes that give rise to the observed catalytic activity. Advanced in situ electron microscopy and X-ray photoelectron spectroscopy are used to demonstrate that major restructuring and compositional changesmore » occur along the path to catalytic function for selective alcohol oxidation. Transient kinetic measurements correlate the restructuring to three types of oxygen on the surface. The direct influence of changes in surface silver concentration and restructuring at the nanoscale on oxidation activity is demonstrated. Finally, our results demonstrate that characterization of these dynamic changes is necessary to unlock the full potential of bimetallic catalytic materials.« less

Catalytic hydrothermal pretreatment of corncob into xylose and furfural via solid acid catalyst.

PubMed

Li, Huiling; Deng, Aojie; Ren, Junli; Liu, Changyu; Lu, Qi; Zhong, Linjie; Peng, Feng; Sun, Runcang

2014-04-01

Selectively catalytic hydrothermal pretreatment of corncob into xylose and furfural has been developed in this work using solid acid catalyst (SO4(2-)/TiO2-ZrO2/La(3+)). The effects of corncob-to-water ratio, reaction temperature and residence time on the performance of catalytic hydrothermal pretreatment were investigated. Results showed that the solid residues contained mainly lignin and cellulose, which was indicative of the efficient removal of hemicelluloses from corncob by hydrothermal method. The prepared catalyst with high thermal stability and strong acid sites originated from the acid functional groups was confirmed to contribute to the hydrolysis of polysaccharides into monosaccharides followed by dehydration into furfural. Highest furfural yield (6.18 g/100g) could be obtained at 180°C for 120 min with 6.80 g/100g xylose yield when the corncob/water ratio of was 10:100. Therefore, selectively catalytic hydrothermal pretreatment of lignocellulosic biomass into important platform chemicals by solid acids is considered to be a potential treatment for biodiesel and chemical production. Copyright © 2014 Elsevier Ltd. All rights reserved.

Optimizing carbon efficiency of jet fuel range alkanes from cellulose co-fed with polyethylene via catalytically combined processes.

PubMed

Zhang, Xuesong; Lei, Hanwu; Zhu, Lei; Zhu, Xiaolu; Qian, Moriko; Yadavalli, Gayatri; Yan, Di; Wu, Joan; Chen, Shulin

2016-08-01

Enhanced carbon yields of renewable alkanes for jet fuels were obtained through the catalytic microwave-induced co-pyrolysis and hydrogenation process. The well-promoted ZSM-5 catalyst had high selectivity toward C8-C16 aromatic hydrocarbons. The raw organics with improved carbon yield (∼44%) were more principally lumped in the jet fuel range at the catalytic temperature of 375°C with the LDPE to cellulose (representing waste plastics to lignocellulose) mass ratio of 0.75. It was also observed that the four species of raw organics from the catalytic microwave co-pyrolysis were almost completely converted into saturated hydrocarbons; the hydrogenation process was conducted in the n-heptane medium by using home-made Raney Ni catalyst under a low-severity condition. The overall carbon yield (with regards to co-reactants of cellulose and LDPE) of hydrogenated organics that mostly match jet fuels was sustainably enhanced to above 39%. Meanwhile, ∼90% selectivity toward jet fuel range alkanes was attained. Copyright © 2016 Elsevier Ltd. All rights reserved.

Bottom-Up Catalytic Approach towards Nitrogen-Enriched Mesoporous Carbons/Sulfur Composites for Superior Li-S Cathodes

PubMed Central

Sun, Fugen; Wang, Jitong; Chen, Huichao; Qiao, Wenming; Ling, Licheng; Long, Donghui

2013-01-01

We demonstrate a sustainable and efficient approach to produce high performance sulfur/carbon composite cathodes via a bottom-up catalytic approach. The selective oxidation of H2S by a nitrogen-enriched mesoporous carbon catalyst can produce elemental sulfur as a by-product which in-situ deposit onto the carbon framework. Due to the metal-free catalytic characteristic and high catalytic selectivity, the resulting sulfur/carbon composites have almost no impurities that thus can be used as cathode materials with compromising battery performance. The layer-by-layer sulfur deposition allows atomic sulfur binding strongly with carbon framework, providing efficient immobilization of sulfur. The nitrogen atoms doped on the carbon framework can increase the surface interactions with polysulfides, leading to the improvement in the trapping of polysulfides. Thus, the composites exhibit a reversible capacity of 939 mAh g−1 after 100 cycles at 0.2 C and an excellent rate capability of 527 mAh g−1 at 5 C after 70 cycles. PMID:24084754

Remote carboxylation of halogenated aliphatic hydrocarbons with carbon dioxide

NASA Astrophysics Data System (ADS)

Juliá-Hernández, Francisco; Moragas, Toni; Cornella, Josep; Martin, Ruben

2017-05-01

Catalytic carbon-carbon bond formation has enabled the streamlining of synthetic routes when assembling complex molecules. It is particularly important when incorporating saturated hydrocarbons, which are common motifs in petrochemicals and biologically relevant molecules. However, cross-coupling methods that involve alkyl electrophiles result in catalytic bond formation only at specific and previously functionalized sites. Here we describe a catalytic method that is capable of promoting carboxylation reactions at remote and unfunctionalized aliphatic sites with carbon dioxide at atmospheric pressure. The reaction occurs via selective migration of the catalyst along the hydrocarbon side-chain with excellent regio- and chemoselectivity, representing a remarkable reactivity relay when compared with classical cross-coupling reactions. Our results demonstrate that site-selectivity can be switched and controlled, enabling the functionalization of less-reactive positions in the presence of a priori more reactive ones. Furthermore, we show that raw materials obtained in bulk from petroleum processing, such as alkanes and unrefined mixtures of olefins, can be used as substrates. This offers an opportunity to integrate a catalytic platform en route to valuable fatty acids by transforming petroleum-derived feedstocks directly.

Catalytic dehydration of ethanol using transition metal oxide catalysts.

PubMed

Zaki, T

2005-04-15

The aim of this work is to study catalytic ethanol dehydration using different prepared catalysts, which include Fe(2)O(3), Mn(2)O(3), and calcined physical mixtures of both ferric and manganese oxides with alumina and/or silica gel. The physicochemical properties of these catalysts were investigated via X-ray powder diffraction (XRD), acidity measurement, and nitrogen adsorption-desorption at -196 degrees C. The catalytic activities of such catalysts were tested through conversion of ethanol at 200-500 degrees C using a catalytic flow system operated under atmospheric pressure. The results obtained indicated that the dehydration reaction on the catalyst relies on surface acidity, whereas the ethylene production selectivity depends on the catalyst chemical constituents.

Direct catalytic cross-coupling of organolithium compounds

NASA Astrophysics Data System (ADS)

Giannerini, Massimo; Fañanás-Mastral, Martín; Feringa, Ben L.

2013-08-01

Catalytic carbon-carbon bond formation based on cross-coupling reactions plays a central role in the production of natural products, pharmaceuticals, agrochemicals and organic materials. Coupling reactions of a variety of organometallic reagents and organic halides have changed the face of modern synthetic chemistry. However, the high reactivity and poor selectivity of common organolithium reagents have largely prohibited their use as a viable partner in direct catalytic cross-coupling. Here we report that in the presence of a Pd-phosphine catalyst, a wide range of alkyl-, aryl- and heteroaryl-lithium reagents undergo selective cross-coupling with aryl- and alkenyl-bromides. The process proceeds quickly under mild conditions (room temperature) and avoids the notorious lithium halogen exchange and homocoupling. The preparation of key alkyl-, aryl- and heterobiaryl intermediates reported here highlights the potential of these cross-coupling reactions for medicinal chemistry and material science.

PdNP Decoration of Halloysite Lumen via Selective Grafting of Ionic Liquid onto the Aluminol Surfaces and Catalytic Application.

PubMed

Dedzo, Gustave K; Ngnie, Gaëlle; Detellier, Christian

2016-02-01

The synthesis of selectively deposited palladium nanoparticles (PdNPs) inside tubular halloysite lumens is reported. This specific localization was directed by the selective modification of the aluminol surfaces of the clay mineral through stable Al-O-C bonds. An ionic liquid (1-(2-hydroxyethyl)-3-methylimidazolium) was grafted onto halloysite following the guest displacement method (generally used for kaolinite) using halloysite-DMSO preintercalate. The characterization of this clay nanohybrid material (XRD, NMR, TGA) showed characteristics reminiscent of similar materials synthesized from kaolinite. The grafting on halloysite lumens was also effective without using the DMSO preintercalate. The presence of these new functionalities in halloysite directs the synthesis of uniform PdNPs with size ranging between 3 and 6 nm located exclusively in the lumens. This results from the selective adsorption of PdNPs precursors in functionalized lumens through an anion exchange mechanism followed by in situ reduction. In contrast, the unmodified clay mineral displayed nanoparticles both inside and outside the tubes. These catalysts showed significant catalytic activity for the reduction of 4-nitrophenol (4-NP). The most efficient catalysts were recycled up to three times without reducing significantly the catalytic activities.

The protein cofactor allows the sequence of an RNase P ribozyme to diversify by maintaining the catalytically active structure of the enzyme.

PubMed Central

Kim, J J; Kilani, A F; Zhan, X; Altman, S; Liu, F

1997-01-01

To study the effect proteins have on the catalysis and evolution of RNA enzymes, we simulated evolution of RNase P catalytic M1 RNA in vitro, in the presence and absence of its C5 protein cofactor. In the presence of C5, functional M1 sequence variants (not catalytically active in the absence of C5) were selected in addition to those identical to M1. C5 maintains the catalytically active structure of the variants and allows for an enhanced spectrum of M1 molecules to function in the context of a ribonucleoprotein (RNP) complex. The generation of an RNP enzyme, requiring both RNA and protein components, from a catalytically active RNA molecule has implications for how modern RNP complexes evolved from ancestral RNAs. PMID:9174096

Method and apparatus for determining weldability of thin sheet metal

DOEpatents

Goodwin, Gene M.; Hudson, Joseph D.

1988-01-01

A fixture is provided for testing thin sheet metal specimens to evaluate hot-cracking sensitivity for determining metal weldability on a heat-to-heat basis or through varying welding parameters. A test specimen is stressed in a first direction with a load selectively adjustable over a wide range and then a weldment is passed along over the specimen in a direction transverse to the direction of strain to evaluate the hot-cracking characteristics of the sheet metal which are indicative of the weldability of the metal. The fixture provides evaluations of hot-cracking sensitivity for determining metal weldability in a highly reproducible manner with minimum human error.

Elevated temperature crack growth

NASA Technical Reports Server (NTRS)

Yau, J. F.; Malik, S. N.; Kim, K. S.; Vanstone, R. H.; Laflen, J. H.

1985-01-01

The objective of the Elevated Temperature Crack Growth Project is to evaluate proposed nonlinear fracture mechanics methods for application to combustor liners of aircraft gas turbine engines. During the first year of this program, proposed path-independent (P-I) integrals were reviewed for such applications. Several P-I integrals were implemented into a finite-element postprocessor which was developed and verified as part of the work. Alloy 718 was selected as the analog material for use in the forthcoming experimental work. A buttonhead, single-edge notch specimen was designed and verified for use in elevated-temperature strain control testing with significant inelastic strains. A crack mouth opening displacement measurement device was developed for further use.

Analysis of a hybrid-undirectional buffer strip laminate

NASA Technical Reports Server (NTRS)

Dharani, L. R.; Goree, J. G.

1983-01-01

A method of analysis capable of predicting accurately the fracture behavior of a unidirectional composite laminate containing symmetrically placed buffer strips is presented. As an example, for a damaged graphite/epoxy laminate, the results demonstrate the manner in which to select the most efficient combination of buffer strip properties necessary to inhibit crack growth. Ultimate failure of the laminate after the arrest can occur under increasing load either by continued crack extension through the buffer strips or the crack can jump the buffer strips. For some typical hybrid materials it is found that a buffer strip spacing to width ratio of about four to one is the most efficient.