Method for removing acid gases from a gaseous stream

DOEpatents

Gorin, Everett; Zielke, Clyde W.

1981-01-01

In a process for hydrocracking a heavy aromatic polynuclear carbonaceous feedstock containing reactive alkaline constituents to produce liquid hydrocarbon fuels boiling below about 475.degree. C. at atmospheric pressure by contacting the feedstock with hydrogen in the presence of a molten metal halide catalyst, thereafter separating a gaseous stream containing hydrogen, at least a portion of the hydrocarbon fuels and acid gases from the molten metal halide and regenerating the molten metal halide, thereby producing a purified molten metal halide stream for recycle to the hydrocracking zone, an improvement comprising; contacting the gaseous acid gas, hydrogen and hydrocarbon fuels-containing stream with the feedstock containing reactive alkaline constituents to remove acid gases from the acid gas containing stream. Optionally at least a portion of the hydrocarbon fuels are separated from gaseous stream containing hydrogen, hydrocarbon fuels and acid gases prior to contacting the gaseous stream with the feedstock.

Synthesis of H/Bentonite and Ni/Al2O3-bentonite and its application to produce biogasoline from nyamplung seed (Calophyllum inophillum Linn) oil by catalytic hydrocracking

NASA Astrophysics Data System (ADS)

Marini, A. T.; Wijaya, K.; Sasongko, N. A.

2018-03-01

Hydrocracking process of Nyamplung (Calophyllum inophillum Linn) seed oil to produce biogasoline using H/bentonite and Ni/Al2O3-bentonite that pillared by Al2O3 as catalyst had been conducted. Bentonite was activated by acidification using HF 1% and H2SO4 0.5 M. Ni metal was impregnated into bentonite with two steps reaction; therewas intercalation with Al2O3kegging ion and Ni metal impregnation using NiCl2 metal salt. Catalysts were characterized by infrared spectrophotometer (FTIR), X-ray diffraction (XRD), X-ray fluorescence (XRF), BET, TEM and ammonia adsorption. Hydrocracking reaction was variated by Ni/Al2O3-bentonite and H/bentonite with ratio catalyst/oil 1:100. Biocrude was prepared by extraction by using ethanol 96%. Hydrocracking oil products were further analyzed by GC-MS. The results show that the acidity of bentonite by activation using HF 1% and H2SO4 0.5 M has been increased from 62.58 to 64.62 mmol/g. Impregnation process also increased the acidity of bentonite from 62.58 to 64.89 mmol/g. Activation using HF 1% and H2SO4 0.5 M, intercalation by Al2O3 and impregnation by Ni metal were increasing the crystallinity, surface area, total volume pore and average pore size of bentonite. These techniques were also causeddealumination of bentonite. The hydrocracking process successfully synthesized hydrocarbons with a number of carbon chain between C5-C20 which include bio-gasoline group compounds. Moreover, catalytic processes by H/bentonite and Ni/Al2O3-bentonite also successfully produced 39.83% and 60.37% of biogasoline yields, respectively.

Reactor apparatus

DOEpatents

Echtler, J. Paul

1981-01-01

A reactor apparatus for hydrocracking a polynuclear aromatic hydrocarbonaceous feedstock to produce lighter hydrocarbon fuels by contacting the hydrocarbonaceous feedstock with hydrogen in the presence of a molten metal halide catalyst.

Novel bimetallic dispersed catalysts for temperature-programmed coal liquefaction

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

Chunshan, Song; Kirby, S.; Schmidt, E.

1995-12-31

The objective of this project is to explore bimetallic dispersed catalysts for more efficient coal liquefaction. Coal liquefaction involves cleavage of methylene, dimethylene and ether bridges connecting various aromatic units and the reactions of various oxygen functional groups. This paper describes recent results on (1) hydrodeoxygenation of O-containing polycyclic model compounds using novel organometallic catalyst precursors; and (2) activity and selectivity of dispersed Fe catalysts from organometallic and inorganic precursors for hydrocracking of 4-(1-naphthylmethyl) bibenzyl. The results showed that some iron containing catalysts have higher activity in the sulfur-free form, contrary to conventional wisdom. Adding sulfur to Fe precursors withmore » Cp-ligands decreased the activity of the resulting catalyst. This is in distinct contrast to the cases with iron pentacarbonyl and superfine Fe{sub 2}O{sub 3}, where S addition increased their catalytic activity substantially. A positive correlation between sulfur addition and increased activity can be seen, but a reversed trend between Fe cluster size and hydrocracking conversion could be observed, for carbonyl-type Fe precursors. It is apparent that the activity and selectivity of Fe catalysts for NMBB conversion depends strongly on both the type of ligand environment, the oxidation state and the number of intermetal bonds in the molecular precursor.« less

Process for upgrading wax from Fischer-Tropsch synthesis

DOEpatents

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

1987-01-01

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

Regeneration of zinc chloride hydrocracking catalyst

DOEpatents

Zielke, Clyde W.

1979-01-01

Improved rate of recovery of zinc values from the solids which are carried over by the effluent vapors from the oxidative vapor phase regeneration of spent zinc chloride catalyst is achieved by treatment of the solids with both hydrogen chloride and calcium chloride to selectively and rapidly recover the zinc values as zinc chloride.

Influence of Solvent on Liquid Phase Hydrodeoxygenation of Furfural-Acetone Condensation Adduct using Ni/Al2O3-ZrO2 Catalysts

NASA Astrophysics Data System (ADS)

Ulfa, S. M.; Mahfud, A.; Nabilah, S.; Rahman, M. F.

2017-02-01

Influence of water and acidic protic solvent on hydrodeoxygenation (HDO) of the furfural-acetone adduct (FAA) over Ni/Al2O3-ZrO2 (NiAZ) catalysts were investigated. The HDO of FAA was carried out in a batch reactor at 150°C for 8 hours. The NiAZ catalysts were home-made catalysts which were prepared by wet impregnation method with 10 and 20% nickel loading. The HDO reaction of FAA using 10NiAZ in water at 150°C gave alkane and oxygenated hydrocarbons at 31.41% with selectivity over tridecane (C13) in 6.67%. On the other hand, a reaction using acetic acid:water (1:19 v/v) in similar reaction condition gave only oxygenated compounds and hydrocracking product (C8-C10). The formation of tridecane (C13) was proposed by hydrogenation of C=O and C=C followed by decarboxylation without hydrocracking process. The presence of water facilitated decarboxylation mechanism by stabilized dehydrogenated derivatives of FAA.

In situ {sup 13}C MAS NMR study of n-hexane conversion on Pt and Pd supported on basic materials. II. On the mechanism of isomerization and hydrocracking

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

Ivanova, I.I.; Seirvert, M.; Pasau-Claerbout, A.

{sup 13}C MAS NMR spectroscopy was performed in situ to investigate the mechanisms of n-hexane isomerization and hydrocracking on Pt and Pd supported on Al-stabilized magnesia (Pt/Mg(Al)O and Pd/Mg(Al)O), and Pt on KL zeolite (Pt/KL). All the catalysts had high metal dispersion, the metal particle sizes being 13, 11, and 18 {Angstrom}, respectively. n-Hexane 1-{sup 13}C was used for in situ label tracer experiments. {sup 13}C MAS NMR spectra were obtained during the time course of the reaction at 573 and 653 K. The NMR results were then quantified, and the reaction kinetics were studied. Identification of the primary andmore » secondary labeled reaction products led to the conclusion that both cyclic and bond-shift isomerization mechanisms operate on the three catalysts. In the case of Pt/Mg(Al)O, the cyclic mechanism accounts for 80% of the isomerization products. In the case of Pt/KL and Pd/Mg(Al)O, the contribution of bond-shift reactions increases due to restricted formation of the methylcyclopentane intermediate on the former and to suppressed hydrogenolysis of methylcyclopentane on the latter. A nonselective cyclic isomerization mechanism operates on magnesia catalysts, while on Pt/KL selective bisecondary bond rupturing occurs. Mechanistic pathways of bond-shift and hydrocracking reactions involve both 1,3- and 2,4-metallocyclobutane intermediates in the case of magnesia-supported catalysts, while in the case of the Pt/KL catalyst a 1,3-metallocyclobutane intermediate is preferentially formed. Only terminal scission occurs on Pt/KL. The Pd catalyst demonstrates enhanced activity in demethylation. The observed differences in the mechanistic pathways are explained on the basis of the specific properties of the metal and support. 64 refs., 14 figs., 6 tabs.« less

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.

Low-pressure hydrocracking of coal-derived Fischer-Tropsch waxes to diesel

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

Dieter Leckel

2007-06-15

Coal-derived low-temperature Fischer-Tropsch (LTFT) wax was hydrocracked at pressures of 3.5-7.0 MPa using silica-alumina-supported sulfided NiW/NiMo and an unsulfided noble metal catalyst, modified with MoO{sub 3}. A low-pressure operation at 3.5 MPa produced a highly isomerized diesel, having low cloud points (from -12 to -28{sup o}C) combined with high cetane numbers (69-73). These properties together with the extremely low sulfur ({lt}5 ppm) and aromatic ({lt}0.5%) contents place coal/liquid (CTL) derived distillates as highly valuable blending components to achieve Eurograde diesel specifications. The upgrading of coal-based LTFT waxes through hydrocracking to high-quality diesel fuel blend components in combination with commercial-feasible coal-integratedmore » gasification combined cycle (coal-IGCC) CO{sub 2} capture and storage schemes should make CTL technology more attractive. 28 refs., 7 figs., 8 tabs.« less

Determination of heavy polycyclic aromatic hydrocarbons by non-aqueous reversed phase liquid chromatography: Application and limitation in refining streams.

PubMed

Panda, Saroj K; Muller, Hendrik; Al-Qunaysi, Thunayyan A; Koseoglu, Omer R

2018-01-19

The heavy polycyclic aromatic hydrocarbons (HPAHs) cause detrimental effects to hydrocracker operations by deactivating the catalysts and depositing in the downstream of the reactor/ exchangers. Therefore, it is essential to continuously monitor the accumulation of HPAHs in a hydrocracker unit. To accurately measure the concentration of HPAHs, the development of a fast and reliable analytical method is inevitable. In this work, an analytical method based on non-aqueous reversed phase chromatography in combination with high resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) was developed. As a first step, five different types of stationary phases were evaluated for the separation of HPAHs in non-aqueous mode and the best suited phase was further used for the fractionation of HPAHs in a fractionator bottom sample obtained from a refinery hydrocracker unit. The eight major fractions or peaks obtained from the separation were further characterized by UV spectroscopy and FT-ICR MS and the compounds in the fractions were tentatively confirmed as benzoperylene, coronene, methylcoronene, naphthenocoronene, benzocoronene, dibenzoperylene, naphthocoronene and ovalene. The developed liquid chromatography method can be easily adapted in a refinery laboratory for the quantitation of HPAHs in hydrocracking products. The method was further tested to check the interference of sulfur aromatics and/or large alkylated aromatic hydrocarbons on the determination of HPAHs in hydrocracking products. Copyright © 2017 Elsevier B.V. All rights reserved.

Preparation and characterization of NiW-nHA composite catalyst for hydrocracking

NASA Astrophysics Data System (ADS)

Zhou, Gang; Hou, Yongzhao; Liu, Lei; Liu, Hongru; Liu, Can; Liu, Jing; Qiao, Huiting; Liu, Wenyong; Fan, Yubo; Shen, Shituan; Rong, Long

2012-11-01

The synthesis, characterization and catalytic capability of the NiW-nano-hydroxyapatite (NiW-nHA) composite were investigated in this paper. The NiW-nHA catalyst was prepared by a co-precipitation method. Then Fourier transform infrared (FT-IR) spectroscopy, transmission electron microscopy (TEM), X-ray diffraction (XRD) and energy dispersive spectroscopy (EDX) were used to analyze this material. In addition, the catalytic capacity of the NiW-nHA composite was also examined by FT-IR and gas chromatography (GC). The results of FT-IR analysis indicated that Ni, W and nHA combined closely. TEM observation revealed that this catalyst was needle shaped and the crystal retained a nanometer size. XRD data also suggested that a new phase of CaWO4 appeared and the lattice parameters of nHA changed in this system. nHA was the carrier of metals. The rates of Ni/W-loading were 73.24% and 65.99% according to the EDX data, respectively. Furthermore, the conversion of 91.88% Jatropha oil was achieved at 360 °C and 3 MPa h-1 over NiW-nHA catalyst. The straight chain alkanes ranging from C15 to C18 were the main components in the production. The yield of C15-C18 alkanes was up to 83.56 wt%. The reaction pathway involved hydrocracking of the C&z.dbd;C bonds of these triglycerides from Jatropha oil. This paper developed a novel non-sulfided catalyst to obtain a ``green biofuel'' from vegetable oil.

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

NASA Astrophysics Data System (ADS)

Savitri, Effendi, R.; Tursiloadi, S.

2016-02-01

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

Separation of catalyst from Fischer-Tropsch slurry

DOEpatents

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

1998-10-27

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

Pillared montmorillonite catalysts for coal liquefaction

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

Sharma, R.K.; Olson, E.S.

1994-12-31

Pillared clays contain large micropores and have considerable potential for catalytic hydrogenation and cleavage of coal macromolecules. Pillared montmorillonite-supported catalysts were prepared by the intercalation of polynuclear hydroxychromium cations and subsequent impregnation of nickel and molybdenum. Infrared and thermogravimetric studies of pyridine-adsorbed catalysts indicated the presence of both Lewis and Bronsted acid sites. Thus, the catalysts have both acidic properties that can aid in hydrocracking and cleavage of carbon-heteroatom bonds as well as hydrogen-activating bimetallic sites. These catalysts were applied to the hydrodesulfurization and liquefaction of coal-derived intermediates. The reactions of model organosulfur compounds and coal liquids were carried outmore » at 300{degrees}-400{degrees}C for 3 hours in the presence of 1000 psi of molecular hydrogen. Reaction products were analyzed by GC/FT-IR/MS/AED. The catalysts have been found to be very effective in removing sulfur from model compounds as well as liquefaction products.« less

Separation of catalyst from Fischer-Tropsch slurry

DOEpatents

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

1998-10-27

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

Demetallation and hydrocracking of Arab heavy 650{degrees}F{sup +} resid over CoMo/carbon supported catalysts

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

Rankel, L.A.

1993-12-31

Arab Heavy 650{degrees}F{sup +} atmospheric resid has been hydroprocessed over different CoMo/activated carbon catalysts and the results compared to processing with a conventional CoMo/alumina catalyst. Demetallation activity for the activated carbon catalysts depends on the activated carbon chosen as well as the way the Co and Mo metals are applied to the carbon. Hydroprocessing Arab Heavy 650{degrees}F{sup +} resid at 1500 psig showed that 87% demetallation over CoMo/Darco activated carbon was produced vs {approximately}73% demetallation over CoMo/alumina at about the same 1000{degrees}F conversion with 200-400 SCF/BBL less H-consumption. Desulfurization activity and CCR conversion were 10-20% higher for CoMo/alumina vs CoMo/Darcomore » activated carbon, consistent with higher H-consumption. Potential advantages for resid processing over carbon supported catalysts induce high levels of demetallation, reduced costs for carbon vs alumina, and easy recovery of metals by catalysts combustion.« less

Conversion of crop seed oils to jet fuel and associated methods

DOEpatents

Ginosar, Daniel M.; Petkovic, Lucia M.; Thompson, David N.

2010-05-18

Aspects of the invention include methods to produce jet fuel from biological oil sources. The method may be comprised of two steps: hydrocracking and reforming. The process may be self-sufficient in heat and hydrogen.

Hydrocracking of Jatropha Oil over non-sulfided PTA-NiMo/ZSM-5 Catalyst

PubMed Central

Yang, Xiaosong; Liu, Jing; Fan, Kai; Rong, Long

2017-01-01

The PTA-NiMo/ZSM-5 catalyst impregnated with phosphotungstic acid (PTA) was designed for the transformation of Jatropha oil into benzene, toluene, and xylenes (BTX) aromatics. The produced catalyst was characterized by N2 adsorption-desorption, powder X-ray diffraction (XRD), Fourier transform infrared (FT-IR), X-ray photoelectron spectroscopy (XPS), and the temperature-programmed desorption of ammonia (NH3-TPD). The catalytic performance was evaluated by gas chromatography (GC). The liquid products were 70 wt% of the feed oil, and the majority of the liquid products were BTX. The aromatization activity of the catalyst was improved by the addition of PTA and the hierarchical process. The favorable PTA amount was 20 wt% and the yield of BTX was 59 wt% at 380 °C, 3 MPa, H2/oil (v/v) = 1000 and LHSV = 1 h−1 over the PTA20-NiMo/HZ0.5 catalyst (PTA 20 wt%) without sulfurization. PMID:28134313

Platinum-mordenite catalysts for n-Hexane isomerization: Characterization by X-ray absorption spectroscopy and chemical probes

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

Otten, M.M.; Clayton, M.J.; Lamb, H.H.

Platinum-mordenite (Pt-MOR) catalysts were prepared from NH{sub 4}-MOR by ion exchange with (Pt{sup II}(NH{sub 3}){sub 4})(OH){sub 2}, calcination in O{sub 2} at 350{degrees}C, and reduction in H{sub 2} at 350{degrees}C. The resultant Pt-H-MOR was active for n-hexane isomerization and hydrocracking via bifunctional catalysis at 240-300{degrees}C and 1 atm. The observed activation energies for C{sub 6} branched-isomer formation are unusually low, suggesting that the isomerization rates were controlled by pore diffusion. A Pt-KH-MOR catalyst was prepared by ion exchange with aqueous KNO{sub 3} and re-reduction at 350{degrees}C; elemental analysis evidenced 90% exchange of protons for K{sup +} ions. The product distributionmore » and observed activation energies for C{sub 6} branched-isomer formation over Pt-KH-MOR are consistent with n-hexane isomerization via bifunctional catalysis. Hydrocracking was strongly suppressed, and light hydrocarbons were formed primarily by Pt-catalyzed hydrogenolysis. From in-situ extended X-ray absorption fine structure spectroscopy and H{sub 2} temperature-programmed desorption, we conclude that the Pt-MOR catalysts consist of small Pt clusters hosted within the mordenite crystals. The PtL{sub III}X-ray absorption near-edge structure (XANES) spectra of Pt-H-MOR and Pt-KH-MOR are closely similar, suggesting that the electronic structure of the Pt clusters is unaffected by mordenite acid-base chemistry. The infrared spectrum of CO adsorbed on Pt-H-MOR contains an intense band at 2084 cm{sup -1}, which is assigned to linear CO moieties on Pt clusters. The infrared spectrum of CO adsorbed on Pt-KH-MOR evidences a red shift of the linear CO band, which the authors suggest is due to electrostatic interactions between carbonyl O atoms and nearby K{sup +} ions. 45 refs., 9 figs., 6 tabs.« less

Synthesis of Mesoporous α-Fe2O3 Nanoparticles by Non-ionic Soft Template and Their Applications to Heavy Oil Upgrading

NASA Astrophysics Data System (ADS)

Park, Chulwoo; Jung, Jinhwan; Lee, Chul Wee; Cho, Joungmo

2016-12-01

This paper reports the synthetic route of 3-D network shape α-Fe2O3 from aqueous solutions of iron precursor using a non-ionic polymeric soft-template, Pluronic P123. During the synthesis of α-Fe2O3, particle sizes, crystal phases and morphologies were significantly influenced by pH, concentrations of precursor and template. The unique shape of worm-like hematite was obtained only when a starting solution was prepared by a weakly basic pH condition and a very specific composition of constituents. The synthesized nanocrystal at this condition had a narrow pore size distribution and high surface area compared to the bulk α-Fe2O3 or the one synthesized from lower pH conditions. The hydrocracking performance was tested over the synthesized iron oxide catalysts with different morphologies. The worm-like shape of iron oxide showed a superior performance, including overall yield of liquid fuel product and coke formation, over the hydrocracking of heavy petroleum oil.

Synthesis of Mesoporous α-Fe2O3 Nanoparticles by Non-ionic Soft Template and Their Applications to Heavy Oil Upgrading

PubMed Central

Park, Chulwoo; Jung, Jinhwan; Lee, Chul Wee; Cho, Joungmo

2016-01-01

This paper reports the synthetic route of 3-D network shape α-Fe2O3 from aqueous solutions of iron precursor using a non-ionic polymeric soft-template, Pluronic P123. During the synthesis of α-Fe2O3, particle sizes, crystal phases and morphologies were significantly influenced by pH, concentrations of precursor and template. The unique shape of worm-like hematite was obtained only when a starting solution was prepared by a weakly basic pH condition and a very specific composition of constituents. The synthesized nanocrystal at this condition had a narrow pore size distribution and high surface area compared to the bulk α-Fe2O3 or the one synthesized from lower pH conditions. The hydrocracking performance was tested over the synthesized iron oxide catalysts with different morphologies. The worm-like shape of iron oxide showed a superior performance, including overall yield of liquid fuel product and coke formation, over the hydrocracking of heavy petroleum oil. PMID:27966663

Synthesis of Mesoporous α-Fe2O3 Nanoparticles by Non-ionic Soft Template and Their Applications to Heavy Oil Upgrading.

PubMed

Park, Chulwoo; Jung, Jinhwan; Lee, Chul Wee; Cho, Joungmo

2016-12-14

This paper reports the synthetic route of 3-D network shape α-Fe 2 O 3 from aqueous solutions of iron precursor using a non-ionic polymeric soft-template, Pluronic P123. During the synthesis of α-Fe 2 O 3 , particle sizes, crystal phases and morphologies were significantly influenced by pH, concentrations of precursor and template. The unique shape of worm-like hematite was obtained only when a starting solution was prepared by a weakly basic pH condition and a very specific composition of constituents. The synthesized nanocrystal at this condition had a narrow pore size distribution and high surface area compared to the bulk α-Fe 2 O 3 or the one synthesized from lower pH conditions. The hydrocracking performance was tested over the synthesized iron oxide catalysts with different morphologies. The worm-like shape of iron oxide showed a superior performance, including overall yield of liquid fuel product and coke formation, over the hydrocracking of heavy petroleum oil.

Coal liquefaction process

DOEpatents

Skinner, Ronald W.; Tao, John C.; Znaimer, Samuel

1985-01-01

This invention relates to an improved process for the production of liquid carbonaceous fuels and solvents from carbonaceous solid fuels, especially coal. The claimed improved process includes the hydrocracking of the light SRC mixed with a suitable hydrocracker solvent. The recycle of the resulting hydrocracked product, after separation and distillation, is used to produce a solvent for the hydrocracking of the light solvent refined coal.

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

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

PubMed

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

2015-11-01

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

An investigation into the effects of different existing states of aluminum isopropoxide on copper-based catalysts for direct synthesis of dimethyl ether from syngas

NASA Astrophysics Data System (ADS)

Sun, Kai; Wang, Peng; Bian, Zhongkai; Huang, Wei

2018-01-01

Aluminum isopropoxide (AIP) is a vital raw material to produce high surface area alumina catalyst, which is used for catalytic applications, such as hydrocracking, Fischer-Tropsch and STD (syngas to dimethyl ether) reactions. However, the different existing states have an effect on hydrolysis and condensation in the process of precursor preparation. The Cu/Zn/Al slurry catalysts were prepared by aluminum isopropoxide, which were liquid state, crystalline state and solid state, utilizing a complete liquid phase preparation technology. In the dimethyl ether (DME) synthesis reaction, the aluminum resource of crystalline state was prepared for slurry catalyst, which presented high CO conversion and DME selectivity of 54.32% and 69.74%, respectively. Characterization results indicated that different forms of AIP have the variant coordination numbers of Al-O and polymerization degrees, and the catalyst prepared by crystalline state consists amount of tetra-coordinated Al and few hexa-coordinated Al, which can exert different hydrolysis and condensation process compared with other aluminum sources, and finally it contributes to the strong interaction between active site copper species and Zn/Al species, confirming more Cu+ is responsible for the synthesis of DME in the slurry reactor.

Process for conversion of lignin to reformulated hydrocarbon gasoline

DOEpatents

Shabtai, Joseph S.; Zmierczak, Wlodzimierz W.; Chornet, Esteban

1999-09-28

A process for converting lignin into high-quality reformulated hydrocarbon gasoline compositions in high yields is disclosed. The process is a two-stage, catalytic reaction process that produces a reformulated hydrocarbon gasoline product with a controlled amount of aromatics. In the first stage, a lignin material is subjected to a base-catalyzed depolymerization reaction in the presence of a supercritical alcohol as a reaction medium, to thereby produce a depolymerized lignin product. In the second stage, the depolymerized lignin product is subjected to a sequential two-step hydroprocessing reaction to produce a reformulated hydrocarbon gasoline product. In the first hydroprocessing step, the depolymerized lignin is contacted with a hydrodeoxygenation catalyst to produce a hydrodeoxygenated intermediate product. In the second hydroprocessing step, the hydrodeoxygenated intermediate product is contacted with a hydrocracking/ring hydrogenation catalyst to produce the reformulated hydrocarbon gasoline product which includes various desirable naphthenic and paraffinic compounds.

Oil from hydrocracking as a raw material for the production of white oils

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

Potanina, V.A.; Dremova, T.I.; Ponomareva, T.P.

1984-01-01

This article investigates the feasibility of using distillate oil from hydrocracking for white oil production. A process technology has been developed in the USSR for the manufacture of high-quality oils by hydrocracking a heavy distillate feed in high-pressure equipment. The neutral and hydrocracked oil sample and a blend of these stocks were subjected to treatment with oleum, neutralization with 65% ethyl alcohol, and contact finishing to obtain white oils. The physicochemical properties of the white oils are given. It is determined that the hydrocracked oil can be used as the raw material in manufacturing perfume oil meeting the standard GOSTmore » 4225-76, and that the blends can be used to obtain pharmaceutical white oil meeting the standard GOST 3164-78.« less

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

PubMed

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

2017-01-25

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

Catalyst for microelectromechanical systems microreactors

DOEpatents

Morse, Jeffrey D [Martinez, CA; Sopchak, David A [Livermore, CA; Upadhye, Ravindra S [Pleasanton, CA; Reynolds, John G [San Ramon, CA; Satcher, Joseph H [Patterson, CA; Gash, Alex E [Brentwood, CA

2010-06-29

A microreactor comprising a silicon wafer, a multiplicity of microchannels in the silicon wafer, and a catalyst coating the microchannels. In one embodiment the catalyst coating the microchannels comprises a nanostructured material. In another embodiment the catalyst coating the microchannels comprises an aerogel. In another embodiment the catalyst coating the microchannels comprises a solgel. In another embodiment the catalyst coating the microchannels comprises carbon nanotubes.

Catalyst for microelectromechanical systems microreactors

DOEpatents

Morse, Jeffrey D [Martinez, CA; Sopchak, David A [Livermore, CA; Upadhye, Ravindra S [Pleasanton, CA; Reynolds, John G [San Ramon, CA; Satcher, Joseph H [Patterson, CA; Gash, Alex E [Brentwood, CA

2011-11-15

A microreactor comprising a silicon wafer, a multiplicity of microchannels in the silicon wafer, and a catalyst coating the microchannels. In one embodiment the catalyst coating the microchannels comprises a nanostructured material. In another embodiment the catalyst coating the microchannels comprises an aerogel. In another embodiment the catalyst coating the microchannels comprises a solgel. In another embodiment the catalyst coating the microchannels comprises carbon nanotubes.

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

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

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

1994-12-31

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

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.

Effect of oxygen compounds addition on the hydrocracking of coal derived liquid

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

Sato, Yoshiki; Kodera, Yoichi; Kamo, Tohru

1998-12-31

Coal derived liquid from liquefaction, coking and low temperature pyrolysis contains considerable amounts of alkylphenols with alkylbenzenes and alkylnaphthalenes. To produce and purify useful chemicals from coal-derived liquid, hydrocracking and hydrotreating of alkylphenol mixture is a very important process. In this study the effects of oxygen compounds such as dimethylcarbonate (DMC) addition on the hydrocracking of alkylphenols and coal-derived liquid were investigated to decrease hydrogen consumption due to the production of water from the removal of OH group. From the hydrocracking of 3,5-dimethylphenol (3,5-DMP) without DMC at 700 C, residence time of 3--10 sec under hydrogen-to-reactant molar ratio of moremore » than 10 using atmospheric flow apparatus with quartz reactor, m-xylene and m-cresol were produced with the production ratio of 1:1.8. However the dehydroxylation to produce m-xylene was decreased by the addition of 10% DMC with the 50% increased production ratio of 1:2.7. These are considered due to the strong interaction between OH group and DMC. Similar reaction behavior was observed in the hydrocracking of 2,5-DMP and the production ratio of (o-cresol + m-cresol)/p-xylene slightly increased from 3.0 to 3.5 by the addition of DMC. On the other hand, the products distribution did not change with and without DMC in the case of 2,6-DMP. This indicates the interaction is hindered by steric effect by the neighboring CH{sub 3} group. The effect of other oxygen compounds on the hydrocracking and the products distribution from the hydrocracking of coal-derived liquids is also discussed.« less

Calcium and lanthanum solid base catalysts for transesterification

DOEpatents

Ng, K. Y. Simon; Yan, Shuli; Salley, Steven O.

2015-07-28

In one aspect, a heterogeneous catalyst comprises calcium hydroxide and lanthanum hydroxide, wherein the catalyst has a specific surface area of more than about 10 m.sup.2/g. In another aspect, a heterogeneous catalyst comprises a calcium compound and a lanthanum compound, wherein the catalyst has a specific surface area of more than about 10 m.sup.2/g, and a total basicity of about 13.6 mmol/g. In further another aspect, a heterogeneous catalyst comprises calcium oxide and lanthanum oxide, wherein the catalyst has a specific surface area of more than about 10 m.sup.2/g. In still another aspect, a process for preparing a catalyst comprises introducing a base precipitant, a neutral precipitant, and an acid precipitant to a solution comprising a first metal ion and a second metal ion to form a precipitate. The process further comprises calcining the precipitate to provide the catalyst.

Catalyseur d'hydrocraquage à base de sulfure de NiMo déposé sur une zéolithe HEMT modifiée

NASA Astrophysics Data System (ADS)

Baalala, M.; Becue, T.; Leglise, J.; Manoli, J. M.; van Gestel, J. N. M.; Lamotte, J.; Bensitel, M.; Goupil, J. M.; Cornet, D.

1999-02-01

Treating a NH4EMT zeolite with a solution of (NH4)2SiF6 at 80 °C affords a solid containing amorphous SiO2 intimately mixed with the zeolite. This acidic support EMT-Si was loaded with NiMo sulfide in order to prepare a bifunctional catalyst, which was tested for the hydrogenation of benzene and the hydrocracking of n-heptane. This NiMo/EMT-Si catalyst was found more active for hydrogenation than the analogous NiMo/HY. This is ascribed to a higher dispersion of the NiMo sulfide, which is almost equally shared between the internal mesopores in the modified EMT solid, and the fissures, which were created throughout the zeolite grains upon inserting the NiMo sulfide. The catalyst with the EMT-Si support was also found more active than the NiMo/HY for the hydrocracking of heptane, with a slightly higher selectivity into heptane isomers. Le traitement d'une zéolithe NH4EMT par une solution de (NH4)2SiF6 fournit un solide comportant une phase SiO2 amorphe intimement mélangée aux parties intactes de la zéolithe. Sur ce support acide EMT-Si, on a greffé un sulfure de NiMo afin de préparer un catalyseur bifonctionnel qui a été testé dans les réactions d'hydrogénation du benzène et d'hydrocraquage du n-heptane. Ce catalyseur NiMo/EMT-Si s'avère plus actif en hydrogénation que son analogue NiMo/HY, en raison d'une meilleure dispersion du sulfure de NiMo. Sur le solide EMT modifié, le sulfure se répartit à peu près également entre les mésopores internes et les fissures crées dans les grains de zéolithe lors de l'insertion du sulfure de NiMo. Au contraire sur le support Y, une partie du sulfure est externe aux grains de zéolithe et inactive en catalyse. Le catalyseur NiMo/EMT-Si est aussi trouvé plus actif que le NiMo/HY en hydrocraquage du n-heptane, et un peu plus sélectif en isomères.

Bio-aviation fuel production from hydroprocessing castor oil promoted by the nickel-based bifunctional catalysts.

PubMed

Liu, Siyang; Zhu, Qingqing; Guan, Qingxin; He, Liangnian; Li, Wei

2015-05-01

Bio-aviation fuel was firstly synthesized by hydroprocessing castor oil in a continuous-flow fixed-bed microreactor with the main objective to obtain the high yield of aviation fuel and determine the elemental compositions of the product phases as well as the reaction mechanism. Highest aviation range alkane yields (91.6 wt%) were achieved with high isomer/n-alkane ratio (i/n) 4.4-7.2 over Ni supported on acidic zeolites. In addition, different fuel range alkanes can be obtained by adjusting the degree of hydrodeoxygenation (HDO) and hydrocracking. And the observations are rationalized by a set of reaction pathways for the various product phases. Copyright © 2015 Elsevier Ltd. All rights reserved.

Reducing fischer-tropsch catalyst attrition losses in high agitation reaction systems

DOEpatents

Singleton, Alan H.; Oukaci, Rachid; Goodwin, James G.

2001-01-01

A method for reducing catalyst attrition losses in hydrocarbon synthesis processes conducted in high agitation reaction systems; a method of producing an attrition-resistant catalyst; a catalyst produced by such method; a method of producing an attrition-resistant catalyst support; and a catalyst support produced by such method. The inventive method of reducing catalyst attrition losses comprises the step of reacting a synthesis gas in a high agitation reaction system in the presence of a catalyst. In one aspect, the catalyst preferably comprises a .gamma.-alumina support including an amount of titanium effective for increasing the attrition resistance of the catalyst. In another aspect, the catalyst preferably comprises a .gamma.-alumina support which has been treated, after calcination, with an acidic, aqueous solution. The acidic aqueous solution preferably has a pH of not more than about 5. In another aspect, the catalyst preferably comprises cobalt on a .gamma.-alumina support wherein the cobalt has been applied to the .gamma.-alumina support by totally aqueous, incipient wetness-type impregnation. In another aspect, the catalyst preferably comprises cobalt on a .gamma.-alumina support with an amount of a lanthana promoter effective for increasing the attrition resistance of the catalyst. In another aspect, the catalyst preferably comprises a .gamma.-alumina support produced from boehmite having a crystallite size, in the 021 plane, in the range of from about 30 to about 55 .ANG.ngstrons. In another aspect, the inventive method of producing an attrition-resistant catalyst comprises the step of treating a .gamma.-alumina support, after calcination of and before adding catalytic material to the support, with an acidic solution effective for increasing the attrition resistance of the catalyst. In another aspect, the inventive method of producing an attrition-resistant catalyst support comprises the step of treating calcined .gamma.-alumina with an acidic, aqueous solution effective for increasing the attrition resistance of the .gamma.-alumina.

Hydro-isomerization of n-hexane on bi-functional catalyst: Effect of total and hydrogen partial pressures

NASA Astrophysics Data System (ADS)

Thoa, Dao Thi Kim; Loc, Luu Cam

2017-09-01

The effect of both total pressure and hydrogen partial pressure during n-hexane hydro-isomerization over platinum impregnated on HZSM-5 was studied. n-Hexane hydro-isomerization was conducted at atmospheric pressure and 0.7 MPa to observe the influence of total pressure. In order to see the effect of hydrogen partial pressure, the reaction was taken place at different partial pressure of hydrogen varied from 307 hPa to 718 hPa by dilution with nitrogen to keep the total pressure at 0.1 MPa. Physico-chemical characteristics of catalyst were determined by the methods of nitrogen physi-sorption BET, SEM, XRD, TEM, NH3-TPD, TPR, and Hydrogen Pulse Chemi-sorption. Activity of catalyst in the hydro-isomerization of n-hexane was studied in a micro-flow reactor in the temperature range of 225-325 °C; the molar ratio H2/ hydrocarbon: 5.92, concentration of n-hexane: 9.2 mol.%, GHSV 2698 h-1. The obtained catalyst expressed high acid density, good reducing property, high metal dispersion, and good balance between metallic and acidic sites. It is excellent contact for n-hexane hydro-isomerization. At 250 °C, n-hexane conversion and selectivity were as high as 59-76 % and 85-99 %, respectively. It was found that catalytic activity was promoted either by total pressure or hydrogen partial pressure. At total pressure of 0.7 MPa while hydrogen partial pressure of 718 hPa, catalyst produced 63 RON liquid product containing friendly environmental iso-paraffins which is superior blending stock for green gasoline. Hydrogen did not only preserve catalyst actives by depressing hydrocracking and removing coke precursors but also facilitated hydride transfer step in the bi-functional bi-molecular mechanism.

Conversion of 2,3-butanediol to 2-butanol, olefins and fuels

DOEpatents

Lilga, Michael A.; Lee, Guo-Shuh; Lee, Suh-Jane

2016-12-13

Embodiments of an integrated method for step-wise conversion of 2,3-butanediol to 2-butanol, and optionally to hydrocarbons, are disclosed. The method includes providing an acidic catalyst, exposing a composition comprising aqueous 2,3-butanediol to the acidic catalyst to produce an intermediate composition comprising methyl ethyl ketone, providing a hydrogenation catalyst that is spatially separated from the acidic catalyst, and subsequently exposing the intermediate composition to the hydrogenation catalyst to produce a composition comprising 2-butanol. The method may further include subsequently exposing the composition comprising 2-butanol to a deoxygenation catalyst, and deoxygenating the 2-butanol to form hydrocarbons. In some embodiments, the hydrocarbons comprise olefins, such as butenes, and the method may further include subsequently exposing the hydrocarbons to a hydrogenation catalyst to form saturated hydrocarbons.

Catalyst system comprising a first catalyst system tethered to a supported catalyst

DOEpatents

Angelici, Robert J.; Gao, Hanrong

1998-08-04

The present invention provides new catalyst formats which comprise a supported catalyst tethered to a second and different catalyst by a suitable tethering ligand. A preferred system comprises a heterogeneous supported metal catalyst tethered to a homogeneous catalyst. This combination of homogeneous and heterogeneous catalysts has a sufficient lifetime and unusually high catalytic activity in arene hydrogenations, and potentially many other reactions as well, including, but not limited to hydroformylation, hydrosilation, olefin oxidation, isomerization, hydrocyanation, olefin metathesis, olefin polymerization, carbonylation, enantioselective catalysis and photoduplication. These catalysts are easily separated from the products, and can be reused repeatedly, making these systems very economical.

Catalyst system comprising a first catalyst system tethered to a supported catalyst

DOEpatents

Angelici, R.J.; Gao, H.

1998-08-04

The present invention provides new catalyst formats which comprise a supported catalyst tethered to a second and different catalyst by a suitable tethering ligand. A preferred system comprises a heterogeneous supported metal catalyst tethered to a homogeneous catalyst. This combination of homogeneous and heterogeneous catalysts has a sufficient lifetime and unusually high catalytic activity in arene hydrogenations, and potentially many other reactions as well, including, but not limited to hydroformylation, hydrosilication, olefin oxidation, isomerization, hydrocyanidation, olefin metathesis, olefin polymerization, carbonylation, enantioselective catalysis and photoduplication. These catalysts are easily separated from the products, and can be reused repeatedly, making these systems very economical. 2 figs.

Catalyst systems and uses thereof

DOEpatents

Ozkan, Umit S [Worthington, OH; Holmgreen, Erik M [Columbus, OH; Yung, Matthew M [Columbus, OH

2012-07-24

A method of carbon monoxide (CO) removal comprises providing an oxidation catalyst comprising cobalt supported on an inorganic oxide. The method further comprises feeding a gaseous stream comprising CO, and oxygen (O.sub.2) to the catalyst system, and removing CO from the gaseous stream by oxidizing the CO to carbon dioxide (CO.sub.2) in the presence of the oxidation catalyst at a temperature between about 20 to about 200.degree. C.

Process for hydrocracking carbonaceous material to provide fuels or chemical feed stock

DOEpatents

Duncan, Dennis A.

1980-01-01

A process is disclosed for hydrocracking coal or other carbonaceous material to produce various aromatic hydrocarbons including benzene, toluene, xylene, ethylbenzene, phenol and cresols in variable relative concentrations while maintaining a near constant maximum temperature. Variations in relative aromatic concentrations are achieved by changing the kinetic severity of the hydrocracking reaction by altering the temperature profile up to and quenching from the final hydrocracking temperature. The relative concentration of benzene to the alkyl and hydroxyl aromatics is increased by imposing increased kinetic severity above that corresponding to constant heating rate followed by immediate quenching at about the same rate to below the temperature at which dehydroxylation and dealkylation reactions appreciably occur. Similarly phenols, cresols and xylenes are produced in enhanced concentrations by adjusting the temperature profile to provide a reduced kinetic severity relative to that employed when high benzene concentrations are desired. These variations in concentrations can be used to produce desired materials for chemical feed stocks or for fuels.

Enhancement of alkylation catalysts for improved supercritical fluid regeneration

DOEpatents

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

2009-09-22

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

Enhancement of alkylation catalysts for improved supercritical fluid regeneration

DOEpatents

Ginosar, Daniel M.; Petkovic, Lucia M.

2010-12-28

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

Use of aluminum phosphate as the dehydration catalyst in single step dimethyl ether process

DOEpatents

Peng, Xiang-Dong; Parris, Gene E.; Toseland, Bernard A.; Battavio, Paula J.

1998-01-01

The present invention pertains to a process for the coproduction of methanol and dimethyl ether (DME) directly from a synthesis gas in a single step (hereafter, the "single step DME process"). In this process, the synthesis gas comprising hydrogen and carbon oxides is contacted with a dual catalyst system comprising a physical mixture of a methanol synthesis catalyst and a methanol dehydration catalyst. The present invention is an improvement to this process for providing an active and stable catalyst system. The improvement comprises the use of an aluminum phosphate based catalyst as the methanol dehydration catalyst. Due to its moderate acidity, such a catalyst avoids the coke formation and catalyst interaction problems associated with the conventional dual catalyst systems taught for the single step DME process.

Multi-stage catalyst systems and uses thereof

DOEpatents

Ozkan, Umit S [Worthington, OH; Holmgreen, Erik M [Columbus, OH; Yung, Matthew M [Columbus, OH

2009-02-10

Catalyst systems and methods provide benefits in reducing the content of nitrogen oxides in a gaseous stream containing nitric oxide (NO), hydrocarbons, carbon monoxide (CO), and oxygen (O.sub.2). The catalyst system comprises an oxidation catalyst comprising a first metal supported on a first inorganic oxide for catalyzing the oxidation of NO to nitrogen dioxide (NO.sub.2), and a reduction catalyst comprising a second metal supported on a second inorganic oxide for catalyzing the reduction of NO.sub.2 to nitrogen (N.sub.2).

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

DOEpatents

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

1986-01-01

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

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

DOEpatents

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

1987-01-01

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

Mesoporous Phosphate Heterostructures: Synthesis and Application on Adsorption and Catalysis

NASA Astrophysics Data System (ADS)

Moreno-Tost, Ramón; Jiménez-Jiménez, José; Infantes-Molina, Antonia; Cavalcante, Celio L.; Azevedo, Diana C. S.; Soriano, María Dolores; López Nieto, José Manuel; Jiménez-López, Antonio; Rodríguez-Castellón, Enrique

Porous phosphate heterostructures (PPHs) are solids formed by a layered metal(IV) phosphate expanded with silica galleries obtained by combining the two main strategies for obtaining mesoporous materials [pillared layered structures (PLS') and MCM-41]. The different synthetic pathways for obtaining mesoporous phosphate structures with silica galleries with Zr- or Ti-doped silica, the study of their structural, textural and acid properties, its functionalisation with different organic substances such as propionitrile, 3-aminopropyl triethoxysilane, (3-mercaptopropyl)trimethoxysilane, vinyltrimethoxysilane, phenyltriethoxysilane and 3-(triethoxysilyl)propionitrile are discussed. The preparation of metal-supported catalysts and their application in gas separation, adsorption and catalysis are reviewed. Specifically, the use of Cu- and Fe-exchanged PPH for the adsorption of benzothiophene and the separation of propane/propene is the main application as adsorbent. The hydrotreating of aromatic hydrocarbons using ruthenium-impregnated catalysts via hydrogenation and hydrogenolysis/hydrocracking for the production of clean diesel fuels, the selective catalytic reduction of NO from stationary and mobile sources by using Cu-PPH with 1, 3 and 7 wt% of Cu and the selective oxidation of hydrogen sulphide to sulphur with vanadium-containing PPH are the three catalytic reactions of environmental interest studied.

Low platinum catalyst and method of preparation

DOEpatents

Liu, Di-Jia; Chong, Lina

2017-11-21

A low platinum catalyst and method for making same. The catalyst comprises platinum-transition metal bimetallic alloy microcrystallites over a transition metal-nitrogen-carbon composite. A method of making a catalyst comprises preparation of transition metal organic frameworks, infusion of platinum, thermal treatment, and reduction to form the microcrystallites and composite.

Method for the regeneration of spent molten zinc chloride

DOEpatents

Zielke, Clyde W.; Rosenhoover, William A.

1981-01-01

In a process for regenerating spent molten zinc chloride which has been used in the hydrocracking of coal or ash-containing polynuclear aromatic hydrocarbonaceous materials derived therefrom and which contains zinc chloride, zinc oxide, zinc oxide complexes and ash-containing carbonaceous residue, by incinerating the spent molten zinc chloride to vaporize the zinc chloride for subsequent condensation to produce a purified molten zinc chloride: an improvement comprising the use of clay in the incineration zone to suppress the vaporization of metals other than zinc. Optionally water is used in conjunction with the clay to further suppress the vaporization of metals other than zinc.

Enhanced catalyst for conversion of syngas to liquid motor fuels

DOEpatents

Coughlin, Peter K.; Rabo, Jule A.

1985-01-01

Synthesis gas comprising carbon monoxide and hydrogen is converted to C.sub.5.sup.+ hydrocarbons suitable for use as liquid motor fuels by contact with a dual catalyst system capable of enhancing the selectivity of said conversion to motor fuel range hydrocarbons and the quality of the resulting motor fuel product. The catalyst composition employs a Fischer-Tropsch catalyst, together with a co-catalyst/support component comprising SAPO silicoaluminophosphate, non-zeolitic molecular sieve catalyst.

Enhanced catalyst for conversion of syngas to liquid motor fuels

DOEpatents

Coughlin, P.K.; Rabo, J.A.

1985-12-03

Synthesis gas comprising carbon monoxide and hydrogen is converted to C[sub 5][sup +] hydrocarbons suitable for use as liquid motor fuels by contact with a dual catalyst system capable of enhancing the selectivity of said conversion to motor fuel range hydrocarbons and the quality of the resulting motor fuel product. The catalyst composition employs a Fischer-Tropsch catalyst, together with a co-catalyst/support component comprising a SAPO silicoaluminophosphate, non-zeolitic molecular sieve catalyst.

Method of depositing a catalyst on a fuel cell electrode

DOEpatents

Dearnaley, Geoffrey; Arps, James H.

2000-01-01

Fuel cell electrodes comprising a minimal load of catalyst having maximum catalytic activity and a method of forming such fuel cell electrodes. The method comprises vaporizing a catalyst, preferably platinum, in a vacuum to form a catalyst vapor. A catalytically effective amount of the catalyst vapor is deposited onto a carbon catalyst support on the fuel cell electrode. The electrode preferably is carbon cloth. The method reduces the amount of catalyst needed for a high performance fuel cell electrode to about 0.3 mg/cm.sup.2 or less.

Combined catalysts for the combustion of fuel in gas turbines

DOEpatents

Anoshkina, Elvira V.; Laster, Walter R.

2012-11-13

A catalytic oxidation module for a catalytic combustor of a gas turbine engine is provided. The catalytic oxidation module comprises a plurality of spaced apart catalytic elements for receiving a fuel-air mixture over a surface of the catalytic elements. The plurality of catalytic elements includes at least one primary catalytic element comprising a monometallic catalyst and secondary catalytic elements adjacent the primary catalytic element comprising a multi-component catalyst. Ignition of the monometallic catalyst of the primary catalytic element is effective to rapidly increase a temperature within the catalytic oxidation module to a degree sufficient to ignite the multi-component catalyst.

Enhanced conversion of syngas to liquid motor fuels

DOEpatents

Coughlin, Peter K.; Rabo, Jule A.

1986-01-01

Synthesis gas comprising carbon monoxide and hydrogen is converted to C.sub.5.sup.+ hydrocarbons suitable for use as liquid motor fuels by contact with a dual catalyst system capable of enhancing the selectivity of said conversion to motor fuel range hydrocarbons and the quality of the resulting motor fuel product. The catalyst composition employs a Fischer-Tropsch catalyst, together with a co-catalyst/support component comprising SAPO silicoaluminophosphate, non-zeolitic molecular sieve catalyst.

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

DOEpatents

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

2004-06-08

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

Methods of making alkyl esters

DOEpatents

Elliott, Brian

2010-08-03

A method comprising contacting an alcohol, a feed comprising one or more glycerides and equal to or greater than 2 wt % of one or more free fatty acids, and a solid acid catalyst, a nanostructured polymer catalyst, or a sulfated zirconia catalyst in one or more reactors, and recovering from the one or more reactors an effluent comprising equal to or greater than about 75 wt % alkyl ester and equal to or less than about 5 wt % glyceride.

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

DOEpatents

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

2013-01-08

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

Ruthenium on rutile catalyst, catalytic system, and method for aqueous phase hydrogenations

DOEpatents

Elliot, Douglas C.; Werpy, Todd A.; Wang, Yong; Frye, Jr., John G.

2001-01-01

An essentially nickel- and rhenium-free catalyst is described comprising ruthenium on a titania support where the titania is greater than 75% rutile. A catalytic system containing a nickel-free catalyst comprising ruthenium on a titania support where the titania is greater than 75% rutile, and a method using this catalyst in the hydrogenation of an organic compound in the aqueous phase is also described.

Selective catalytic reduction system and process for treating NOx emissions using a palladium and rhodium or ruthenium catalyst

DOEpatents

Sobolevskiy, Anatoly [Orlando, FL; Rossin, Joseph A [Columbus, OH; Knapke, Michael J [Columbus, OH

2011-07-12

A process for the catalytic reduction of nitrogen oxides (NOx) in a gas stream (29) in the presence of H.sub.2 is provided. The process comprises contacting the gas stream with a catalyst system (38) comprising zirconia-silica washcoat particles (41), a pre-sulfated zirconia binder (44), and a catalyst combination (40) comprising palladium and at least one of rhodium, ruthenium, or a mixture of ruthenium and rhodium.

Catalyst for coal liquefaction process

DOEpatents

Huibers, Derk T. A.; Kang, Chia-Chen C.

1984-01-01

An improved catalyst for a coal liquefaction process; e.g., the H-Coal Process, for converting coal into liquid fuels, and where the conversion is carried out in an ebullated-catalyst-bed reactor wherein the coal contacts catalyst particles and is converted, in addition to liquid fuels, to gas and residual oil which includes preasphaltenes and asphaltenes. The improvement comprises a catalyst selected from the group consisting of the oxides of nickel molybdenum, cobalt molybdenum, cobalt tungsten, and nickel tungsten on a carrier of alumina, silica, or a combination of alumina and silica. The catalyst has a total pore volume of about 0.500 to about 0.900 cc/g and the pore volume comprises micropores, intermediate pores and macropores, the surface of the intermediate pores being sufficiently large to convert the preasphaltenes to asphaltenes and lighter molecules. The conversion of the asphaltenes takes place on the surface of micropores. The macropores are for metal deposition and to prevent catalyst agglomeration. The micropores have diameters between about 50 and about 200 angstroms (.ANG.) and comprise from about 50 to about 80% of the pore volume, whereas the intermediate pores have diameters between about 200 and 2000 angstroms (.ANG.) and comprise from about 10 to about 25% of the pore volume, and the macropores have diameters between about 2000 and about 10,000 angstroms (.ANG.) and comprise from about 10 to about 25% of the pore volume. The catalysts are further improved where they contain promoters. Such promoters include the oxides of vanadium, tungsten, copper, iron and barium, tin chloride, tin fluoride and rare earth metals.

Catalysts, systems and methods to reduce NOX in an exhaust gas stream

DOEpatents

Castellano, Christopher R.; Moini, Ahmad; Koermer, Gerald S.; Furbeck, Howard

2010-07-20

Catalysts, systems and methods are described to reduce NO.sub.x emissions of an internal combustion engine. In one embodiment, an emissions treatment system for an exhaust stream is provided having an SCR catalyst comprising silver tungstate on an alumina support. The emissions treatment system may be used for the treatment of exhaust streams from diesel engines and lean burn gasoline engines. An emissions treatment system may further comprise an injection device operative to dispense a hydrocarbon reducing agent upstream of the catalyst.

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.

Process for the synthesis of aliphatic alcohol-containing mixtures

DOEpatents

Greene, Marvin I.; Gelbein, Abraham P.

1984-01-01

A process for the synthesis of mixtures which include saturated aliphatic alcohols is disclosed. In the first step of the process, the first catalyst activation stage, a catalyst, which comprises the oxides of copper, zinc, aluminum, potassium and one or two additional metals selected from the group consisting of chromium, magnesium, cerium, cobalt, thorium and lanthanum, is partially activated. In this step, a reducing gas stream, which includes hydrogen and at least one inert gas, flows past the catalyst at a space velocity of up to 5,000 liters (STP) per hour, per kilogram of catalyst. The partially activated catalyst is then subjected to the second step of the process, second-stage catalyst activation. In this step, the catalyst is contacted by an activation gas stream comprising hydrogen and carbon monoxide present in a volume ratio of 0.5:1 and 4:1, respectively, at a temperature of 200.degree. to 450.degree. C. and a pressure of between 35 and 200 atmospheres. The activation gas flows at a space velocity of from 1,000 to 20,000 liters (STP) per hour, per kilogram of catalyst. Second-stage activation continues until the catalyst is contacted with at least 500,000 liters (STP) of activation gas per kilogram of catalyst. The fully activated catalyst, in the third step of the process, contacts a synthesis gas stream comprising hydrogen and carbon monoxide.

Process for the synthesis of aliphatic alcohol-containing mixtures

DOEpatents

Greene, M.I.; Gelbein, A.P.

1984-10-16

A process for the synthesis of mixtures which include saturated aliphatic alcohols is disclosed. In the first step of the process, the first catalyst activation stage, a catalyst, which comprises the oxides of copper, zinc, aluminum, potassium and one or two additional metals selected from the group consisting of chromium, magnesium, cerium, cobalt, thorium and lanthanum, is partially activated. In this step, a reducing gas stream, which includes hydrogen and at least one inert gas, flows past the catalyst at a space velocity of up to 5,000 liters (STP) per hour, per kilogram of catalyst. The partially activated catalyst is then subjected to the second step of the process, second-stage catalyst activation. In this step, the catalyst is contacted by an activation gas stream comprising hydrogen and carbon monoxide present in a volume ratio of 0.5:1 and 4:1, respectively, at a temperature of 200 to 450 C and a pressure of between 35 and 200 atmospheres. The activation gas flows at a space velocity of from 1,000 to 20,000 liters (STP) per hour, per kilogram of catalyst. Second-stage activation continues until the catalyst is contacted with at least 500,000 liters (STP) of activation gas per kilogram of catalyst. The fully activated catalyst, in the third step of the process, contacts a synthesis gas stream comprising hydrogen and carbon monoxide.

Selective catalytic reduction system and process for treating NOx emissions using a zinc or titanium promoted palladium-zirconium catalyst

DOEpatents

Sobolevskiy, Anatoly [Orlando, FL; Rossin, Joseph A [Columbus, OH; Knapke, Michael J [Columbus, OH

2011-08-02

A process and system (18) for reducing NO.sub.x in a gas using hydrogen as a reducing agent is provided. The process comprises contacting the gas stream (29) with a catalyst system (38) comprising sulfated zirconia washcoat particles (41), palladium, a pre-sulfated zirconia binder (44), and a promoter (45) comprising at least one of titanium, zinc, or a mixture thereof. The presence of zinc or titanium increases the resistance of the catalyst system to a sulfur and water-containing gas stream.

Process for hydrocracking carbonaceous material in liquid carrier

DOEpatents

Duncan, Dennis A.

1980-01-01

Solid carbonaceous material is hydrocracked to provide aliphatic and aromatic hydrocarbons for use as gaseous and liquid fuels or chemical feed stock. Particulate carbonaceous material such as coal in slurry with recycled product oil is preheated in liquid state to a temperature of 600.degree.-1200.degree. F. in the presence of hydrogen gas. The product oil acts as a sorbing agent for the agglomerating bitumins to minimize caking within the process. In the hydrocracking reactor, the slurry of oil and carbonaceous particles is heated within a tubular passageway to vaporize the oil and form a gas-solid mixture which is further heated to a hydropyrolysis temperature in excess of 1200.degree. F. The gas-solid mixture is quenched by contact with additional oil to condense normally liquid hydrocarbons for separation from the gases. A fraction of the hydrocarbon liquid product is recycled for quenching and slurrying with the carbonaceous feed. Hydrogen is recovered from the gas for recycle and additional hydrogen is produced by gasification of residual char.

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

Chu, C.C.

A process is described of dehydrogenating para-ethyltoluene to selectively form para-methylstyrene comprising contacting to para-ethyltoluene under dehydrogenation reaction conditions with a catalyst composition comprising: (a) from about 30% to 60% by weight of iron oxide, calculated as ferric oxide; (b) from about 13% to 48% by weight of a potassium compound, calculated as potassium oxide; and (c) from about 0% to 5% by weight of a chromium compound, calculated as chromic oxide. The improvement is described comprising dehydrogenating the para-ethyltoluene with a catalyst composition comprising, in addition to the components (a), (b) and (c), a modifying component (d) capable ofmore » rendering the para-methylstyrene-containing dehydrogenation reaction effluent especially resistant to the subsequent formation of popcorn polymers when the dehydrogenation of para-ethyltoluene is conducted over the modified catalyst, the modifying component (d) being a bismuth compound present to the extent of from about 1% to 20% by weight of the catalyst composition, calculated as bismuth trioxide.« less

Thermal hydrocracking of coal derived liquid from mild gasification (production of phenols, BTX and naphthalenes)

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

Sato, Yoshiki; Kodera, Yoichi; Kamo, Tohru

1997-12-31

Coal derived liquid from mild gasification contains more than 40% of alkylphenols with alkylnaphthalenes and a small amount of benzofuran, naphthol and condensed aromatic derivatives. In this study, thermal hydrocracking of the coal derived liquid, and related model compounds have been investigated using a small atmospheric flow apparatus at temperatures of 700--770 C with residence time of 3--10 sec, and hydrogen-to-reactant molar ratio of about 3--10. In the experiments using m-cresol and 2,5-dimethylphenol, dealkylation and dehydroxylation proceeded concurrently with high selectivity in the presence of excess hydrogen. The rates of hydrocracking of m-cresol and 2,5-dimethylphenol were in accordance with first-ordermore » rate law with respect to reactant. This indicates that the same kinetic equation for the demethylation of alkylbenzenes can be applied. Rates of demethylation and dehydroxylation for cresols and dimethylphenols have been measured at 700 C by using toluene as an internal reference, and discussed in terms of chemical structure. Thermal hydrocracking of the coal derived liquid produced 20--40 wt% gases and 60--80 wt% liquids. Gaseous products mainly consisted of carbon monoxide and methane with small amounts of C{sub 2} and C{sub 3} hydrocarbon gases. Liquid products, obtained at 770 C, contained 24 wt% of BTX, 40 wt% of phenol and cresols, and 12 wt% of naphthalene and methylnaphthalenes. Yield of useful chemicals, having simple aromatic structure in the liquid product increased with temperature and residence time.« less

Process for conversion of lignin to reformulated, partially oxygenated gasoline

DOEpatents

Shabtai, Joseph S.; Zmierczak, Wlodzimierz W.; Chornet, Esteban

2001-01-09

A high-yield process for converting lignin into reformulated, partially oxygenated gasoline compositions of high quality is provided. The process is a two-stage catalytic reaction process that produces a reformulated, partially oxygenated gasoline product with a controlled amount of aromatics. In the first stage of the process, a lignin feed material is subjected to a base-catalyzed depolymerization reaction, followed by a selective hydrocracking reaction which utilizes a superacid catalyst to produce a high oxygen-content depolymerized lignin product mainly composed of alkylated phenols, alkylated alkoxyphenols, and alkylbenzenes. In the second stage of the process, the depolymerized lignin product is subjected to an exhaustive etherification reaction, optionally followed by a partial ring hydrogenation reaction, to produce a reformulated, partially oxygenated/etherified gasoline product, which includes a mixture of substituted phenyl/methyl ethers, cycloalkyl methyl ethers, C.sub.7 -C.sub.10 alkylbenzenes, C.sub.6 -C.sub.10 branched and multibranched paraffins, and alkylated and polyalkylated cycloalkanes.

Synthesis and analysis of jet fuel from shale oil and coal syncrudes

NASA Technical Reports Server (NTRS)

Gallagher, J. P.; Collins, T. A.; Nelson, T. J.; Pedersen, M. J.; Robison, M. G.; Wisinski, L. J.

1976-01-01

Thirty-two jet fuel samples of varying properties were produced from shale oil and coal syncrudes, and analyzed to assess their suitability for use. TOSCO II shale oil and H-COAL and COED syncrudes were used as starting materials. The processes used were among those commonly in use in petroleum processing-distillation, hydrogenation and catalytic hydrocracking. The processing conditions required to meet two levels of specifications regarding aromatic, hydrogen, sulfur and nitrogen contents at two yield levels were determined and found to be more demanding than normally required in petroleum processing. Analysis of the samples produced indicated that if the more stringent specifications of 13.5% hydrogen (min.) and 0.02% nitrogen (max.) were met, products similar in properties to conventional jet fuels were obtained. In general, shale oil was easier to process (catalyst deactivation was seen when processing coal syncrudes), consumed less hydrogen and yielded superior products. Based on these considerations, shale oil appears to be preferred to coal as a petroleum substitute for jet fuel production.

Photo-oxidation catalysts

DOEpatents

Pitts, J Roland [Lakewood, CO; Liu, Ping [Irvine, CA; Smith, R Davis [Golden, CO

2009-07-14

Photo-oxidation catalysts and methods for cleaning a metal-based catalyst are disclosed. An exemplary catalyst system implementing a photo-oxidation catalyst may comprise a metal-based catalyst, and a photo-oxidation catalyst for cleaning the metal-based catalyst in the presence of light. The exposure to light enables the photo-oxidation catalyst to substantially oxidize absorbed contaminants and reduce accumulation of the contaminants on the metal-based catalyst. Applications are also disclosed.

Catalytic converter for purifying exhaust gases of internal combustion engines

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

Kakinuma, A.; Oya, H.

1980-06-24

A catalytic converter for purifying the exhaust gases of internal combustion engines is comprised of a cylindrical shell comprising a pair of half shells which form an inlet chamber, a catalyst chamber, and an outlet chamber, a catalyst element provided in the catalyst chamber, a cylindrical sealing member provided in the inlet chamber, and a damper member provided between the cylindrical shell and the sealing member. The sealing member engages to the cylindrical shell for sealing the gap between the cylindrical shell and the catalyst element.

Catalytic functionalities of supported sulfides. I. Effect of support and additives on the CoMo catalyst

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

Muralidhar, G.; Massoth, F.E.; Shabtai, J.

1984-01-01

C-S hydrogenolysis (HDS) of thiophene, hydrogenation (HYD) of 1-hexene, and hydrocracking (HCG) of 2,4,4-trimethyl-1-pentene, were used as separate model test reactions to differentiate and assess the catalytic functionalities of sulfided CoMo catalysts, and their dependence on the nature of the support and incorporation of additives. Rate constants and relative catalyst activities for these three reaction types were determined. HDS and HYD activities of CoMo supported on different types of Al/sub 2/O/sub 3/ were higher, while the HCG activity was lower compared with CoMo supported on SiO/sub 2/-Al/sub 2/O/sub 3/, SiO/sub 2/-MgO, or TiO/sub 2/. For SiO/sub 2/-Al/sub 2/O/sub 3/ supportsmore » both HDS and HYD activities decreased with increase in SiO/sub 2/ content from 10 to 75%, while HCG activity showed the opposite trend. Additives to a finished CoMo catalyst at 0.5% level caused variations in HDS and HCG activities, while HYD was essentially unaffected. HDS was promoted by NH/sub 4/HF/sub 2/ and NH/sub 4/Cl, but depressed by NaNO/sub 3/, Ca(NO/sub 3/)/sub 2/, and H/sub 3/BO/sub 3/. HCG was promoted by NH/sub 4/HF/sub 2/, NH/sub 4/Cl, and H/sub 3/BO/sub 3/. Additives at 5% level, prior to or after CoMo impregnation, showed a strong depressing effect on HDS and a lesser effect on HYD, while HCG was strongly promoted by NH/sub 4/HF/sub 2/, Ti isopropoxide, and H/sub 3/BO/sub 3/. The changes in catalytic functionalities are rationalized in terms of different interactions between CoMo phase, support, and additives. 3 tables, 1 figure.« less

Organic conductive films for semiconductor electrodes

DOEpatents

Frank, Arthur J.

1984-01-01

According to the present invention, improved electrodes overcoated with conductive polymer films and preselected catalysts are provided. The electrodes typically comprise an inorganic semiconductor overcoated with a charge conductive polymer film comprising a charge conductive polymer in or on which is a catalyst or charge-relaying agent.

Attrition resistant gamma-alumina catalyst support

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

Singleton, Alan H.; Oukaci, Rachid; Goodwin, James G.

2006-03-14

A .gamma.-alumina catalyst support having improved attrition resistance produced by a method comprising the steps of treating a particulate .gamma.-alumina material with an acidic aqueous solution comprising water and nitric acid and then, prior to adding any catalytic material thereto, calcining the treated .gamma.-alumina.

Process for the production of liquid hydrocarbons

DOEpatents

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

2006-06-27

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

Mobil lube dewaxing technologies

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

Baker, C.L.; McGuiness, M.P.

1995-09-01

Currently, the lube refining industry is in a period of transition, with both hydroprocessing and catalytic dewaxing gathering momentum as replacements for solvent extraction and solvent dewaxing. In addition, lube product quality requirements have been increasing, both in the US and abroad. Mobil has developed a broad array of dewaxing catalytic technologies which can serve refiners throughout the stages of this transition. In the future, lube feedstocks which vary in source and wax content will become increasingly important, requiring an optimized system for highest performance. The Mobil Lube Dewaxing (MLDW) process is the work-horse of the catalytic dewaxing technologies, beingmore » a robust, low cost technology suitable for both solvent extracted and hydrocracked feeds. The Mobil Selective Dewaxing (MSDW) process has been recently introduced in response to the growth of hydroprocessing. MSDW requires either severely hydrotreated or hydrocracked feeds and provides improved lube yields and VI. For refiners with hydrocrackers and solvent dewaxing units, Mobil Wax Isomerization (MWI) technology can make higher VI base stocks to meet the growing demand for very high quality lube products. A review of these three technologies is presented in this paper.« less

Parametric study of two-stage hydropyrolysis of lignocellulosic biomass for production of gaseous and light aromatic hydrocarbons.

PubMed

Zheng, Nan; Zhang, Jie; Wang, Jie

2017-11-01

Non-catalytic hydropyrolysis of pinewood and its components was carried out using a two-stage reactor. The main aim of this work is to investigate the hydrodeoxygenation and hydrogenation of volatile matter in the post hydrocracking reactor for oriented production of gaseous and light aromatic hydrocarbons. A portion of volatile matter, which evolved from hemicellulose, neutral extractives and lignin below 275°C, was found to be thoroughly hydrodeoxygenated preventing the release of CO 2 and CO. Increasing hydrocracking temperature from 600°C to 750°C and pressure from 1.0MPa to 5.0MPa strongly facilitated the hydrogenation reactions to target products. The summed yield of CH 4 and C 2 H 6 (dry biomass basis) reached up to 33.2% at a hydrocracking temperature of 750°C and 5.0MPa, with a concomitant 5.1% yield of BTX. All components in pinewood significantly contributed to the production of CH 4 and BTX by hydropyrolysis, differing from the case of pyrolysis. Copyright © 2017 Elsevier Ltd. All rights reserved.

Techno-economic and resource analysis of hydroprocessed renewable jet fuel.

PubMed

Tao, Ling; Milbrandt, Anelia; Zhang, Yanan; Wang, Wei-Cheng

2017-01-01

Biomass-derived jet fuel is an alternative jet fuel (AJF) showing promise of reducing the dependence on fossil fuel and greenhouse gas emissions. Hydroprocessed esters and fatty acids (HEFA) concept is also known as one of the pathways for producing bio jet fuel. HEFA fuel was approved by the American Society for Testing and Materials in 2011, and can be blended up to 50% with conventional jet fuel. Since then, several HEFA economic and life-cycle assessments have been published in literature. However, there have been limited analyses on feedstock availability, composition, and their impact on hydrocarbon yield (particularly jet blendstock yield) and overall process economics. This study examines over 20 oil feedstocks, their geographic distribution and production levels, oil yield, prices, and chemical composition. The results of our compositional analysis indicate that most oils contain mainly C 16 and C 18 fatty acids except pennycress, yellow grease, and mustard, which contain higher values and thus would require hydrocracking to improve jet fuel production. Coconut oil has a large content of shorter carbon fatty acids, making it a good feedstock candidate for renewable gasoline instead of jet substitutes' production. Techno-economic analysis (TEA) was performed for five selected oil feedstocks-camelina, pennycress, jatropha, castor bean, and yellow grease-using the HEFA process concept. The resource analysis indicates that oil crops currently grown in the United States (namely soybean) have relatively low oil yield when compared to oil crops grown in other parts of the world, such as palm, coconut, and jatropha. Also, non-terrestrial oil sources, such as animal fats and greases, have relatively lower prices than terrestrial oil crops. The minimum jet fuel selling price for these five resources ranges between $3.8 and $11.0 per gallon. The results of our TEA and resource studies indicate the key cost drivers for a biorefinery converting oil to jet hydrocarbons are as follows: oil price, conversion plant capacity, fatty acid profile, addition of hydrocracker, and type of hydroprocessing catalysts.

Organic conductive films for semiconductor electrodes

DOEpatents

Frank, A.J.

1984-01-01

According to the present invention, improved electrodes overcoated with conductive polymer films and preselected catalysts are provided. The electrodes typically comprise an inorganic semiconductor over-coated with a charge conductive polymer film comprising a charge conductive polymer in or on which is a catalyst or charge-relaying agent.

Subnanometer to nanometer transition metal CO oxidation catalysts

DOEpatents

Vajda, Stefan; Fortunelli, Alessandro; Yasumatsu, Hisato

2017-12-26

The present invention provides a catalyst defined in part by a conductive substrate; a film overlaying a surface of the substrate; and a plurality of metal clusters supported by the layer, wherein each cluster comprises between 8 and 11 atoms. Further provided is a catalyst defined in part by a conductive substrate; a layer overlaying a surface of the substrate; and a plurality of metal clusters supported by the layer, wherein each cluster comprises at least two metals.

Hydrogen storage material and related processes

DOEpatents

Soloveichik, Grigorii Lev [Latham, NY; Andrus, Matthew John [Cape Canaveral, FL

2012-06-05

Disclosed herein is a composition comprising a complex hydride and a borohydride catalyst wherein the borohydride catalyst comprises a BH.sub.4 group, and a group IV metal, a group V metal, or a combination of a group IV and a group V metal. Also disclosed herein are methods of making the composition.

Hydrogen storage material and related processes

DOEpatents

Soloveichik; Grigorii Lev , Andrus; Matthew John

2010-07-13

Disclosed herein is a composition comprising a complex hydride and a borohydride catalyst wherein the borohydride catalyst comprises a BH.sub.4 group, and a group IV metal, a group V metal, or a combination of a group IV and a group V metal. Also disclosed herein are methods of making the composition.

Method of forming supported doped palladium containing oxidation catalysts

DOEpatents

Mohajeri, Nahid

2014-04-22

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

Method for producing iron-based catalysts

DOEpatents

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

1999-01-01

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

Photocatalytic polyoxometalate compositions of tungstovanadates and uses as water oxidation catalysts

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

Hill, Craig L.; Gueletii, Iourii V.; Song, Jie

This disclosure relates to photocatalytic polyoxometalate compositions of tungstovanadates and uses as water oxidation catalysts. In certain embodiments, the disclosure relates to compositions comprising water, a complex of a tetra-metal oxide cluster and VW.sub.9O.sub.34 ligands, and a photosensitizer. Typically, the metal oxide cluster is Co. In certain embodiments, the disclosure relates to electrodes and other devices comprising water oxidation catalysts disclosed herein and uses in generating fuels and electrical power from solar energy.

NO[sub x] reduction by sulfur tolerant coronal-catalytic apparatus and method

DOEpatents

Mathur, V.K.; Breault, R.W.; McLarnon, C.R.; Medros, F.G.

1992-09-15

This invention presents an NO[sub x] environment effective reduction apparatus comprising a sulfur tolerant coronal-catalyst such as high dielectric coronal-catalysts like glass wool, ceramic-glass wool or zirconium glass wool and method of use. In one embodiment the invention comprises an NO[sub x] reduction apparatus of sulfur tolerant coronal-catalyst adapted and configured for hypercritical presentation to an NO[sub x] bearing gas stream at a minimum of at least about 75 watts/cubic meter. 7 figs.

NO.sub.x reduction by sulfur tolerant coronal-catalytic apparatus and method

DOEpatents

Mathur, Virendra K.; Breault, Ronald W.; McLarnon, Christopher R.; Medros, Frank G.

1993-01-01

This invention presents an NO.sub.x environment effective reduction apparatus comprising a sulfur tolerant coronal-catalyst such as high dielectric coronal-catalysts like glass wool, ceramic-glass wool or zirconium glass wool and method of use. In one embodiment the invention comprises an NO.sub.x reduction apparatus of sulfur tolerant coronal-catalyst adapted and configured for hypercritical presentation to an NO.sub.x bearing gas stream at a minimum of at least about 75 watts/cubic meter.

NO.sub.x reduction by sulfur tolerant coronal-catalytic apparatus and method

DOEpatents

Mathur, Virendra K.; Breault, Ronald W.; McLarnon, Christopher R.; Medros, Frank G.

1992-01-01

This invention presents an NO.sub.x environment effective reduction apparatus comprising a sulfur tolerant coronal-catalyst such as high dielectric coronal-catalysts like glass wool, ceramic-glass wool or zirconium glass wool and method of use. In one embodiment the invention comprises an NO.sub.x reduction apparatus of sulfur tolerant coronal-catalyst adapted and configured for hypercritical presentation to an NO.sub.x bearing gas stream at a minimum of at least about 75 watts/cubic meter.

NOx reduction by sulfur tolerant coronal-catalytic apparatus and method

DOEpatents

Mathur, V.K.; Breault, R.W.; McLarnon, C.R.; Medros, F.G.

1993-08-31

This invention presents an NO[sub x] environment effective reduction apparatus comprising a sulfur tolerant coronal-catalyst such as high dielectric coronal-catalysts like glass wool, ceramic-glass wool or zirconium glass wool and method of use. In one embodiment the invention comprises an NO[sub x] reduction apparatus of sulfur tolerant coronal-catalyst adapted and configured for hypercritical presentation to an NO[sub x] bearing gas stream at a minimum of at least about 75 watts/cubic meter.

Synthesis of attrition-resistant heterogeneous catalysts using templated mesoporous silica

DOEpatents

Pham, Hien N.; Datye, Abhaya K.

2003-04-15

The present invention relates to catalysts in mesoporous structures. In a preferred embodiment, the invention comprises a method for encapsulating a dispersed insoluble compound in a mesoporous structure comprising combining a soluble oxide precursor, a solvent, and a surfactant to form a mixture; dispersing an insoluble compound in the mixture; spray-drying the mixture to produce dry powder; and calcining the powder to yield a porous structure comprising the dispersed insoluble compound.

Apparatus for purifying exhaust gases of internal combustion engines

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

Kakinuma, A.; Oya, H.

1980-06-03

Apparatus for purifying the exhaust gases of internal combustion engines is disclosed that is comprised of a pair of upstream exhaust pipes, a catalytic converter, and a downstream exhaust pipe. The catalytic converter comprises a cylindrical shell having an inlet chamber, a catalyst chamber, an outlet chamber, and a monolithic catalyst element in the catalyst chamber. The inlet chamber has inlet ports communicating with the upstream exhaust pipes respectively and axial lines of the inlet ports cross each other in the inlet chamber. In the inlet chamber, a diffusion means is provided to diffuse the exhaust gas for uniformly distributingmore » it to the catalyst element.« less

Production of aromatics from di- and polyoxygenates

DOEpatents

Beck, Taylor; Blank, Brian; Jones, Casey; Woods, Elizabeth; Cortright, Randy

2016-08-02

Methods, catalysts, and reactor systems for producing in high yield aromatic chemicals and liquid fuels from a mixture of oxygenates comprising di- and polyoxygenates are disclosed. Also disclosed are methods, catalysts, and reactor systems for producing aromatic chemicals and liquid fuels from oxygenated hydrocarbons such as carbohydrates, sugars, sugar alcohols, sugar degradation products, and the like; and methods, catalysts, and reactor systems for producing the mixture of oxygenates from oxygenated hydrocarbons such as carbohydrates, sugars, sugar alcohols, sugar degradation products, and the like. The disclosed catalysts for preparing the mixture of oxygenates comprise a Ni.sub.nSn.sub.m alloy and a crystalline alumina support.

Production of aromatics from di- and polyoxygenates

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

Beck, Taylor; Blank, Brian; Jones, Casey

Methods, catalysts, and reactor systems for producing in high yield aromatic chemicals and liquid fuels from a mixture of oxygenates comprising di- and polyoxygenates are disclosed. Also disclosed are methods, catalysts, and reactor systems for producing aromatic chemicals and liquid fuels from oxygenated hydrocarbons such as carbohydrates, sugars, sugar alcohols, sugar degradation products, and the like; and methods, catalysts, and reactor systems for producing the mixture of oxygenates from oxygenated hydrocarbons such as carbohydrates, sugars, sugar alcohols, sugar degradation products, and the like. The disclosed catalysts for preparing the mixture of oxygenates comprise a Ni.sub.nSn.sub.m alloy and a crystalline aluminamore » support.« less

Production of aromatics from di- and polyoxygenates

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

Beck, Taylor; Blank, Brian; Jones, Casey

Methods, catalysts, and reactor systems for producing in high yield aromatic chemicals and liquid fuels from a mixture of oxygenates comprising di- and polyoxygenates are disclosed. Also disclosed are methods, catalysts, and reactor systems for producing aromatic chemicals and liquid fuels from oxygenated hydrocarbons such as carbohydrates, sugars, sugar alcohols, sugar degradation products, and the like; and methods, catalysts, and reactor systems for producing the mixture of oxygenates from oxygenated hydrocarbons such as carbohydrates, sugars, sugar alcohols, sugar degradation products, and the like. The disclosed catalysts for preparing the mixture of oxygenates comprise a Group VIII metal and a crystallinemore » alumina support.« less

Non-precious metal catalysts prepared from precursor comprising cyanamide

DOEpatents

Chung, Hoon Taek; Zelenay, Piotr

2015-10-27

Catalyst comprising graphitic carbon and methods of making thereof; said graphitic carbon comprising a metal species, a nitrogen-containing species and a sulfur containing species. A catalyst for oxygen reduction reaction for an alkaline fuel cell was prepared by heating a mixture of cyanamide, carbon black, and a salt selected from an iron sulfate salt and an iron acetate salt at a temperature of from about 700.degree. C. to about 1100.degree. C. under an inert atmosphere. Afterward, the mixture was treated with sulfuric acid at elevated temperature to remove acid soluble components, and the resultant mixture was heated again under an inert atmosphere at the same temperature as the first heat treatment step.

Partial oxidation catalyst

DOEpatents

Krumpelt, Michael; Ahmed, Shabbir; Kumar, Romesh; Doshi, Rajiv

2000-01-01

A two-part catalyst comprising a dehydrogenation portion and an oxide-ion conducting portion. The dehydrogenation portion is a group VIII metal and the oxide-ion conducting portion is selected from a ceramic oxide crystallizing in the fluorite or perovskite structure. There is also disclosed a method of forming a hydrogen rich gas from a source of hydrocarbon fuel in which the hydrocarbon fuel contacts a two-part catalyst comprising a dehydrogenation portion and an oxide-ion conducting portion at a temperature not less than about 400.degree. C. for a time sufficient to generate the hydrogen rich gas while maintaining CO content less than about 5 volume percent. There is also disclosed a method of forming partially oxidized hydrocarbons from ethanes in which ethane gas contacts a two-part catalyst comprising a dehydrogenation portion and an oxide-ion conducting portion for a time and at a temperature sufficient to form an oxide.

Catalysts and methods of using the same

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

Slowing, Igor Ivan; Kandel, Kapil

2017-02-14

The present invention provides a catalyst including a mesoporous silica nanoparticle and a catalytic material comprising iron. In various embodiments, the present invention provides methods of using and making the catalyst. In some examples, the catalyst can be used to hydrotreat fatty acids or to selectively remove fatty acids from feedstocks.

Metallocene catalyst containing bulky organic group

DOEpatents

Marks, T.J.; Ja, L.; Yang, X.

1996-03-26

An ionic metallocene catalyst for olefin polymerization which comprises: (1) a cyclopentadienyl-type ligand, a Group IVB transition metal, and alkyl, aryl, or hydride substituents, as a cation, and (2) a weakly coordinating anion comprising boron substituted with halogenated, such as tetrafluoro-aryl substituents preferably containing silylalkyl substitution, such as para-silyl t-butyldimethyl.

Metallocene catalyst containing bulky organic group

DOEpatents

Marks, Tobin J.; Ja, Li; Yang, Xinmin

1996-03-26

An ionic metallocene catalyst for olefin polymerization which comprises: (1) a cyclopentadienyl-type ligand, a Group IVB transition metal, and alkyl, aryl, or hydride substituents, as a cation, and (2) a weakly coordinating anion comprising boron substituted with halogenated, such as tetra fluoro, aryl substituents preferably containing silylalkyl substitution, such as para-silyl t-butyldimethyl.

Conversion of 2,3-butanediol to butadiene

DOEpatents

Lilga, Michael A.; Frye, Jr, John G.; Lee, Suh-Jane; Albrecht, Karl O.

2016-09-06

A composition comprising 2,3-butanediol is dehydrated to methyl vinyl carbinol and/or 1,3-butadiene by exposure to a catalyst comprising (a) M.sub.xO.sub.y wherein M is a rare earth metal, a group IIIA metal, Zr, or a combination thereof, and x and y are based upon an oxidation state of M, or (b) M.sup.3.sub.a(PO.sub.4).sub.b where M.sup.3 is a group IA, a group IIA metal, a group IIIA metal, or a combination thereof, and a and b are based upon the oxidation state of M.sup.3. Embodiments of the catalyst comprising M.sub.xO.sub.y may further include M.sup.2, wherein M.sup.2 is a rare earth metal, a group IIA metal, Zr, Al, or a combination thereof. In some embodiments, 2,3-butanediol is dehydrated to methyl vinyl carbinol and/or 1,3-butadiene by a catalyst comprising M.sub.xO.sub.y, and the methyl vinyl carbinol is subsequently dehydrated to 1,3-butadiene by exposure to a solid acid catalyst.

Methods for polymer synthesis

DOEpatents

Allen, Scott D.; Simoneau, Christopher A.; Keefe, William D.; Conuel, Jeff R.

2016-12-06

The present invention provides methods for reducing induction periods in epoxide-CO.sub.2 copolymerizations. In certain embodiments, the methods include the step of contacting an epoxide with CO.sub.2 in the presence of two catalysts: an epoxide hydrolysis catalyst and an epoxide CO.sub.2 copolymerization catalyst. In another aspect, the invention provides catalyst compositions comprising a mixture of an epoxide hydrolysis catalyst and an epoxide CO.sub.2 copolymerization catalyst.

Process for producing ethanol from syngas

DOEpatents

Krause, Theodore R; Rathke, Jerome W; Chen, Michael J

2013-05-14

The invention provides a method for producing ethanol, the method comprising establishing an atmosphere containing methanol forming catalyst and ethanol forming catalyst; injecting syngas into the atmosphere at a temperature and for a time sufficient to produce methanol; and contacting the produced methanol with additional syngas at a temperature and for a time sufficient to produce ethanol. The invention also provides an integrated system for producing methanol and ethanol from syngas, the system comprising an atmosphere isolated from the ambient environment; a first catalyst to produce methanol from syngas wherein the first catalyst resides in the atmosphere; a second catalyst to product ethanol from methanol and syngas, wherein the second catalyst resides in the atmosphere; a conduit for introducing syngas to the atmosphere; and a device for removing ethanol from the atmosphere. The exothermicity of the method and system obviates the need for input of additional heat from outside the atmosphere.

Catalytic conversion of alcohols to hydrocarbons with low benzene content

DOEpatents

Narula, Chaitanya K.; Davison, Brian H.; Keller, Martin

2016-09-06

A method for converting an alcohol to a hydrocarbon fraction having a lowered benzene content, the method comprising: converting said alcohol to a hydrocarbon fraction by contacting said alcohol, under conditions suitable for converting said alcohol to said hydrocarbon fraction, with a metal-loaded zeolite catalyst catalytically active for converting said alcohol to said hydrocarbon fraction, and contacting said hydrocarbon fraction with a benzene alkylation catalyst, under conditions suitable for alkylating benzene, to form alkylated benzene product in said hydrocarbon fraction. Also described is a catalyst composition useful in the method, comprising a mixture of (i) a metal-loaded zeolite catalyst catalytically active for converting said alcohol to said hydrocarbon, and (ii) a benzene alkylation catalyst, in which (i) and (ii) may be in a mixed or separated state. A reactor for housing the catalyst and conducting the reaction is also described.

Catalytic conversion of alcohols to hydrocarbons with low benzene content

DOEpatents

Narula, Chaitanya K.; Davison, Brian H.; Keller, Martin

2016-03-08

A method for converting an alcohol to a hydrocarbon fraction having a lowered benzene content, the method comprising: converting said alcohol to a hydrocarbon fraction by contacting said alcohol, under conditions suitable for converting said alcohol to said hydrocarbon fraction, with a metal-loaded zeolite catalyst catalytically active for converting said alcohol to said hydrocarbon fraction, and contacting said hydrocarbon fraction with a benzene alkylation catalyst, under conditions suitable for alkylating benzene, to form alkylated benzene product in said hydrocarbon fraction. Also described is a catalyst composition useful in the method, comprising a mixture of (i) a metal-loaded zeolite catalyst catalytically active for converting said alcohol to said hydrocarbon, and (ii) a benzene alkylation catalyst, in which (i) and (ii) may be in a mixed or separated state. A reactor for housing the catalyst and conducting the reaction is also described.

Hydrocracking of cumene over Ni/Al 2O 3 as influenced by CeO 2 doping and γ-irradiation

NASA Astrophysics Data System (ADS)

El-Shobaky, G. A.; Doheim, M. M.; Ghozza, A. M.

2004-01-01

Cumene hydrocracking was carried out over pure and doped Ni/Al 2O 3 solids and also, on these solids after exposure to different doses of γ-rays between 0.4 and 1.6 MGy. The dopant concentration was varied between 1 and 4 mol% CeO 2. Pure and doped samples were subjected to heat treatment at 400°C and cumene hydrocracking reaction was carried out using various solids at temperatures between 250°C and 400°C by means of micropulse technique. The results showed that both CeO 2 doping and γ-irradiation of the investigated system brought about an increase in its specific surface area. γ-irradiation of pure samples increased their catalytic activities effectively. However, the doping caused a decrease in the catalytic activity. γ-irradiation of the doped samples brought about a net decrease in the catalytic activity. The catalytic reaction products over different investigated solids were ethylbenzene as a major product together with different amounts of toluene, benzene and C 1-C 3 gaseous hydrocarbons. The selectivity towards the formation of various reaction products varies with the reaction temperature, doping and γ-irradiation.

Effect of pretreating of host oil on coprocessing

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

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

1995-12-31

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

Attrition resistant Fischer-Tropsch catalyst and support

DOEpatents

Singleton, Alan H.; Oukaci, Rachid; Goodwin, James G.

2004-05-25

A catalyst support having improved attrition resistance and a catalyst produced therefrom. The catalyst support is produced by a method comprising the step of treating calcined .gamma.-alumina having no catalytic material added thereto with an acidic aqueous solution having an acidity level effective for increasing the attrition resistance of the calcined .gamma.-alumina.

Method of preparing meso-haloalkylporphyrins

DOEpatents

Wijesekera, Tilak; Lyons, James E.; Ellis, Jr., Paul E.; Bhinde, Manoj V.

1998-01-01

Transition metal complexes of meso-haloalkylporphyrins, wherein the haloalkyl groups contain 2 to 8 carbon atoms have been found to be highly effective catalysts for oxidation of alkanes and for the decomposition of hydroperoxides. Also disclosed is a process for the preparation of meso-halocarbyl-porphyrins which comprises contacting a halocarbyl dipyrromethane with a halocarbyl-substituted aldehyde in the presence of an acid granular solid catalyst. Also disclosed is a process for the preparation of meso-halocarbyl-porphyrins which comprises contacting a halocarbyl dipyrromethane with a halocarbyl-substituted aldehyde in the presence of an acid granular solic catalyst.

Methods of fabrication of graphene nanoribbons

DOEpatents

Zhang, Yuegang

2015-06-23

Methods of fabricating graphene nanoribbons include depositing a catalyst layer on a substrate. A masking layer is deposited on the catalyst layer. The masking layer and the catalyst layer are etched to form a structure on the substrate, the structure comprising a portion of the catalyst layer and a portion of the masking layer disposed on the catalyst layer, with sidewalls of the catalyst layer being exposed. A graphene layer is formed on a sidewall of the catalyst layer with a carbon-containing gas.

Prospects of pyrolysis oil from plastic waste as fuel for diesel engines: A review

NASA Astrophysics Data System (ADS)

Mangesh, V. L.; Padmanabhan, S.; Ganesan, S.; PrabhudevRahul, D.; Reddy, T. Dinesh Kumar

2017-05-01

The purpose ofthis study is to review the existing literature about chemical recycling of plastic waste and its potential as fuel for diesel engines. This is a review covering on the field of converting waste plastics into liquid hydrocarbon fuels for diesel engines. Disposal and recycling of waste plastics have become an incremental problem and environmental threat with increasing demand for plastics. One of the effective measures is by converting waste plastic into combustible hydrocarbon liquid as an alternative fuel for running diesel engines. Continued research efforts have been taken by researchers to convert waste plastic in to combustible pyrolysis oil as alternate fuel for diesel engines. An existing literature focuses on the study of chemical structure of the waste plastic pyrolysis compared with diesel oil. Converting waste plastics into fuel oil by different catalysts in catalytic pyrolysis process also reviewed in this paper. The methodology with subsequent hydro treating and hydrocracking of waste plastic pyrolysis oil can reduce unsaturated hydrocarbon bonds which would improve the combustion performance in diesel engines as an alternate fuel.

Solid fuel volatilization to produce synthesis gas

DOEpatents

Schmidt, Lanny D.; Dauenhauer, Paul J.; Degenstein, Nick J.; Dreyer, Brandon J.; Colby, Joshua L.

2014-07-29

A method comprising contacting a carbon and hydrogen-containing solid fuel and a metal-based catalyst in the presence of oxygen to produce hydrogen gas and carbon monoxide gas, wherein the contacting occurs at a temperature sufficiently high to prevent char formation in an amount capable of stopping production of the hydrogen gas and the carbon monoxide gas is provided. In one embodiment, the metal-based catalyst comprises a rhodium-cerium catalyst. Embodiments further include a system for producing syngas. The systems and methods described herein provide shorter residence time and high selectivity for hydrogen and carbon monoxide.

Method for improving catalyst function in auto-thermal and partial oxidation reformer-based processors

DOEpatents

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

2014-08-26

The invention provides a method for reforming fuel, the method comprising contacting the fuel to an oxidation catalyst so as to partially oxidize the fuel and generate heat; warming incoming fuel with the heat while simultaneously warming a reforming catalyst with the heat; and reacting the partially oxidized fuel with steam using the reforming catalyst.

Carbon nanotubes grown on bulk materials and methods for fabrication

DOEpatents

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

2011-11-08

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

Synthesis of terminal alkenes from internal alkenes and ethylene via olefin metathesis

DOEpatents

Schrodi, Yann [Agoura Hills, CA

2011-11-29

This invention relates generally to olefin metathesis, and more particularly relates to the synthesis of terminal alkenes from internal alkenes using a cross-metathesis reaction catalyzed by a selected olefin metathesis catalyst. In one embodiment of the invention, for example, a method is provided for synthesizing a terminal olefin, the method comprising contacting an olefinic substrate comprised of at least one internal olefin with ethylene, in the presence of a metathesis catalyst, wherein the catalyst is present in an amount that is less than about 1000 ppm relative to the olefinic substrate, and wherein the metathesis catalyst has the structure of formula (II) ##STR00001## wherein the various substituents are as defined herein. The invention has utility, for example, in the fields of catalysis, organic synthesis, and industrial chemistry.

Synthesis of terminal alkenes from internal alkenes and ethylene via olefin metathesis

DOEpatents

Schrodi, Yann

2013-07-09

This invention relates generally to olefin metathesis, and more particularly relates to the synthesis of terminal alkenes from internal alkenes using a cross-metathesis reaction catalyzed by a selected olefin metathesis catalyst. In one embodiment of the invention, for example, a method is provided for synthesizing a terminal olefin, the method comprising contacting an olefinic substrate comprised of at least one internal olefin with ethylene, in the presence of a metathesis catalyst, wherein the catalyst is present in an amount that is less than about 1000 ppm relative to the olefinic substrate, and wherein the metathesis catalyst has the structure of formula (II) ##STR00001## wherein the various substituents are as defined herein. The invention has utility, for example, in the fields of catalysis, organic synthesis, and industrial chemistry.

Synthesis of terminal alkenes from internal alkenes and ethylene via olefin metathesis

DOEpatents

Schrodi, Yann

2016-02-09

This invention relates generally to olefin metathesis, and more particularly relates to the synthesis of terminal alkenes from internal alkenes using a cross-metathesis reaction catalyzed by a selected olefin metathesis catalyst. In one embodiment of the invention, for example, a method is provided for synthesizing a terminal olefin, the method comprising contacting an olefinic substrate comprised of at least one internal olefin with ethylene, in the presence of a metathesis catalyst, wherein the catalyst is present in an amount that is less than about 1000 ppm relative to the olefinic substrate, and wherein the metathesis catalyst has the structure of formula (II) ##STR00001## wherein the various substituents are as defined herein. The invention has utility, for example, in the fields of catalysis, organic synthesis, and industrial chemistry.

Synthesis of terminal alkenes from internal alkenes and ethylene via olefin metathesis

DOEpatents

Schrodi, Yann

2015-09-22

This invention relates generally to olefin metathesis, and more particularly relates to the synthesis of terminal alkenes from internal alkenes using a cross-metathesis reaction catalyzed by a selected olefin metathesis catalyst. In one embodiment of the invention, for example, a method is provided for synthesizing a terminal olefin, the method comprising contacting an olefinic substrate comprised of at least one internal olefin with ethylene, in the presence of a metathesis catalyst, wherein the catalyst is present in an amount that is less than about 1000 ppm relative to the olefinic substrate, and wherein the metathesis catalyst has the structure of formula (II) ##STR00001## wherein the various substituents are as defined herein. The invention has utility, for example, in the fields of catalysis, organic synthesis, and industrial chemistry.

Catalyst and process for converting synthesis gas to liquid motor fuels

DOEpatents

Coughlin, Peter K.

1987-01-01

The addition of an inert metal component, such as gold, silver or copper, to a Fischer-Tropsch catalyst comprising cobalt enables said catalyst to convert synthesis gas to liquid motor fuels at about 240.degree.-370.degree. C. with advantageously reduced selectivity of said cobalt for methane in said conversion. The catalyst composition can advantageously include a support component, such as a molecular sieve, co-catalyst/support component or a combination of such support components.

Catalyst for converting synthesis gas to liquid motor fuels

DOEpatents

Coughlin, Peter K.

1986-01-01

The addition of an inert metal component, such as gold, silver or copper, to a Fischer-Tropsch catalyst comprising cobalt enables said catalyst to convert synthesis gas to liquid motor fuels at about 240.degree.-370.degree. C. with advantageously reduced selectivity of said cobalt for methane in said conversion. The catalyst composition can advantageously include a support component, such as a molecular sieve, co-catalyst/support component or a combination of such support components.

Semipermeable polymers and method for producing same

DOEpatents

Buschmann, Wayne E [Boulder, CO

2012-04-03

A polyamide membrane comprising reaction product of an anhydrous solution comprising an anhydrous solvent, at least one polyfunctional secondary amine and a pre-polymer deposition catalyst; and an anhydrous, organic solvent solution comprising a polyfunctional aromatic amine-reactive reactant comprising one ring. A composite semipermeable membrane comprising the polyamide membrane on a porous support. A method of making a composite semipermeable membrane by coating a porous support with an anhydrous solution comprising an anhydrous solvent, a polyfunctional secondary amine and a pre-polymer deposition catalyst, to form an activated pre-polymer layer on the porous support and contacting the activated pre-polymer layer with an anhydrous, organic solvent solution comprising a polyfunctional amine-reactive reactant to interfacially condense the amine-reactive reactant with the polyfunctional secondary amine, thereby forming a cross-linked, interfacial polyamide layer on the porous support. A method of impregnating a composite semipermeable membrane with nanoparticles selected from heavy metals and/or oxides of heavy metals.

Method for making oxygen-reducing catalyst layers

DOEpatents

O'Brien, Dennis P.; Schmoeckel, Alison K.; Vernstrom, George D.; Atanasoski, Radoslav; Wood, Thomas E.; O'Neill, David G.

2010-06-22

Methods are provided for making oxygen-reducing catalyst layers, which include simultaneous or sequential stops of physical vapor depositing an oxygen-reducing catalytic material onto a substrate, the catalytic material comprising a transition metal that is substantially free of platinum; and thermally treating the catalytic material. At least one of the physical vapor deposition and the thermal treatment is performed in a processing environment comprising a nitrogen-containing gas.

Novel Catalyst for the Chirality Selective Synthesis of Single Walled Carbon Nanotubes

DTIC Science & Technology

2015-05-12

hierarchical structures comprising nitrogen- doped reduced GO (rGO) and acid- oxidized SWCNTs was produced using a linear hydrothermal microreactor. Fiber...structures comprising nitrogen- doped reduced GO (rGO) and acidoxidized SWCNTs was produced using a linear hydrothermal microreactor. Fiber micro... doped into Co/SiO2 catalysts to change their chirality selectivity. Further, enrichment of (9,8) nanotubes was carried out by extraction using fluorene

Method for making methanol

DOEpatents

Mednick, R. Lawrence; Blum, David B.

1987-01-01

Methanol is made in a liquid-phase methanol reactor by entraining a methanol-forming catalyst in an inert liquid and contacting said entrained catalyst with a synthesis gas comprising hydrogen and carbon monoxide.

Catalysts for conversion of syngas to liquid motor fuels

DOEpatents

Rabo, Jule A.; Coughlin, Peter K.

1987-01-01

Synthesis gas comprising carbon monoxide and hydrogen is converted to C.sub.5.sup.+ hydrocarbons suitable for use as liquid motor fuels by contact with a dual catalyst composition capable of ensuring the production of only relatively minor amounts of heavy products boiling beyond the diesel oil range. The catalyst composition, having desirable stability during continuous production operation, employs a Fischer-Tropsch catalyst, together with a co-catalyst/support component. The latter component is a steam-stabilized zeolite Y catalyst of hydrophobic character, desirably in acid-extracted form.

Techno-economic and resource analysis of hydroprocessed renewable jet fuel

DOE PAGES

Tao, Ling; Milbrandt, Anelia; Zhang, Yanan; ...

2017-11-09

Biomass-derived jet fuel is an alternative jet fuel (AJF) showing promise of reducing the dependence on fossil fuel and greenhouse gas emissions. Hydroprocessed esters and fatty acids (HEFA) concept is also known as one of the pathways for producing bio jet fuel. HEFA fuel was approved by the American Society for Testing and Materials in 2011, and can be blended up to 50% with conventional jet fuel. Since then, several HEFA economic and life-cycle assessments have been published in literature. However, there have been limited analyses on feedstock availability, composition, and their impact on hydrocarbon yield (particularly jet blendstock yield)more » and overall process economics. Our study examines over 20 oil feedstocks, their geographic distribution and production levels, oil yield, prices, and chemical composition. The results of our compositional analysis, thus, indicate that most oils contain mainly C16 and C18 fatty acids except pennycress, yellow grease, and mustard, which contain higher values and thus would require hydrocracking to improve jet fuel production. Coconut oil has a large content of shorter carbon fatty acids, making it a good feedstock candidate for renewable gasoline instead of jet substitutes' production. Techno-economic analysis (TEA) was performed for five selected oil feedstocks - camelina, pennycress, jatropha, castor bean, and yellow grease - using the HEFA process concept. The resource analysis indicates that oil crops currently grown in the United States (namely soybean) have relatively low oil yield when compared to oil crops grown in other parts of the world, such as palm, coconut, and jatropha. Also, non-terrestrial oil sources, such as animal fats and greases, have relatively lower prices than terrestrial oil crops. The minimum jet fuel selling price for these five resources ranges between $3.8 and $11.0 per gallon. The results of our TEA and resource studies indicate the key cost drivers for a biorefinery converting oil to jet hydrocarbons are as follows: oil price, conversion plant capacity, fatty acid profile, addition of hydrocracker, and type of hydroprocessing catalysts.« less

Techno-economic and resource analysis of hydroprocessed renewable jet fuel

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

Tao, Ling; Milbrandt, Anelia; Zhang, Yanan

Biomass-derived jet fuel is an alternative jet fuel (AJF) showing promise of reducing the dependence on fossil fuel and greenhouse gas emissions. Hydroprocessed esters and fatty acids (HEFA) concept is also known as one of the pathways for producing bio jet fuel. HEFA fuel was approved by the American Society for Testing and Materials in 2011, and can be blended up to 50% with conventional jet fuel. Since then, several HEFA economic and life-cycle assessments have been published in literature. However, there have been limited analyses on feedstock availability, composition, and their impact on hydrocarbon yield (particularly jet blendstock yield)more » and overall process economics. Our study examines over 20 oil feedstocks, their geographic distribution and production levels, oil yield, prices, and chemical composition. The results of our compositional analysis, thus, indicate that most oils contain mainly C16 and C18 fatty acids except pennycress, yellow grease, and mustard, which contain higher values and thus would require hydrocracking to improve jet fuel production. Coconut oil has a large content of shorter carbon fatty acids, making it a good feedstock candidate for renewable gasoline instead of jet substitutes' production. Techno-economic analysis (TEA) was performed for five selected oil feedstocks - camelina, pennycress, jatropha, castor bean, and yellow grease - using the HEFA process concept. The resource analysis indicates that oil crops currently grown in the United States (namely soybean) have relatively low oil yield when compared to oil crops grown in other parts of the world, such as palm, coconut, and jatropha. Also, non-terrestrial oil sources, such as animal fats and greases, have relatively lower prices than terrestrial oil crops. The minimum jet fuel selling price for these five resources ranges between $3.8 and $11.0 per gallon. The results of our TEA and resource studies indicate the key cost drivers for a biorefinery converting oil to jet hydrocarbons are as follows: oil price, conversion plant capacity, fatty acid profile, addition of hydrocracker, and type of hydroprocessing catalysts.« less

Bimetal catalysts

DOEpatents

Ng, K. Y. Simon; Salley, Steve O.; Wang, Huali

2017-10-03

A catalyst comprises a carbide or nitride of a metal and a promoter element. The metal is selected from the group consisting of Mo, W, Co, Fe, Rh or Mn, and the promoter element is selected from the group consisting of Ni, Co, Al, Si, S or P, provided that the metal and the promoter element are different. The catalyst also comprises a mesoporous support having a surface area of at least about 170 m.sup.2 g.sup.-1, wherein the carbide or nitride of the metal and the promoter element is supported by the mesoporous support, and is in a non-sulfided form and in an amorphous form.

Polymer system for gettering hydrogen

DOEpatents

Shepodd, Timothy Jon; Whinnery, LeRoy L.

2000-01-01

A novel composition comprising organic polymer molecules having carbon-carbon double bonds, for removing hydrogen from the atmosphere within enclosed spaces. Organic polymers molecules containing carbon-carbon double bonds throughout their structures, preferably polybutadiene, polyisoprene and derivatives thereof, intimately mixed with an insoluble catalyst composition, comprising a hydrogenation catalyst and a catalyst support, preferably Pd supported on carbon, provide a hydrogen getter composition useful for removing hydrogen from enclosed spaces even in the presence of contaminants such as common atmospheric gases, water vapor, carbon dioxide, ammonia, oil mists, and water. The hydrogen getter composition disclosed herein is particularly useful for removing hydrogen from enclosed spaces containing potentially explosive mixtures of hydrogen and oxygen.

Polymer formulations for gettering hydrogen

DOEpatents

Shepodd, Timothy Jon; Whinnery, LeRoy L.

1998-11-17

A novel composition comprising organic polymer molecules having carbon-carbon double bonds, for removing hydrogen from the atmosphere within enclosed spaces. Organic polymers molecules containing carbon-carbon double bonds throughout their structures, preferably polybutadiene, polyisoprene and derivatives thereof, intimately mixed with an insoluble catalyst composition, comprising a hydrogenation catalyst and a catalyst support, preferably Pd supported on carbon, provide a hydrogen getter composition useful for removing hydrogen from enclosed spaces even in the presence of contaminants such as common atmospheric gases, water vapor, carbon dioxide, ammonia, oil mists, and water. The hydrogen getter composition disclosed herein is particularly useful for removing hydrogen from enclosed spaces containing potentially explosive mixtures of hydrogen and oxygen.

Nitrogen oxides storage catalysts containing cobalt

DOEpatents

Lauterbach, Jochen; Snively, Christopher M.; Vijay, Rohit; Hendershot, Reed; Feist, Ben

2010-10-12

Nitrogen oxides (NO.sub.x) storage catalysts comprising cobalt and barium with a lean NO.sub.x storage ratio of 1.3 or greater. The NO.sub.x storage catalysts can be used to reduce NO.sub.x emissions from diesel or gas combustion engines by contacting the catalysts with the exhaust gas from the engines. The NO.sub.x storage catalysts can be one of the active components of a catalytic converter, which is used to treat exhaust gas from such engines.

Nanostructured catalyst supports

DOEpatents

Zhu, Yimin; Goldman, Jay L.; Qian, Baixin; Stefan, Ionel C.

2012-10-02

The present invention relates to SiC nanostructures, including SiC nanopowder, SiC nanowires, and composites of SiC nanopowder and nanowires, which can be used as catalyst supports in membrane electrode assemblies and in fuel cells. The present invention also relates to composite catalyst supports comprising nanopowder and one or more inorganic nanowires for a membrane electrode assembly.

Method for the photocatalytic conversion of methane

DOEpatents

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

1998-02-24

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

Method for the photocatalytic conversion of methane

DOEpatents

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

1998-01-01

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

Catalysts and process for hydrogenolysis of sugar alcohols to polyols

DOEpatents

Chopade, Shubham P [East Lansing, MI; Miller, Dennis J [Okemos, MI; Jackson, James E [Haslett, MI; Werpy, Todd A [West Richland, WA; Frye, Jr., John G [Richland, WA; Zacher, Alan H [Richland, WA

2001-09-18

The present invention provides a process for preparation of low molecular weight polyols from high molecular weight polyols in a hydrogenolysis reaction under elevated temperature and hydrogen pressure. The process comprises providing in a reaction mixture the polyols, a base, and a metal catalyst prepared by depositing a transition metal salt on an inert support, reducing the metal salt to the metal with hydrogen, and passivating the metal with oxygen, and wherein the catalyst is reduced with hydrogen prior to the reaction. In particular, the process provides for the preparation of glycerol, propylene glycol, and ethylene glycol from sugar alcohols such as sorbitol or xylitol. In a preferred process, the metal catalyst comprises ruthenium which is deposited on an alumina, titania, or carbon support, and the dispersion of the ruthenium on the support increases during the hydrogenolysis reaction.

Catalytic conversion of hydrocarbons to hydrogen and high-value carbon

DOEpatents

Shah, Naresh; Panjala, Devadas; Huffman, Gerald P.

2005-04-05

The present invention provides novel catalysts for accomplishing catalytic decomposition of undiluted light hydrocarbons to a hydrogen product, and methods for preparing such catalysts. In one aspect, a method is provided for preparing a catalyst by admixing an aqueous solution of an iron salt, at least one additional catalyst metal salt, and a suitable oxide substrate support, and precipitating metal oxyhydroxides onto the substrate support. An incipient wetness method, comprising addition of aqueous solutions of metal salts to a dry oxide substrate support, extruding the resulting paste to pellet form, and calcining the pellets in air is also discloses. In yet another aspect, a process is provided for producing hydrogen from an undiluted light hydrocarbon reactant, comprising contacting the hydrocarbon reactant with a catalyst as described above in a reactor, and recovering a substantially carbon monoxide-free hydrogen product stream. In still yet another aspect, a process is provided for catalytic decomposition of an undiluted light hydrocarbon reactant to obtain hydrogen and a valuable multi-walled carbon nanotube coproduct.

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

DOEpatents

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

2013-07-09

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

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

DOEpatents

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

2012-05-08

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

Oxygen-reducing catalyst layer

DOEpatents

O'Brien, Dennis P [Maplewood, MN; Schmoeckel, Alison K [Stillwater, MN; Vernstrom, George D [Cottage Grove, MN; Atanasoski, Radoslav [Edina, MN; Wood, Thomas E [Stillwater, MN; Yang, Ruizhi [Halifax, CA; Easton, E Bradley [Halifax, CA; Dahn, Jeffrey R [Hubley, CA; O'Neill, David G [Lake Elmo, MN

2011-03-22

An oxygen-reducing catalyst layer, and a method of making the oxygen-reducing catalyst layer, where the oxygen-reducing catalyst layer includes a catalytic material film disposed on a substrate with the use of physical vapor deposition and thermal treatment. The catalytic material film includes a transition metal that is substantially free of platinum. At least one of the physical vapor deposition and the thermal treatment is performed in a processing environment comprising a nitrogen-containing gas.

CATALYTIC STEAM REFORMING OF CHLOROCARBONS: CATALYST COMPARISONS. (R826694C633)

EPA Science Inventory

Catalyst candidates for steam reforming chlorocarbons have been screened for activity using methyl chloride as a model reactant. At 500°C, a H₂O/C ratio of about 10 and a GHSV of 254 000 h^-1, catalysts comprising 0.5% loading of the metals ...

CATALYTIC STEAM REFORMING OF CHLOROCARBONS: CATALYST COMPARISONS. (R822721C633)

EPA Science Inventory

Catalyst candidates for steam reforming chlorocarbons have been screened for activity using methyl chloride as a model reactant. At 500°C, a H₂O/C ratio of about 10 and a GHSV of 254 000 h^-1, catalysts comprising 0.5% loading of the metals o...

Polymer formulations for gettering hydrogen

DOEpatents

Shepodd, T.J.; Whinnery, L.L.

1998-11-17

A novel composition is described comprising organic polymer molecules having carbon-carbon double bonds, for removing hydrogen from the atmosphere within enclosed spaces. Organic polymers molecules containing carbon-carbon double bonds throughout their structures, preferably polybutadiene, polyisoprene and derivatives thereof, intimately mixed with an insoluble catalyst composition, comprising a hydrogenation catalyst and a catalyst support, preferably Pd supported on carbon, provide a hydrogen getter composition useful for removing hydrogen from enclosed spaces even in the presence of contaminants such as common atmospheric gases, water vapor, carbon dioxide, ammonia, oil mists, and water. The hydrogen getter composition disclosed herein is particularly useful for removing hydrogen from enclosed spaces containing potentially explosive mixtures of hydrogen and oxygen. 1 fig.

Production of alpha-hydroxy carboxylic acids and esters from higher sugars using tandem catalyst systems

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

Orazov, Marat; Davis, Mark E.

The present disclosure is directed to methods and composition used in the preparation of alpha-hydroxy carboxylic acids and esters from higher sugars using a tandem catalyst system comprising retro-aldol catalysts and Lewis acid catalysts. In some embodiments, these alpha-hydroxy carboxylic acids may be prepared from pentoses and hexoses. The retro-aldol and Lewis catalysts may be characterized by their respective ability to catalyze a 1,2-carbon shift reaction and a 1,2-hydride shift reaction on an aldose or ketose substrate.

Chemicals from low temperature liquid-phase cracking of coals

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

Sato, Y.; Kodera, Y.; Kamo, T.

1999-07-01

Mild gasification and low temperature pyrolysis are considered to be the most promising process for high-moisture subbituminous and lignite coal to produce upgraded solid fuel with high heating value and low sulfur, and to produce a useful liquid product. However effective technology to prevent spontaneous combustion of solid product and to utilize oxygen-rich liquid product has not yet been reported to enhance commercial feasibility of these process. In this study, liquid-phase cracking of low rank coal at 350--450 C under 2 MPa of initial nitrogen atmosphere has been studied to produce upgraded coal and value added liquid product. Liquid-phase crackingmore » of Wyoming subbituminous Buckskin coal using iron oxide catalyst in the presence of t-decalin at 440C gave 10 wt% of liquid product, 12 wt% of gases and 74 wt% of upgraded coal with small amount of water. Gaseous product consisted of mainly carbon dioxide (62wt%) and methane. Therefore, cracking of carboxylic function took place effectively in these conditions. Liquid product contains BTX, phenols and alkylphenols. Concentrated chemicals of BTX, phenol and cresols from the liquid products by hydrocracking and hydrotreating will be discussed.« less

Methods for dehydration of sugars and sugar alcohols

DOEpatents

Holladay, Johnathan E [Kennewick, WA; Hu, Jianli [Kennewick, WA; Zhang, Xinjie [Burlington, MA; Wang, Yong [Richland, WA

2010-08-10

The invention includes a method of dehydration of a sugar using a dehydration catalyst and a co-catalyst within a reactor. A sugar is introduced and H.sub.2 is flowed through the reactor at a pressure of less than or equal to about 300 psig to convert at least some of the sugar into an anhydrosugar product. The invention includes a process for producing isosorbide. A starting material comprising sorbitol is flowed into a reactor. H.sub.2 is counter flowed through the reactor. The starting material is exposed to a catalyst in the presence of a co-catalyst which comprises at least one metal. The exposing is conducted at a hydrogen pressure of less than or equal to 300 psig within the reactor and the hydrogen removes at least some of any water present during the exposing and inhibits formation of colored byproducts.

Coal liquefaction and hydrogenation

DOEpatents

Schindler, Harvey D.; Chen, James M.

1985-01-01

Disclosed is a coal liquefaction process using two stages. The first stage liquefies the coal and maximizes the product while the second stage hydrocracks the remainder of the coal liquid to produce solvent.

Catalysts for the selective oxidation of hydrogen sulfide to sulfur

DOEpatents

Srinivas, Girish; Bai, Chuansheng

2000-08-08

This invention provides catalysts for the oxidation of hydrogen sulfide. In particular, the invention provides catalysts for the partial oxidation of hydrogen sulfide to elemental sulfur and water. The catalytically active component of the catalyst comprises a mixture of metal oxides containing titanium oxide and one or more metal oxides which can be selected from the group of metal oxides or mixtures of metal oxides of transition metals or lanthanide metals. Preferred metal oxides for combination with TiO.sub.2 in the catalysts of this invention include oxides of V, Cr, Mn, Fe, Co, Ni, Cu, Nb, Mo, Tc, Ru, Rh, Hf, Ta, W, Au, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu. Catalysts which comprise a homogeneous mixture of titanium oxide and niobium (Nb) oxide are also provided. A preferred method for preparing the precursor homogenous mixture of metal hydroxides is by coprecipitation of titanium hydroxide with one or more other selected metal hydroxides. Catalysts of this invention have improved activity and/or selectivity for elemental sulfur production. Further improvements of activity and/or selectivity can be obtained by introducing relatively low amounts (up to about 5 mol %)of a promoter metal oxide (preferably of metals other than titanium and that of the selected second metal oxide) into the homogeneous metal/titanium oxide catalysts of this invention.

System for reactivating catalysts

DOEpatents

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

2010-03-02

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

Fischer-Tropsch activity for non-promoted cobalt-on-alumina catalysts

DOEpatents

Singleton, Alan H.; Oukaci, Rachid; Goodwin, James G.

2001-01-01

Cobalt catalysts, and processes employing these inventive catalysts, for hydrocarbon synthesis. The inventive catalyst comprises cobalt on an alumina support and is not promoted with any noble or near noble metals. In one aspect of the invention, the alumina support preferably includes a dopant in an amount effective for increasing the activity of the inventive catalyst. The dopant is preferably a titanium dopant. In another aspect of the invention, the cobalt catalyst is preferably reduced in the presence of hydrogen at a water vapor partial pressure effective to increase the activity of the cobalt catalyst for hydrocarbon synthesis. The water vapor partial pressure is preferably in the range of from 0 to about 0.1 atmospheres.

Plasmatron-catalyst system

DOEpatents

Bromberg, Leslie; Cohn, Daniel R.; Rabinovich, Alexander; Alexeev, Nikolai

2004-09-21

A plasmatron-catalyst system. The system generates hydrogen-rich gas and comprises a plasmatron and at least one catalyst for receiving an output from the plasmatron to produce hydrogen-rich gas. In a preferred embodiment, the plasmatron receives as an input air, fuel and water/steam for use in the reforming process. The system increases the hydrogen yield and decreases the amount of carbon monoxide.

Plasmatron-catalyst system

DOEpatents

Bromberg, Leslie; Cohn, Daniel R.; Rabinovich, Alexander; Alexeev, Nikolai

2007-10-09

A plasmatron-catalyst system. The system generates hydrogen-rich gas and comprises a plasmatron and at least one catalyst for receiving an output from the plasmatron to produce hydrogen-rich gas. In a preferred embodiment, the plasmatron receives as an input air, fuel and water/steam for use in the reforming process. The system increases the hydrogen yield and decreases the amount of carbon monoxide.

Cathodes for lithium-air battery cells with acid electrolytes

DOEpatents

Xing, Yangchuan; Huang, Kan; Li, Yunfeng

2016-07-19

In various embodiments, the present disclosure provides a layered metal-air cathode for a metal-air battery. Generally, the layered metal-air cathode comprises an active catalyst layer, a transition layer bonded to the active catalyst layer, and a backing layer bonded to the transition layer such that the transition layer is disposed between the active catalyst layer and the backing layer.

A trifunctional mesoporous silica-based, highly active catalyst for one-pot, three-step cascade reactions.

PubMed

Biradar, Ankush V; Patil, Vijayshinha S; Chandra, Prakash; Doke, Dhananjay S; Asefa, Tewodros

2015-05-18

We report the synthesis of a trifunctional catalyst containing amine, sulphonic acid and Pd nanoparticle catalytic groups anchored on the pore walls of SBA-15. The catalyst efficiently catalyzes one-pot three-step cascade reactions comprising deacetylation, Henry reaction and hydrogenation, giving up to ∼100% conversion and 92% selectivity to the final product.

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

DOEpatents

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

2008-08-05

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

Ruthenium carbonyl catalyst supported on ceric oxide for preparation of olefins from synthesis gas

DOEpatents

Pierantozzi, R.

1985-04-02

A catalyst comprising a ruthenium carbonyl compound deposited on a cerium oxide-containing support material provides for the selective synthesis of low molecular weight olefinic hydrocarbons from mixtures of hydrogen and carbon monoxide.

Ruthenium carbonyl catalyst supported on ceric oxide for preparation of olefins from synthesis gas

DOEpatents

Pierantozzi, Ronald

1985-01-01

A catalyst comprising a ruthenium carbonyl compound deposited on a cerium oxide-containing support material provides for the selective synthesis of low molecular weight olefinic hydrocarbons from mixtures of hydrogen and carbon monoxide.

Neutral bimetallic transition metal phenoxyiminato catalysts and related polymerization methods

DOEpatents

Marks, Tobin J [Evanston, IL; Rodriguez, Brandon A [Evanston, IL; Delferro, Massimiliano [Chicago, IL

2012-08-07

A catalyst composition comprising a neutral bimetallic diphenoxydiiminate complex of group 10 metals or Ni, Pd or Pt is disclosed. The compositions can be used for the preparation of homo- and co-polymers of olefinic monomer compounds.

Transition metal-catalyzed process for addition of amines to carbon-carbon double bonds

DOEpatents

Hartwig, John F.; Kawatsura, Motoi; Loeber, Oliver

2002-01-01

The present invention is directed to a process for addition of amines to carbon-carbon double bonds in a substrate, comprising: reacting an amine with a compound containing at least one carbon-carbon double bond in the presence a transition metal catalyst under reaction conditions effective to form a product having a covalent bond between the amine and a carbon atom of the former carbon-carbon double bond. The transition metal catalyst comprises a Group 8 metal and a ligand containing one or more 2-electron donor atoms. The present invention is also directed to enantioselective reactions of amine compounds with compounds containing carbon-carbon double bonds, and a calorimetric assay to evaluate potential catalysts in these reactions.

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

DOEpatents

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

2011-05-17

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

Electrochemical device for converting carbon dioxide to a reaction product

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

Masel, Richard I.; Chen, Qingmei; Liu, Zengcai

An electrochemical device converts carbon dioxide to a reaction product. The device includes an anode and a cathode, each comprising a quantity of catalyst. The anode and cathode each has reactant introduced thereto. A polymer electrolyte membrane is interposed between the anode and the cathode. At least a portion of the cathode catalyst is directly exposed to gaseous carbon dioxide during electrolysis. The average current density at the membrane is at least 20 mA/cm.sup.2, measured as the area of the cathode gas diffusion layer that is covered by catalyst, and CO selectivity is at least 50% at a cell potentialmore » of 3.0 V. In some embodiments, the polymer electrolyte membrane comprises a polymer in which a constituent monomer is (p-vinylbenzyl)-R, where R is selected from the group consisting of imidazoliums, pyridiniums and phosphoniums. In some embodiments, the polymer electrolyte membrane is a Helper Membrane comprising a polymer containing an imidazolium ligand, a pyridinium ligand, or a phosphonium ligand.« less

Nitrated metalloporphyrins as catalysts for alkane oxidation

DOEpatents

Ellis, P.E. Jr.; Lyons, J.E.

1994-01-18

Compositions of matter comprising nitro-substituted metal complexes of porphyrins are catalysts for the oxidation of alkanes. The metal is iron, chromium, manganese, ruthenium, copper or cobalt. The porphyrin ring has nitro groups attached thereto in meso and/or [beta]-pyrrolic positions.

Nitrated metalloporphyrins as catalysts for alkane oxidation

DOEpatents

Ellis, Jr., Paul E.; Lyons, James E.

1994-01-01

Compositions of matter comprising nitro-substituted metal complexes of porphyrins are catalysts for the oxidation of alkanes. The metal is iron, chromium, manganese, ruthenium, copper or cobalt. The porphyrin ring has nitro groups attached thereto in meso and/or .beta.-pyrrolic positions.

Method of making chalcogen catalysts for polymer electrolyte fuel cells

DOEpatents

Choi, Jong-Ho; Zelenay, Piotr; Wieckowski, Andrzej; Cao, Dianxue

2010-12-14

A method of making an electrode catalyst material using aqueous solutions. The electrode catalyst material includes a support comprising at least one transition metal and at least one chalcogen disposed on a surface of the transition metal. The method includes reducing a metal powder, mixing the metal powder with an aqueous solution containing at least one inorganic compound of the chalcogen to form a mixture, and providing a reducing agent to the mixture to form nanoparticles of the electrode catalyst. The electrode catalyst may be used in a membrane electrode assembly for a fuel cell.

Zeolite-based SCR catalysts and their use in diesel engine emission treatment

DOEpatents

Narula, Chaitanya K.; Yang, Xiaofan

2016-08-02

A catalyst comprising a zeolite loaded with copper ions and at least one trivalent metal ion other than Al.sup.+3, wherein the catalyst decreases NO.sub.x emissions in diesel exhaust. The trivalent metal ions are selected from, for example, trivalent transition metal ions, trivalent main group metal ions, and/or trivalent lanthanide metal ions. In particular embodiments, the catalysts are selected from Cu--Fe-ZSM5, Cu--La-ZSM-5, Fe--Cu--La-ZSM5, Cu--Sc-ZSM-5, and Cu--In-ZSM5. The catalysts are placed on refractory support materials and incorporated into catalytic converters.

Zeolite-based SCR catalysts and their use in diesel engine emission treatment

DOEpatents

Narula, Chaitanya K; Yang, Xiaofan

2015-03-24

A catalyst comprising a zeolite loaded with copper ions and at least one trivalent metal ion other than Al.sup.+3, wherein the catalyst decreases NO.sub.x emissions in diesel exhaust. The trivalent metal ions are selected from, for example, trivalent transition metal ions, trivalent main group metal ions, and/or trivalent lanthanide metal ions. In particular embodiments, the catalysts are selected from Cu--Fe-ZSM5, Cu--La-ZSM-5, Fe--Cu--La-ZSM5, Cu--Sc-ZSM-5, and Cu--In-ZSM5. The catalysts are placed on refractory support materials and incorporated into catalytic converters.

Catalysis using hydrous metal oxide ion exchanges

DOEpatents

Dosch, Robert G.; Stephens, Howard P.; Stohl, Frances V.

1985-01-01

In a process which is catalyzed by a catalyst comprising an active metal on a carrier, said metal being active as a catalyst for the process, an improvement is provided wherein the catalyst is a hydrous, alkali metal or alkaline earth metal titanate, zirconate, niobate or tantalate wherein alkali or alkaline earth metal cations have been exchanged with a catalytically effective amount of cations of said metal.

Catalysis using hydrous metal oxide ion exchangers

DOEpatents

Dosch, R.G.; Stephens, H.P.; Stohl, F.V.

1983-07-21

In a process which is catalyzed by a catalyst comprising an active metal on a carrier, said metal being active as a catalyst for the process, an improvement is provided wherein the catalyst is a hydrous, alkali metal or alkaline earth metal titanate, zirconate, niobate or tantalate wherein alkali or alkaline earth metal cations have been exchanged with a catalytically effective amount of cations of said metal.

Military jet fuel from shale oil

NASA Technical Reports Server (NTRS)

Coppola, E. N.

1980-01-01

Investigations leading to a specification for aviation turbine fuel produced from whole crude shale oil are described. Refining methods involving hydrocracking, hydrotreating, and extraction processes are briefly examined and their production capabilities are assessed.

Mechanistic Insights into Ring Cleavage and Contraction of Benzene over a Titanium Hydride Cluster.

PubMed

Kang, Xiaohui; Luo, Gen; Luo, Lun; Hu, Shaowei; Luo, Yi; Hou, Zhaomin

2016-09-14

Carbon-carbon bond cleavage of benzene by transition metals is of great fundamental interest and practical importance, as this transformation is involved in the production of fuels and other important chemicals in the industrial hydrocracking of naphtha on solid catalysts. Although this transformation is thought to rely on cooperation of multiple metal sites, molecular-level information on the reaction mechanism has remained scarce to date. Here, we report the DFT studies of the ring cleavage and contraction of benzene by a molecular trinuclear titanium hydride cluster. Our studies suggest that the reaction is initiated by benzene coordination, followed by H2 release, C6H6 hydrometalation, repeated C-C and C-H bond cleavage and formation to give a MeC5H4 unit, and insertion of a Ti atom into the MeC5H4 unit with release of H2 to give a metallacycle product. The C-C bond cleavage and ring contraction of toluene can also occur in a similar fashion, though some details are different due to the presence of the methyl substituent. Obviously, the facile release of H2 from the metal hydride cluster to provide electrons and to alter the charge population at the metal centers, in combination with the flexible metal-hydride connections and dynamic redox behavior of the trimetallic framework, has enabled this unusual transformation to occur. This work has not only provided unprecedented insights into the activation and transformation of benzene over a multimetallic framework but it may also offer help in the design of new molecular catalysts for the activation and transformation of inactive aromatics.

Transition metal complexes supported on metal-organic frameworks for heterogeneous catalysts

DOEpatents

Farha, Omar K.; Hupp, Joseph T.; Delferro, Massimiliano; Klet, Rachel C.

2017-02-07

A robust mesoporous metal-organic framework comprising a hafnium-based metal-organic framework and a single-site zirconium-benzyl species is provided. The hafnium, zirconium-benzyl metal-organic framework is useful as a catalyst for the polymerization of an alkene.

Long life hydrocarbon conversion catalyst and method of making

DOEpatents

Tonkovich, Anna Lee Y [Pasco, WA; Wang, Yong [Richland, WA; Gao, Yufei [Kennewick, WA

2002-11-12

The present invention includes a catalyst that has at least four layers, (1) porous support, (2) buffer layer, (3) interfacial layer, and optionally (4) catalyst layer. The buffer layer provides a transition of thermal expansion coefficient from the porous support to the interfacial layer thereby reducing thermal expansion stress as the catalyst is heated to high operating temperatures. The method of the present invention for making the at least three layer catalyst has the steps of (1) selecting a porous support, (2) solution depositing an interfacial layer thereon, and optionally (3) depositing a catalyst material onto the interfacial layer; wherein the improvement comprises (4) depositing a buffer layer between the porous support and the interfacial layer.

Apparatus for purifying exhaust gases of internal combustion engines

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

Kakinuma, O.; Oya, H.

1980-06-03

Apparatus for purifying the exhaust gases of internal combustion engines is disclosed is comprised of a pair of upstream exhaust pipes, a catalytic converter, and a downstream exhaust pipe. The catalytic converter comprises a shell having an inlet chamber, catalyst chamber, and an outlet chamber. The axial lines of the inlet ports are arranged to cross each other in the inlet chamber at a position near, but upstream of, the upstream facing end of said monolithic catalyst element, so that gas flow can diffuse to the entire plane of the element.

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

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

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

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

Catalytic biomass conversion methods, catalysts, and methods of making the same

DOEpatents

Delgass, William Nicholas; Agrawal, Rakesh; Ribeiro, Fabio Henrique; Saha, Basudeb; Yohe, Sara Lynn; Abu-Omar, Mahdi M; Parsell, Trenton; Dietrich, Paul James; Klein, Ian Michael

2017-10-10

Described herein are processes for one-step delignification and hydrodeoxygenation of lignin fraction a biomass feedstock. The lignin feedstock is derived from by-products of paper production and biorefineries. Additionally described is a process for converting biomass-derived oxygenates to lower oxygen-content compounds and/or hydrocarbons in the liquid or vapor phase in a reactor system containing hydrogen and a catalyst comprised of a hydrogenation function and/or an oxophilic function and/or an acid function. Finally, also described herein is a process for converting biomass-derived oxygenates to lower oxygen-content compounds and/or hydrocarbons in the liquid or vapor phase in a reactor system containing hydrogen and a catalyst comprised of a hydrogenation function and/or an oxophilic function and/or an acid function.

Cyano- and polycyanometallo-porphyrins as catalysts for alkane oxidation

DOEpatents

Ellis, P.E. Jr.; Lyons, J.E.

1995-01-17

New compositions of matter comprising cyano-substituted metal complexes of porphyrins are catalysts for the oxidation of alkanes. The metal is iron, chromium, manganese, ruthenium, copper or cobalt. The porphyrin ring has cyano groups attached thereto in meso and/or [beta]-pyrrolic positions.

Cyano- and polycyanometallo-porphyrins as catalysts for alkane oxidation

DOEpatents

Ellis, P.E. Jr.; Lyons, J.E.

1993-05-18

New compositions of matter comprising cyano-substituted metal complexes of porphyrins are catalysts for the oxidation of alkanes. The metal is iron, chromium, manganese, ruthenium, copper or cobalt. The porphyrin ring has cyano groups attached thereto in meso- and/or [beta]-pyrrolic positions.

Catalysts for coal liquefaction processes

DOEpatents

Garg, Diwakar

1986-01-01

Improved catalysts for catalytic solvent refining or hydroliquefaction of non-anthracitic coal at elevated temperatures under hydrogen pressure in a hydrogen donor solvent comprise a combination of zinc or copper, or a compound thereof, and a Group VI or non-ferrous Group VIII metal, or a compound thereof.

Catalysts for coal liquefaction processes

DOEpatents

Garg, D.

1986-10-14

Improved catalysts for catalytic solvent refining or hydroliquefaction of non-anthracitic coal at elevated temperatures under hydrogen pressure in a hydrogen donor solvent comprise a combination of zinc or copper, or a compound thereof, and a Group VI or non-ferrous Group VIII metal, or a compound thereof.

Cyano- and polycyanometallo-porphyrins as catalysts for alkane oxidation

DOEpatents

Ellis, Jr., Paul E.; Lyons, James E.

1993-01-01

New compositions of matter comprising cyano-substituted metal complexes of porphyrins are catalysts for the oxidation of alkanes. The metal is iron, chromium, manganese, ruthenium, copper or cobalt. The porphyrin ring has cyano groups attached thereto in meso and/or .beta.-pyrrolic positions.

Cyano- and polycyanometallo-porphyrins as catalysts for alkane oxidation

DOEpatents

Ellis, Jr., Paul E.; Lyons, James E.

1995-01-01

New compositions of matter comprising cyano-substituted metal complexes of porphyrins are catalysts for the oxidation of alkanes. The metal is iron, chromium, manganese, ruthenium, copper or cobalt. The porphyrin ring has cyano groups attached thereto in meso and/or .beta.-pyrrolic positions.

Catalysts for the hydrodenitrogenation of organic materials and process for the preparation of the catalysts

DOEpatents

Laine, R.M.; Hirschon, A.S.; Wilson, R.B. Jr.

1987-12-29

A process is described for the preparation of a multimetallic catalyst for the hydrodenitrogenation of an organic feedstock, which process comprises: (a) forming a precatalyst itself comprising: (1) a first metal compound selected from compounds of nickel, cobalt or mixtures thereof; (2) a second metal compound selected from compounds of chromium, molybdenum, tungsten, or mixtures thereof; and (3) an inorganic support; (b) heating the precatalyst of step (a) with a source of sulfide in a first non-oxidizing gas at a temperature and for a time effective to presulfide the precatalyst; (c) adding in a second non-oxidizing gas to the sulfided precatalyst of step (b) an organometallic transition metal moiety selected from compounds of iridium, rhodium, iron, ruthenium, tungsten or mixtures thereof for a time and at a temperature effective to chemically combine the metal components; and (d) optionally heating the chemically combined catalyst of step (b) in vacuum at a temperature and for a time effective to remove residual volatile organic materials. 12 figs.

Fuel cell with Pt/Pd electrocatalyst electrode

DOEpatents

Stonehart, Paul

1983-01-01

An electrode for use in a phosphoric acid fuel cell comprising a graphitized or partially graphitized carbon support having a platinum/palladium electrocatalyst thereon. Preferably, the platinum/palladium catalyst comprises 20 to 65 weight percent palladium.

Low oxygen biomass-derived pyrolysis oils and methods for producing the same

DOEpatents

Marinangeli, Richard; Brandvold, Timothy A; Kocal, Joseph A

2013-08-27

Low oxygen biomass-derived pyrolysis oils and methods for producing them from carbonaceous biomass feedstock are provided. The carbonaceous biomass feedstock is pyrolyzed in the presence of a catalyst comprising base metal-based catalysts, noble metal-based catalysts, treated zeolitic catalysts, or combinations thereof to produce pyrolysis gases. During pyrolysis, the catalyst catalyzes a deoxygenation reaction whereby at least a portion of the oxygenated hydrocarbons in the pyrolysis gases are converted into hydrocarbons. The oxygen is removed as carbon oxides and water. A condensable portion (the vapors) of the pyrolysis gases is condensed to low oxygen biomass-derived pyrolysis oil.

Oxidation catalysts comprising metal exchanged hexaaluminate wherein the metal is Sr, Pd, La, and/or Mn

DOEpatents

Wickham, David [Boulder, CO; Cook, Ronald [Lakewood, CO

2008-10-28

The present invention provides metal-exchanged hexaaluminate catalysts that exhibit good catalytic activity and/or stability at high temperatures for extended periods with retention of activity as combustion catalysts, and more generally as oxidation catalysts, that make them eminently suitable for use in methane combustion, particularly for use in natural gas fired gas turbines. The hexaaluminate catalysts of this invention are of particular interest for methane combustion processes for minimization of the generation of undesired levels (less than about 10 ppm) of NOx species. Metal exchanged hexaaluminate oxidation catalysts are also useful for oxidation of volatile organic compounds (VOC), particularly hydrocarbons. Metal exchanged hexaaluminate oxidation catalysts are further useful for partial oxidation, particularly at high temperatures, of reduced species, particularly hydrocarbons (alkanes and alkenes).

Calcination of calcium carbonate and blend therefor

DOEpatents

Mallow, William A.; Dziuk, Jr., Jerome J.

1989-01-01

A method for calcination of a calcium carbonate material comprising heating the calcium carbonate material to a temperature and for a time sufficient to calcine the material to the degree desired while in the presence of a catalyst; said catalyst comprising at least one fused salt having the formula MCO.sub.3.CaCO.sub.3.CaO.H.sub.2 O.sub.x, wherein M is an alkali metal and x is 0 to 1 and formed by fusing MCO.sub.3 and CaCO.sub.3 in a molar ratio of about 1:2 to 2:1, and a blend adapted to be heated to CaO comprising a calcium carbonate material and at least one such fused salt.

Method of CO and/or CO.sub.2 hydrogenation to higher hydrocarbons using doped mixed-metal oxides

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

Shekhawat, Dushyant; Berry, David A.; Haynes, Daniel J.

2017-03-21

A method of hydrogenation utilizing a reactant gas mixture comprising a carbon oxide and a hydrogen agent, and a hydrogenation catalyst comprising a mixed-metal oxide containing metal sites supported and/or incorporated into the lattice. The mixed-metal oxide comprises a pyrochlore, a brownmillerite, or mixtures thereof doped at the A-site or the B-site. The metal site may comprise a deposited metal, where the deposited metal is a transition metal, an alkali metal, an alkaline earth metal, or mixtures thereof. Contact between the carbon oxide, hydrogen agent, and hydrogenation catalyst under appropriate conditions of temperature, pressure and gas flow rate generate amore » hydrogenation reaction and produce a hydrogenated product made up of carbon from the carbon oxide and some portion of the hydrogen agent. The carbon oxide may be CO, CO.sub.2, or mixtures thereof and the hydrogen agent may be H.sub.2. In a particular embodiment, the hydrogenated product comprises olefins, paraffins, or mixtures thereof.« less

Conversion of olefins to liquid motor fuels

DOEpatents

Rabo, Jule A.; Coughlin, Peter K.

1988-01-01

Linear and/or branched claim C.sub.2 to C.sub.12 olefins are converted to hydrocarbon mixtures suitable for use as liquid motor fuels by contact with a catalyst capable of ensuring the production of desirable products with only a relatively minor amount of heavy products boiling beyond the diesel oil range. The catalyst having desirable stability during continuous production operations, comprises a steam stabilized zeolite Y catalyst of hydrophobic character, desirably in aluminum-extracted form. The olefins such as propylene, may be diluted with inerts, such as paraffins or with water, the latter serving to moderate the acidity of the catalyst, or to further moderate the activity of the aluminum-extracted catalyst, so as to increase the effective life of the catalyst.

Methods of refining and producing isomerized fatty acid esters and fatty acids from natural oil feedstocks

DOEpatents

Snead, Thomas E.; Cohen, Steven A.; Gildon, Demond L.; Beltran, Leslie V.; Kunz, Linda A.; Pals, Tessa M.; Quinn, Jordan R; Behrends, Jr., Raymond T.; Bernhardt, Randal J.

2016-07-05

Methods are provided for refining natural oil feedstocks and producing isomerized esters and acids. The methods comprise providing a C4-C18 unsaturated fatty ester or acid, and isomerizing the fatty acid ester or acid in the presence of heat or an isomerization catalyst to form an isomerized fatty ester or acid. In some embodiments, the methods comprise forming a dibasic ester or dibasic acid prior to the isomerizing step. In certain embodiments, the methods further comprise hydrolyzing the dibasic ester to form a dibasic acid. In certain embodiments, the olefin is formed by reacting the feedstock in the presence of a metathesis catalyst under conditions sufficient to form a metathesized product comprising olefins and esters, separating the olefins from the esters in the metathesized product, and transesterifying the esters in the presence of an alcohol to form a transesterified product having unsaturated esters.

Catalyst activator

DOEpatents

McAdon, Mark H.; Nickias, Peter N.; Marks, Tobin J.; Schwartz, David J.

2001-01-01

A catalyst activator particularly adapted for use in the activation of metal complexes of metals of Group 3-10 for polymerization of ethylenically unsaturated polymerizable monomers, especially olefins, comprising two Group 13 metal or metalloid atoms and a ligand structure including at least one bridging group connecting ligands on the two Group 13 metal or metalloid atoms.

Process for the production of low flammability electrolyte solvents

DOEpatents

Krumdick, Gregory K.; Pupek, Krzysztof; Dzwiniel, Trevor L.

2016-02-16

The invention provides a method for producing electrolyte solvent, the method comprising reacting a glycol with a disilazane in the presence of a catalyst for a time and at a temperature to silylate the glycol, separating the catalyst from the silylated glycol, removing unreacted silazane; and purifying the silylated glycol.

Steam Reforming of Acetic Acid over Co-Supported Catalysts: Coupling Ketonization for Greater Stability

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

Davidson, Stephen D.; Spies, Kurt A.; Mei, Donghai

We report on the markedly improved stability of a novel 2-bed catalytic system, as compared to a conventional 1-bed steam reforming catalyst, for the production of H2 from acetic acid. The 2-bed catalytic system comprises of i) a basic oxide ketonization catalyst for the conversion of acetic acid to acetone, and a ii) Co-based steam reforming catalyst, both catalytic beds placed in sequence within the same unit operation. Steam reforming catalysts are particularly prone to catalytic deactivation when steam reforming acetic acid, used here as a model compound for the aqueous fraction of bio-oil. Catalysts comprising MgAl2O4, ZnO, CeO2, andmore » activated carbon (AC) both with and without Co-addition were evaluated for conversion of acetic acid and acetone, its ketonization product, in the presence of steam. It was found that over the bare oxide support only ketonization activity was observed and coke deposition was minimal. With addition of Co to the oxide support steam reforming activity was facilitated and coke deposition was significantly increased. Acetone steam reforming over the same Co-supported catalysts demonstrated more stable performance and with less coke deposition than with acetic acid feedstock. DFT analysis suggests that over Co surface CHxCOO species are more favorably formed from acetic acid versus acetone. These CHxCOO species are strongly bound to the Co catalyst surface and could explain the higher propensity for coke formation from acetic acid. Based on these findings, in order to enhance stability of the steam reforming catalyst a dual-bed (2-bed) catalyst system was implemented. Comparing the 2-bed and 1-bed (Co-supported catalyst only) systems under otherwise identical reaction conditions the 2-bed demonstrated significantly improved stability and coke deposition was decreased by a factor of 4.« less

Method for regeneration and activity improvement of syngas conversion catalyst

DOEpatents

Lucki, Stanley J.; Brennan, James A.

1980-01-01

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

Pyrolyzed thin film carbon

NASA Technical Reports Server (NTRS)

Harder, Theodore (Inventor); Konishi, Satoshi (Inventor); Miserendino, Scott (Inventor); Tai, Yu-Chong (Inventor); Liger, Matthieu (Inventor)

2010-01-01

A method of making carbon thin films comprises depositing a catalyst on a substrate, depositing a hydrocarbon in contact with the catalyst and pyrolyzing the hydrocarbon. A method of controlling a carbon thin film density comprises etching a cavity into a substrate, depositing a hydrocarbon into the cavity, and pyrolyzing the hydrocarbon while in the cavity to form a carbon thin film. Controlling a carbon thin film density is achieved by changing the volume of the cavity. Methods of making carbon containing patterned structures are also provided. Carbon thin films and carbon containing patterned structures can be used in NEMS, MEMS, liquid chromatography, and sensor devices.

Methanol-tolerant cathode catalyst composite for direct methanol fuel cells

DOEpatents

Zhu, Yimin; Zelenay, Piotr

2006-09-05

A direct methanol fuel cell (DMFC) having a methanol fuel supply, oxidant supply, and its membrane electrode assembly (MEA) formed of an anode electrode and a cathode electrode with a membrane therebetween, a methanol oxidation catalyst adjacent the anode electrode and the membrane, an oxidant reduction catalyst adjacent the cathode electrode and the membrane, comprises an oxidant reduction catalyst layer of Pt.sub.3Cr/C so that oxidation at the cathode of methanol that crosses from the anode through the membrane to the cathode is reduced with a concomitant increase of net electrical potential at the cathode electrode.

Methanol-Tolerant Cathode Catalyst Composite For Direct Methanol Fuel Cells

DOEpatents

Zhu, Yimin; Zelenay, Piotr

2006-03-21

A direct methanol fuel cell (DMFC) having a methanol fuel supply, oxidant supply, and its membrane electrode assembly (MEA) formed of an anode electrode and a cathode electrode with a membrane therebetween, a methanol oxidation catalyst adjacent the anode electrode and the membrane, an oxidant reduction catalyst adjacent the cathode electrode and the membrane, comprises an oxidant reduction catalyst layer of a platinum-chromium alloy so that oxidation at the cathode of methanol that crosses from the anode through the membrane to the cathode is reduced with a concomitant increase of net electrical potential at the cathode electrode.

Chemical production processes and systems

DOEpatents

Holladay, Johnathan E.; Muzatko, Danielle S.; White, James F.; Zacher, Alan H.

2014-06-17

Hydrogenolysis systems are provided that can include a reactor housing an Ru-comprising hydrogenolysis catalyst and wherein the contents of the reactor is maintained at a neutral or acidic pH. Reactant reservoirs within the system can include a polyhydric alcohol compound and a base, wherein a weight ratio of the base to the compound is less than 0.05. Systems also include the product reservoir comprising a hydrogenolyzed polyhydric alcohol compound and salts of organic acids, and wherein the moles of base are substantially equivalent to the moles of salts or organic acids. Processes are provided that can include an Ru-comprising catalyst within a mixture having a neutral or acidic pH. A weight ratio of the base to the compound can be between 0.01 and 0.05 during exposing.

Chemical production processes and systems

DOEpatents

Holladay, Johnathan E; Muzatko, Danielle S; White, James F; Zacher, Alan H

2015-04-21

Hydrogenolysis systems are provided that can include a reactor housing an Ru-comprising hydrogenolysis catalyst and wherein the contents of the reactor is maintained at a neutral or acidic pH. Reactant reservoirs within the system can include a polyhydric alcohol compound and a base, wherein a weight ratio of the base to the compound is less than 0.05. Systems also include the product reservoir comprising a hydrogenolyzed polyhydric alcohol compound and salts of organic acids, and wherein the moles of base are substantially equivalent to the moles of salts or organic acids. Processes are provided that can include an Ru-comprising catalyst within a mixture having a neutral or acidic pH. A weight ratio of the base to the compound can be between 0.01 and 0.05 during exposing.

Catalyst inks and method of application for direct methanol fuel cells

DOEpatents

Zelenay, Piotr; Davey, John; Ren, Xiaoming; Gottesfeld, Shimshon; Thomas, Sharon C.

2004-02-24

Inks are formulated for forming anode and cathode catalyst layers and applied to anode and cathode sides of a membrane for a direct methanol fuel cell. The inks comprise a Pt catalyst for the cathode and a Pt--Ru catalyst for the anode, purified water in an amount 4 to 20 times that of the catalyst by weight, and a perfluorosulfonic acid ionomer in an amount effective to provide an ionomer content in the anode and cathode surfaces of 20% to 80% by volume. The inks are prepared in a two-step process while cooling and agitating the solutions. The final solution is placed in a cooler and continuously agitated while spraying the solution over the anode or cathode surface of the membrane as determined by the catalyst content.

Combination moisture and hydrogen getter

DOEpatents

Harrah, L.A.; Mead, K.E.; Smith, H.M.

1983-09-20

A combination moisture and hydrogen getter comprises (a) a moisture getter comprising a readily oxidizable metal; and (b) a hydrogen getter comprising (1) a solid acetylenic compound and (2) a hydrogenation catalyst. A method of scavenging moisture from a closed container uses the combination moisture and hydrogen getter to irreversibly chemically reduce the moisture and chemically bind the resultant hydrogen.

Combination moisture and hydrogen getter

DOEpatents

Harrah, Larry A.; Mead, Keith E.; Smith, Henry M.

1983-01-01

A combination moisture and hydrogen getter comprises (a) a moisture getter comprising a readily oxidizable metal; and (b) a hydrogen getter comprising (i) a solid acetylenic compound and (ii) a hydrogenation catalyst. A method of scavenging moisture from a closed container uses the combination moisture and hydrogen getter to irreversibly chemically reduce the moisture and chemically bind the resultant hydrogen.

Combination moisture and hydrogen getter

DOEpatents

Not Available

1982-04-29

A combination moisture and hydrogen getter comprises (a) a moisture getter comprising a readily oxidizable metal; and (b) a hydrogen getter comprising (i) a solid acetylenic compound and (ii) a hydrogenation catalyst. A method of scavenging moisture from a closed container uses the combination moisture and hydrogen getter to irreversibly chemically reduce the moisture and chemically bind the reusltant hydrogen.

Hydrous oxide ion-exchange compound catalysts

DOEpatents

Dosch, Robert G.; Stephens, Howard P.

1990-01-01

A catalytic material of improved activity which comprises a hydrous, alkali metal or alkaline earth metal or quaternary ammonium titanate, zirconate, niobate, or tantalate, in which the metal or ammonium cations have been exchange with a catalytically effective quantity of a catalyst metal, and which has been subsequently treated with a solution of a Bronsted acid.

Cyclic Catalytic Upgrading of Chemical Species Using Metal Oxide Materials

NASA Technical Reports Server (NTRS)

White, James H. (Inventor); Rolfe, Sara L. (Inventor); Schutte, Erick J. (Inventor)

2013-01-01

Processes are disclosure which comprise alternately contacting an oxygen-carrying catalyst with a reducing substance, or a lower partial pressure of an oxidizing gas, and then with the oxidizing gas or a higher partial pressure of the oxidizing gas, whereby the catalyst is alternately reduced and then regenerated to an oxygenated state. In certain embodiments, the oxygen-carrying catalyst comprises at least one metal oxide-containing material containing a composition having the following formulas: (a) Ce(sub x)B(sub y)B'(sub z)B''O(sub gamma; wherein B=Ba, Sr, Ca, or Zr; B'=Mn, Co, and/or Fe; B''=Cu; 0.01

Cyclic catalytic upgrading of chemical species using metal oxide materials

DOEpatents

White, James H; Schutte, Erick J; Rolfe, Sara L

2013-05-07

Processes are disclosure which comprise alternately contacting an oxygen-carrying catalyst with a reducing substance, or a lower partial pressure of an oxidizing gas, and then with the oxidizing gas or a higher partial pressure of the oxidizing gas, whereby the catalyst is alternately reduced and then regenerated to an oxygenated state. In certain embodiments, the oxygen-carrying catalyst comprises at least one metal oxide-containing material containing a composition having the following formulas: (a) Ce.sub.xB.sub.yB'.sub.zB''O.sub..delta., wherein B=Ba, Sr, Ca, or Zr; B'=Mn, Co, and/or Fe; B''=Cu; 0.01

Electrocatalyst for alcohol oxidation in fuel cells

DOEpatents

Adzic, Radoslav R.; Marinkovic, Nebojsa S.

2001-01-01

Binary and ternary electrocatalysts are provided for oxidizing alcohol in a fuel cell. The binary electrocatalyst includes 1) a substrate selected from the group consisting of NiWO.sub.4 or CoWO.sub.4 or a combination thereof, and 2) Group VIII noble metal catalyst supported on the substrate. The ternary electrocatalyst includes 1) a substrate as described above, and 2) a catalyst comprising Group VIII noble metal, and ruthenium oxide or molybdenum oxide or a combination thereof, said catalyst being supported on said substrate.

Hydrothermal performance of catalyst supports

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

Elam, Jeffrey W.; Marshall, Christopher L.; Libera, Joseph A.

A high surface area catalyst with a mesoporous support structure and a thin conformal coating over the surface of the support structure. The high surface area catalyst support is adapted for carrying out a reaction in a reaction environment where the thin conformal coating protects the support structure within the reaction environment. In various embodiments, the support structure is a mesoporous silica catalytic support and the thin conformal coating comprises a layer of metal oxide resistant to the reaction environment which may be a hydrothermal environment.

Supported catalysts using nanoparticles as the support material

DOEpatents

Wong, Michael S.; Wachs, Israel E.; Knowles, William V.

2010-11-02

A process for making a porous catalyst, comprises a) providing an aqueous solution containing a nanoparticle precursor, b) forming a composition containing nanoparticles, c) adding a first catalytic component or precursor thereof and a pore-forming agent to the composition containing nanoparticles and allowing the first catalytic component, the pore-forming agent, and the nanoparticles form an organic-inorganic structure, d) removing water from the organic-inorganic structure; and e) removing the pore-forming agent from the organic-inorganic structure so as to yield a porous catalyst.

Photoreactor with self-contained photocatalyst recapture

DOEpatents

Gering, Kevin L.

2004-12-07

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

Low temperature catalysts for methanol production

DOEpatents

Sapienza, R.S.; Slegeir, W.A.; O'Hare, T.E.; Mahajan, D.

1986-09-30

A catalyst and process useful at low temperatures (below about 160 C) and preferably in the range 80--120 C used in the production of methanol from carbon monoxide and hydrogen are disclosed. The catalyst is used in slurry form and comprises a complex reducing agent derived from the component structure NaH--RONa-M(OAc)[sub 2] where M is selected from the group consisting of Ni, Pd, and Co and R is a lower alkyl group containing 1--6 carbon atoms. This catalyst is preferably used alone but is also effective in combination with a metal carbonyl of a group VI (Mo, Cr, W) metal. The preferred catalyst precursor is Nic (where M = Ni and R = tertiary amyl). Mo(CO)[sub 6] is the preferred metal carbonyl if such component is used. The catalyst is subjected to a conditioning or activating step under temperature and pressure, similar to the parameters given above, to afford the active catalyst.

Low temperature catalysts for methanol production

DOEpatents

Sapienza, R.S.; Slegeir, W.A.; O'Hare, T.E.; Mahajan, D.

1986-10-28

A catalyst and process useful at low temperatures (below about 160 C) and preferably in the range 80--120 C used in the production of methanol from carbon monoxide and hydrogen are disclosed. The catalyst is used in slurry form and comprises a complex reducing agent derived from the component structure NaH--RONa-M(OAc)[sub 2] where M is selected from the group consisting of Ni, Pd, and Co and R is a lower alkyl group containing 1-6 carbon atoms. This catalyst is preferably used alone but is also effective in combination with a metal carbonyl of a group VI (Mo, Cr, W) metal. The preferred catalyst precursor is NiC (where M = Ni and R = tertiary amyl). Mo(CO)[sub 6] is the preferred metal carbonyl if such component is used. The catalyst is subjected to a conditioning or activating step under temperature and pressure, similar to the parameters given above, to afford the active catalyst.

DEFE0023863 Final Report, Technology for GHG Emission Reduction and CostCompetitive MilSpec Jet Fuel Production using CTL

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

Hartvigsen, Joseph J; Dimick, Paul; Laumb, Jason D

Ceramatec Inc, in collaboration with IntraMicron (IM), the Energy & Environmental Research Center (EERC) and Sustainable Energy Solutions, LLC (SES), have completed a three-year research project integrating their respective proprietary technologies in key areas to demonstrate production of a jet fuel from coal and biomass sources. The project goals and objectives were to demonstrate technology capable of producing a “commercially-viable quantity” of jet fuel and make significant progress toward compliance with Section 526 of the Energy Independence and Security Act of 2007 (EISA 2007 §526) lifecycle greenhouse gas (GHG) emissions requirements. The Ceramatec led team completed the demonstration of nominalmore » 2 bbl/day Fischer-Tropsch (FT) synthesis pilot plant design, capable of producing a nominal 1 bbl/day in the Jet-A/JP-8 fraction. This production rate would have a capacity of 1,000 gallons of jet fuel per month and provide the design basis of a 100 bbl/day module producing over 2,000 gallons of jet fuel per day. Co-gasification of coal-biomass blends enables a reduction of lifecycle greenhouse gas emissions from equivalent conventional petroleum derived fuel basis. Due to limits of biomass availability within an economic transportation range, implementation of a significant biomass feed fraction will require smaller plants than current world scale CTL and GTL FT plants. Hence a down-scaleable design is essential. The pilot plant design leverages Intramicron’s MicroFiber Entrapped Catalyst (MFEC) support which increases the catalyst bed thermal conductivity two orders of magnitude, allowing thermal management of the FT reaction exotherm in much larger reactor tubes. In this project, single tube reactors having 4.5 inch outer diameter and multi-tube reactors having 4 inch outer diameters were operated, with productivities as high as 1.5 gallons per day per linear foot of reactor tube. A significant reduction in tube count results from the use of large diameter reactor tubes, with an associated reduction in reactor cost. The pilot plant was designed with provisions for product collection capable of operating with conventional wax producing FT catalysts but was operated with a Chevron hybrid wax-free FT catalyst. Process simplification enabled by elimination of the wax hydrocracking process unit provides economic advantages in scaling to biomass capable plant sizes. Intramicron also provided a sulfur capture system based on their Oxidative Sulfur Removal (OSR) catalyst process. The integrated sulfur removal and FT systems were operated with syngas produced by the Transport Reactor Development Unit (TRDU) gasifier at the University of North Dakota EERC. SES performed modeling of their cryogenic carbon capture process on the energy, cost and CO2 emissions impact of the Coal-biomass synthetic fuel process.« less

Method of CO and/or CO.sub.2 hydrogenation using doped mixed-metal oxides

DOEpatents

Shekhawat, Dushyant; Berry, David A.; Haynes, Daniel J.; Abdelsayed, Victor; Smith, Mark W.; Spivey, James J.

2015-10-06

A method of hydrogenation utilizing a reactant gas mixture comprising a carbon oxide and a hydrogen agent, and a hydrogenation catalyst comprising a mixed-metal oxide containing metal sites supported and/or incorporated into the lattice. The mixed-metal oxide comprises a perovskite, a pyrochlore, a fluorite, a brownmillerite, or mixtures thereof doped at the A-site or the B-site. The metal site may comprise a deposited metal, where the deposited metal is a transition metal, an alkali metal, an alkaline earth metal, or mixtures thereof. Contact between the carbon oxide, hydrogen agent, and hydrogenation catalyst under appropriate conditions of temperature, pressure and gas flow rate generate a hydrogenation reaction and produce a hydrogenated product made up of carbon from the carbon oxide and some portion of the hydrogen agent. The carbon oxide may be CO, CO.sub.2, or mixtures thereof and the hydrogen agent may be H.sub.2. In a particular embodiment, the hydrogenated product comprises an alcohol, an olefin, an aldehyde, a ketone, an ester, an oxo-product, or mixtures thereof.

Charge transfer mediator based systems for electrocatalytic oxygen reduction

DOEpatents

Stahl, Shannon S.; Gerken, James B.; Anson, Colin W.

2017-11-07

Disclosed are systems for the electrocatalytic reduction of oxygen, having redox mediator/redox catalyst pairs and an electrolyte solution in contact with an electrode. The redox mediator is included in the electrolyte solution, and the redox catalyst may be included in the electrolyte solution, or alternatively, may be in contact with the electrolyte solution. In one form a cobalt redox catalyst is used with a quinone redox mediator. In another form a nitrogen oxide redox catalyst is used with a nitroxyl type redox mediator. The systems can be used in electrochemical cells wherein neither the anode nor the cathode comprise an expensive metal such as platinum.

Charge transfer mediator based systems for electrocatalytic oxygen reduction

DOEpatents

Stahl, Shannon S.; Gerken, James B.; Anson, Colin W.

2017-07-18

Disclosed are systems for the electrocatalytic reduction of oxygen, having redox mediator/redox catalyst pairs and an electrolyte solution in contact with an electrode. The redox mediator is included in the electrolyte solution, and the redox catalyst may be included in the electrolyte solution, or alternatively, may be in contact with the electrolyte solution. In one form a cobalt redox catalyst is used with a quinone redox mediator. In another form a nitrogen oxide redox catalyst is used with a nitroxyl type redox mediator. The systems can be used in electrochemical cells wherein neither the anode nor the cathode comprise an expensive metal such as platinum.

Methods of refining and producing dibasic esters and acids from natural oil feedstocks

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

Snead, Thomas E; Cohen, Steven A; Gildon, Demond L

2015-04-07

Methods are provided for refining natural oil feedstocks and producing dibasic esters and/or dibasic acids. The methods comprise reacting a terminal olefin with an internal olefin in the presence of a metathesis catalyst to form a dibasic ester and/or dibasic acid. In certain embodiments, the olefin esters are formed by reacting the feedstock in the presence of a metathesis catalyst under conditions sufficient to form a metathesized product comprising olefins and esters, separating the olefins from the esters in the metathesized product, and transesterifying the esters in the presence of an alcohol to form a transesterified product having olefin esters.

Methods of refining and producing dibasic esters and acids from natural oil feedstocks

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

Snead, Thomas E.; Cohen, Steven A.; Gildon, Demond L.

2016-03-15

Methods are provided for refining natural oil feedstocks and producing dibasic esters and/or dibasic acids. The methods comprise reacting a terminal olefin with an internal olefin in the presence of a metathesis catalyst to form a dibasic ester and/or dibasic acid. In certain embodiments, the olefin esters are formed by reacting the feedstock in the presence of a metathesis catalyst under conditions sufficient to form a metathesized product comprising olefins and esters, separating the olefins from the esters in the metathesized product, and transesterifying the esters in the presence of an alcohol to form a transesterified product having olefin esters.

Density controlled carbon nanotube array electrodes

DOEpatents

Ren, Zhifeng F [Newton, MA; Tu, Yi [Belmont, MA

2008-12-16

CNT materials comprising aligned carbon nanotubes (CNTs) with pre-determined site densities, catalyst substrate materials for obtaining them and methods for forming aligned CNTs with controllable densities on such catalyst substrate materials are described. The fabrication of films comprising site-density controlled vertically aligned CNT arrays of the invention with variable field emission characteristics, whereby the field emission properties of the films are controlled by independently varying the length of CNTs in the aligned array within the film or by independently varying inter-tubule spacing of the CNTs within the array (site density) are disclosed. The fabrication of microelectrode arrays (MEAs) formed utilizing the carbon nanotube material of the invention is also described.

Conducting metal oxide and metal nitride nanoparticles

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

DiSalvo, Jr., Francis J.; Subban, Chinmayee V.

Conducting metal oxide and nitride nanoparticles that can be used in fuel cell applications. The metal oxide nanoparticles are comprised of for example, titanium, niobium, tantalum, tungsten and combinations thereof. The metal nitride nanoparticles are comprised of, for example, titanium, niobium, tantalum, tungsten, zirconium, and combinations thereof. The nanoparticles can be sintered to provide conducting porous agglomerates of the nanoparticles which can be used as a catalyst support in fuel cell applications. Further, platinum nanoparticles, for example, can be deposited on the agglomerates to provide a material that can be used as both an anode and a cathode catalyst supportmore » in a fuel cell.« less

Low cost fuel cell diffusion layer configured for optimized anode water management

DOEpatents

Owejan, Jon P; Nicotera, Paul D; Mench, Matthew M; Evans, Robert E

2013-08-27

A fuel cell comprises a cathode gas diffusion layer, a cathode catalyst layer, an anode gas diffusion layer, an anode catalyst layer and an electrolyte. The diffusion resistance of the anode gas diffusion layer when operated with anode fuel is higher than the diffusion resistance of the cathode gas diffusion layer. The anode gas diffusion layer may comprise filler particles having in-plane platelet geometries and be made of lower cost materials and manufacturing processes than currently available commercial carbon fiber substrates. The diffusion resistance difference between the anode gas diffusion layer and the cathode gas diffusion layer may allow for passive water balance control.

Method for making hydrogen rich gas from hydrocarbon fuel

DOEpatents

Krumpelt, M.; Ahmed, S.; Kumar, R.; Doshi, R.

1999-07-27

A method of forming a hydrogen rich gas from a source of hydrocarbon fuel in which the hydrocarbon fuel contacts a two-part catalyst comprising a dehydrogenation portion and an oxide-ion conducting portion at a temperature not less than about 400 C for a time sufficient to generate the hydrogen rich gas while maintaining CO content less than about 5 volume percent. There is also disclosed a method of forming partially oxidized hydrocarbons from ethanes in which ethane gas contacts a two-part catalyst comprising a dehydrogenation portion and an oxide-ion conducting portion for a time and at a temperature sufficient to form an oxide. 4 figs.

Method for making hydrogen rich gas from hydrocarbon fuel

DOEpatents

Krumpelt, Michael; Ahmed, Shabbir; Kumar, Romesh; Doshi, Rajiv

1999-01-01

A method of forming a hydrogen rich gas from a source of hydrocarbon fuel in which the hydrocarbon fuel contacts a two-part catalyst comprising a dehydrogenation portion and an oxide-ion conducting portion at a temperature not less than about 400.degree. C. for a time sufficient to generate the hydrogen rich gas while maintaining CO content less than about 5 volume percent. There is also disclosed a method of forming partially oxidized hydrocarbons from ethanes in which ethane gas contacts a two-part catalyst comprising a dehydrogenation portion and an oxide-ion conducting portion for a time and at a temperature sufficient to form an oxide.

Hydrogen gettering packing material, and process for making same

DOEpatents

LeMay, James D.; Thompson, Lisa M.; Smith, Henry Michael; Schicker, James R.

2001-01-01

A hydrogen gettering system for a sealed container is disclosed comprising packing material for use within the sealed container, and a coating film containing hydrogen gettering material on at least a portion of the surface of such packing material. The coating film containing the hydrogen gettering material comprises a mixture of one or more organic materials capable of reacting with hydrogen and one or more catalysts capable of catalyzing the reaction of hydrogen with such one or more organic materials. The mixture of one or more organic materials capable of reacting with hydrogen and the one or more catalysts is dispersed in a suitable carrier which preferably is a curable film-forming material. In a preferred embodiment, the packing material comprises a foam material which is compatible with the coating film containing hydrogen gettering material thereon.

Preparation of .alpha.,.beta.-unsaturated carboxylic acids and esters

DOEpatents

Gogate, Makarand Ratnakar; Spivey, James Jerry; Zoeller, Joseph Robert

1998-01-01

Disclosed is a process for the preparation of .alpha.,.beta.-unsaturated carboxylic acids and esters thereof which comprises contacting formaldehyde or a source of formaldehyde with a carboxylic acid, ester or anhydride in the presence of a catalyst comprising an oxide of niobium.

Preparation of {alpha},{beta}-unsaturated carboxylic acids and esters

DOEpatents

Gogate, M.R.; Spivey, J.J.; Zoeller, J.R.

1998-09-15

Disclosed is a process for the preparation of {alpha},{beta}-unsaturated carboxylic acids and esters thereof which comprises contacting formaldehyde or a source of formaldehyde with a carboxylic acid, ester or anhydride in the presence of a catalyst comprising an oxide of niobium.

Improved hydrous oxide ion-exchange compound catalysts

DOEpatents

Dosch, R.G.; Stephens, H.P.

1986-04-09

Disclosed is a catalytic material of improved activity which comprises a hydrous, alkali metal or alkaline earth metal or quaternary ammonium titanate, zirconate, niobate, or tantalate, in which the metal or ammonium cations have been exchanged with a catalytically effective quantity of a catalyst metal, and which has been subsequently treated with a solution of a Bronsted acid.

Catalytic oxidative dehydrogenation process

DOEpatents

Schmidt, Lanny D.; Huff, Marylin

2002-01-01

A process for the production of a mono-olefin from a gaseous paraffinic hydrocarbon having at least two carbon atoms or mixtures thereof comprising reacting said hydrocarbons and molecular oxygen in the presence of a platinum catalyst. The catalyst consist essentially of platinum supported on alumina or zirconia monolith, preferably zirconia and more preferably in the absence of palladium, rhodium and gold.

Chemicals from coal. Interim report for USBM Synthoil

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

Peters, B.C.

1977-10-01

This document contains the results of an investigation to determine the suitability of the USBM Synthoil Product as a petrochemical feedstock. A sample of the whole crude was distilled into two straight run fractions; 350 to 650/sup 0/F mid-distillate and 650/sup 0/F+ residue. Laboratory studies in metal reactors and computer and mathematical simulations were performed to provide overall material balance data for a conceptual plant. The mid-distillate was hydrocracked to produce naphtha which was further processed by hydrotreating and reforming. The reformate from the mid-distillate was then mathematically hydrodealkylated to convert it to a product slate consisting of methane, LPG's,more » benzene, and fuel, along with the total hydrogen consumed. The value of the products obtained per 100 pounds of mid-distillate was $6.89. The high aromatic yield obtained from the hydrocrackate naphtha makes this fraction very attractive as a petrochemical feedstock. Because the gas oil would be extremely difficult to process, it was not investigated.« less

Iron catalyzed coal liquefaction process

DOEpatents

Garg, Diwakar; Givens, Edwin N.

1983-01-01

A process is described for the solvent refining of coal into a gas product, a liquid product and a normally solid dissolved product. Particulate coal and a unique co-catalyst system are suspended in a coal solvent and processed in a coal liquefaction reactor, preferably an ebullated bed reactor. The co-catalyst system comprises a combination of a stoichiometric excess of iron oxide and pyrite which reduce predominantly to active iron sulfide catalysts in the reaction zone. This catalyst system results in increased catalytic activity with attendant improved coal conversion and enhanced oil product distribution as well as reduced sulfide effluent. Iron oxide is used in a stoichiometric excess of that required to react with sulfur indigenous to the feed coal and that produced during reduction of the pyrite catalyst to iron sulfide.

Catalyst system and process for benzyl ether fragmentation and coal liquefaction

DOEpatents

Zoeller, Joseph Robert

1998-04-28

Dibenzyl ether can be readily cleaved to form primarily benzaldehyde and toluene as products, along with minor amounts of bibenzyl and benzyl benzoate, in the presence of a catalyst system comprising a Group 6 metal, preferably molybdenum, a salt, and an organic halide. Although useful synthetically for the cleavage of benzyl ethers, this cleavage also represents a key model reaction for the liquefaction of coal; thus this catalyst system and process should be useful in coal liquefaction with the advantage of operating at significantly lower temperatures and pressures.

Catalysts for lean burn engine exhaust abatement

DOEpatents

Ott, Kevin C.; Clark, Noline C.; Paffett, Mark T.

2006-08-01

The present invention provides a process for catalytically reducing nitrogen oxides in an exhaust gas stream containing nitrogen oxides and a reductant material by contacting the gas stream under conditions effective to catalytically reduce the nitrogen oxides with a catalyst comprising a aluminum-silicate type material and a minor amount of a metal, the catalyst characterized as having sufficient catalytic activity so as to reduce the nitrogen oxides by at least 60 percent under temperatures within the range of from about 200.degree. C. to about 400.degree. C.

Catalysts For Lean Burn Engine Exhaust Abatement

DOEpatents

Ott, Kevin C.; Clark, Noline C.; Paffett, Mark T.

2004-04-06

The present invention provides a process for catalytically reducing nitrogen oxides in an exhaust gas stream containing nitrogen oxides and a reductant material by contacting the gas stream under conditions effective to catalytically reduce the nitrogen oxides with a catalyst comprising a aluminum-silicate type material and a minor amount of a metal, the catalyst characterized as having sufficient catalytic activity so as to reduce the nitrogen oxides by at least 60 percent under temperatures within the range of from about 200.degree. C. to about 400.degree. C.

Catalysts for lean burn engine exhaust abatement

DOEpatents

Ott, Kevin C.; Clark, Noline C.; Paffett, Mark T.

2003-01-01

The present invention provides a process for catalytically reducing nitrogen oxides in an exhaust gas stream containing nitrogen oxides and a reductant material by contacting the gas stream under conditions effective to catalytically reduce the nitrogen oxides with a catalyst comprising a aluminum-silicate type material and a minor amount of a metal, the catalyst characterized as having sufficient catalytic activity so as to reduce the nitrogen oxides by at least 60 percent under temperatures within the range of from about 200.degree. C. to about 400.degree. C.

Method of preparing size-selected metal clusters

DOEpatents

Elam, Jeffrey W.; Pellin, Michael J.; Stair, Peter C.

2010-05-11

The invention provides a method for depositing catalytic clusters on a surface, the method comprising confining the surface to a controlled atmosphere; contacting the surface with catalyst containing vapor for a first period of time; removing the vapor from the controlled atmosphere; and contacting the surface with a reducing agent for a second period of time so as to produce catalyst-containing nucleation sites.

Methods for treating a metathesis feedstock with metal alkoxides

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

Cohen, Steven A.; Anderson, Donde R.; Wang, Zhe

Various methods are provided for treating and reacting a metathesis feedstock. In one embodiment, the method includes providing a feedstock comprising a natural oil, chemically treating the feedstock with a metal alkoxide under conditions sufficient to diminish catalyst poisons in the feedstock, and, following the treating, combining a metathesis catalyst with the feedstock under conditions sufficient to metathesize the feedstock.

Microemulsion impregnated catalyst composite and use thereof in a synthesis gas conversion process

DOEpatents

Abrevaya, Hayim; Targos, William M.

1987-01-01

A catalyst composition for synthesis gas conversion comprising a ruthenium metal component deposited on a support carrier wherein the average metal particle size is less than about 100 A. The method of manufacture of the composition via a reverse micelle impregnation technique and the use of the composition in a Fischer-Tropsch conversion process is also disclosed.

Method of carbon chain extension using novel aldol reaction

DOEpatents

Silks, Louis A; Gordon, John C; Wu, Ruilan; Hanson, Susan Kloek

2013-07-30

Method of producing C.sub.8-C.sub.15 hydrocarbons. comprising providing a ketone starting material; providing an aldol starting material comprising chloromethylfurfural; mixing the ketone starting material and the aldol starting material in a reaction in the presence of a proline-containing catalyst selected from the group consisting of Zn(Pro).sub.2, Yb(Pro).sub.3, and combinations thereof, or a catalyst having one of the structures (I), (II) or (III), and in the presence of a solvent, wherein the solvent comprises water and is substantially free of organic solvents, where (I), (II) and (III) respectively are: ##STR00001## where R.sub.1 is a C.sub.1-C.sub.6 alkyl moiety, X=(OH) and n=2. ##STR00002## In (III), X may be CH.sub.2, sulfur or selenium, M may be Zn, Mg, or a lanthanide, and R.sub.1 and R.sub.2 each independently may be a methyl, ethyl, phenyl moiety.

Method of carbon chain extension using novel aldol reaction

DOEpatents

Silks, Louis A; Gordon, John C; Wu, Ruilan; Hangson, Susan Kloek

2013-08-13

Method of producing C.sub.8-C.sub.15 hydrocarbons comprising providing a ketone starting material; providing an aldol starting material comprising hydroxymethylfurfural; mixing the ketone starting material and the aldol starting material in a reaction in the presence of a proline-containing catalyst selected from the group consisting of Zn(Pro).sub.2, Yb(Pro).sub.2, and combinations thereof, or a catalyst having one of the structures (I), (II) or (III), and in the presence of a solvent, wherein the solvent comprises water and is substantially free of organic solvents, where (I), (II) and (III) respectively are: ##STR00001## where R.sub.1 is a C.sub.1-C.sub.6 alkyl moiety, X=(OH) and n=2. ##STR00002## In (III), X may be CH.sub.2, sulfur or selenium, M may be Zn, Mg, or a lanthanide, and R.sub.1 and R.sub.2 each independently may be a methyl, ethyl, phenyl moiety.

Process for the regeneration of metallic catalysts

DOEpatents

Katzer, James R.; Windawi, Hassan

1981-01-01

A method for the regeneration of metallic hydrogenation catalysts from the class consisting of Ni, Rh, Pd, Ir, Pt and Ru poisoned with sulfur, with or without accompanying carbon deposition, comprising subjecting the catalyst to exposure to oxygen gas in a concentration of about 1-10 ppm. intermixed with an inert gas of the group consisting of He, A, Xe, Kr, N.sub.2 and air substantially free of oxygen to an extent such that the total oxygen molecule throughout is in the range of about 10 to 20 times that of the hydrogen sulfide molecular exposure producing the catalyst poisoning while maintaining the temperature in the range of about 300.degree. to 500.degree. C.

Method for generating a highly reactive plasma for exhaust gas aftertreatment and enhanced catalyst reactivity

DOEpatents

Whealton, John H.; Hanson, Gregory R.; Storey, John M.; Raridon, Richard J.; Armfield, Jeffrey S.; Bigelow, Timothy S.; Graves, Ronald L.

2002-01-01

A method for non-thermal plasma aftertreatment of exhaust gases the method comprising the steps of providing short risetime, high frequency, high power bursts of low-duty factor microwaves sufficient to generate a plasma discharge and passing a gas to be treated through the discharge so as to cause dissociative reduction of the exhaust gases and enhanced catalyst reactivity through application of the pulsed microwave fields directly to the catalyst material sufficient to cause a polarizability catastrophe and enhanced heating of the metal crystallite particles of the catalyst, and in the presence or absence of the plasma. The invention also includes a reactor for aftertreatment of exhaust gases.

Catalysts for the production of hydrocarbons from carbon monoxide and water

DOEpatents

Sapienza, Richard S.; Slegeir, William A.; Goldberg, Robert I.

1987-04-07

A method of converting low H.sub.2 /CO ratio syngas to carbonaceous products comprising reacting the syngas with water or steam at 200.degree. to 350.degree. C. in the presence of a metal catalyst supported on zinc oxide. Hydrocarbons are produced with a catalyst selected from cobalt, nickel or ruthenium and alcohols are produced with a catalyst selected from palladium, platinium, ruthenium or copper on the zinc oxide support. The ratio of the reactants are such that for alcohols and saturated hydrocarbons: and for olefinic hydrocarbons: where n is the number of carbon atoms in the product and x is the molar amount of water in the reaction mixture.

Heterogeneous catalyst for the production of ethylidene diacetate from acetic anhydride

DOEpatents

Ramprasad, D.; Waller, F.J.

1998-06-16

This invention relates to a process for producing ethylidene diacetate by the reaction of acetic anhydride, acetic acid, hydrogen and carbon monoxide at elevated temperatures and pressures in the presence of an alkyl halide and a heterogeneous, bifunctional catalyst that is stable to hydrogenation and comprises an insoluble polymer having pendant quaternized heteroatoms, some of which heteroatoms are ionically bonded to anionic Group VIII metal complexes, the remainder of the heteroatoms being bonded to iodide. In contrast to prior art processes, no accelerator (promoter) is necessary to achieve the catalytic reaction and the products are easily separated from the catalyst by filtration. The catalyst can be recycled without loss in activity.

Heterogeneous catalyst for the production of ethylidene diacetate from acetic anhydride

DOEpatents

Ramprasad, Dorai; Waller, Francis Joseph

1998-01-01

This invention relates to a process for producing ethylidene diacetate by the reaction of acetic anhydride, acetic acid, hydrogen and carbon monoxide at elevated temperatures and pressures in the presence of an alkyl halide and a heterogeneous, bifunctional catalyst that is stable to hydrogenation and comprises an insoluble polymer having pendant quaternized heteroatoms, some of which heteroatoms are ionically bonded to anionic Group VIII metal complexes, the remainder of the heteroatoms being bonded to iodide. In contrast to prior art processes, no accelerator (promoter) is necessary to achieve the catalytic reaction and the products are easily separated from the catalyst by filtration. The catalyst can be recycled without loss in activity.

Low temperature catalysts for methanol production

DOEpatents

Sapienza, R.S.; Slegeir, W.A.; O'Hare, T.E.; Mahajan, D.

1985-03-12

A catalyst and process useful at low temperatures (below about 160/sup 0/C) and preferably in the range 80 to 120/sup 0/C used in the production of methanol from carbon monoxide and hydrogen is disclosed. The catalyst is used in slurry form and comprises a complex reducing agent derived from the component structure NaH-RONa-M(OAc)/sub 2/ where M is selected from the group consisting of Ni, Pd, and Co and R is a lower alkyl group containing 1 to 6 carbon atoms. This catalyst is preferably used alone but is also effective in combination with a metal carbonyl of a group VI (Mo, Cr, W) metal. The preferred catalyst precursor is Nic (where M = Ni and R = tertiary amyl). Mo(CO)/sub 6/ is the preferred metal carbonyl if such component is used. The catalyst is subjected to a conditioning or activating step under temperature and pressure, similar to the parameters given above, to afford the active catalyst.

Low temperature catalysts for methanol production

DOEpatents

Sapienza, Richard S.; Slegeir, William A.; O'Hare, Thomas E.; Mahajan, Devinder

1986-01-01

A catalyst and process useful at low temperatures (below about 160.degree. C.) and preferably in the range 80.degree.-120.degree. C. used in the production of methanol from carbon monoxide and hydrogen is disclosed. The catalyst is used in slurry form and comprises a complex reducing agent derived from the component structure NaH--RONa--M(OAc).sub.2 where M is selected from the group consisting of Ni, Pd, and Co and R is a lower alkyl group containing 1-6 carbon atoms. This catalyst is preferably used alone but is also effective in combination with a metal carbonyl of a group VI (Mo, Cr, W) metal. The preferred catalyst precursor is Nic (where M=Ni and R=tertiary amyl). Mo(CO).sub.6 is the preferred metal carbonyl if such component is used. The catalyst is subjected to a conditioning or activating step under temperature and pressure, similar to the parameters given above, to afford the active catalyst.

Method of making MEA for PEM/SPE fuel cell

DOEpatents

Hulett, Jay S.

2000-01-01

A method of making a membrane-electrode-assembly (MEA) for a PEM/SPE fuel cell comprising applying a slurry of electrode-forming material directly onto a membrane-electrolyte film. The slurry comprises a liquid vehicle carrying catalyst particles and a binder for the catalyst particles. The membrane-electrolyte is preswollen by contact with the vehicle before the electrode-forming slurry is applied to the membrane-electrolyte. The swollen membrane-electrolyte is constrained against shrinking in the "x" and "y" directions during drying. Following assembly of the fuel cell, the MEA is rehydrated inside the fuel cell such that it swells in the "z" direction for enhanced electrical contact with contiguous electrically conductive components of the fuel cell.

Fibers comprised of epitaxially grown single-wall carbon nanotubes, and a method for added catalyst and continuous growth at the tip

DOEpatents

Kittrell, W. Carter; Wang, Yuhuang; Kim, Myung Jong; Hauge, Robert H.; Smalley, Richard E.; Marek leg, Irene Morin

2010-06-01

The present invention is directed to fibers of epitaxially grown single-wall carbon nanotubes (SWNTs) and methods of making same. Such methods generally comprise the steps of: (a) providing a spun SWNT fiber; (b) cutting the fiber substantially perpendicular to the fiber axis to yield a cut fiber; (c) etching the cut fiber at its end with a plasma to yield an etched cut fiber; (d) depositing metal catalyst on the etched cut fiber end to form a continuous SWNT fiber precursor; and (e) introducing feedstock gases under SWNT growth conditions to grow the continuous SWNT fiber precursor into a continuous SWNT fiber.

Metallization of bacterial cellulose for electrical and electronic device manufacture

DOEpatents

Evans, Barbara R.; O'Neill, Hugh M.; Jansen, Valerie Malyvanh; Woodward, Jonathan

2006-01-17

The employment of metallized bacterial cellulose in the construction of fuel cells and other electronic devices is disclosed. The fuel cell includes an electrolyte membrane comprising a membrane support structure comprising bacterial cellulose, an anode disposed on one side of the electrolyte membrane, and a cathode disposed on an opposite side of the electrolyte membrane. At least one of the anode and the cathode comprises an electrode support structure comprising bacterial cellulose, and a catalyst disposed in or on the electrode support structure.

75 FR 39662 - Foreign-Trade Subzone 116A-Port Arthur, TX; Expansion of Manufacturing Authority; Motiva...

Federal Register 2010, 2011, 2012, 2013, 2014

2010-07-12

... request involves the construction of additional crude distillation, coking, integrated hydrocracker/diesel... proposed expansion would increase the overall crude distillation capacity allowed under FTZ procedures to... certain petrochemical feedstocks (duty-free) by admitting foreign crude oil in non-privileged foreign...

Supported molybdenum oxides as effective catalysts for the catalytic fast pyrolysis of lignocellulosic biomass

DOE PAGES

Murugappan, Karthick; Mukarakate, Calvin; Budhi, Sridhar; ...

2016-07-12

The catalytic fast pyrolysis (CFP) of pine was investigated over 10 wt% MoO 3/TiO 2 and MoO 3/ZrO 2 at 500 °C and H 2 pressures ≤ 0.75 bar. The product distributions were monitored in real time using a molecular beam mass spectrometer (MBMS). Both supported MoO 3 catalysts show different levels of deoxygenation based on the cumulative biomass to MoO 3 mass ratio exposed to the catalytic bed. For biomass to MoO 3 mass ratios <1.5, predominantly olefinic and aromatic hydrocarbons are produced with no detectable oxygen-containing species. For ratios ≥ 1.5, partially deoxygenated species comprised of furans andmore » phenols are observed, with a concomitant decrease of olefinic and aromatic hydrocarbons. For ratios ≥ 5, primary pyrolysis vapours break through the bed, indicating the onset of catalyst deactivation. Product quantification with a tandem micropyrolyzer-GCMS setup shows that fresh supported MoO 3 catalysts convert ca. 27 mol% of the original carbon into hydrocarbons comprised predominantly of aromatics (7 C%), olefins (18 C%) and paraffins (2 C%), comparable to the total hydrocarbon yield obtained with HZSM-5 operated under similar reaction conditions. In conclusion, post-reaction XPS analysis on supported MoO 3/ZrO 2 and MoO 3/TiO 2 catalysts reveal that ca. 50% of Mo surface species exist in their partially reduced forms (i.e., Mo 5+ and Mo 3+), and that catalyst deactivation is likely associated to coking.« less

Preparation of supported electrocatalyst comprising multiwalled carbon nanotubes

DOEpatents

Wu, Gang; Zelenay, Piotr

2013-08-27

A process for preparing a durable non-precious metal oxygen reduction electrocatalyst involves heat treatment of a ball-milled mixture of polyaniline and multiwalled carbon nanotubes in the presence of a Fe species. The catalyst is more durable than catalysts that use carbon black supports. Performance degradation was minimal or absent after 500 hours of operation at constant cell voltage of 0.40 V.

Pyrolytic conversion of plastic and rubber waste to hydrocarbons with basic salt catalysts

DOEpatents

Wingfield, Jr., Robert C.; Braslaw, Jacob; Gealer, Roy L.

1985-01-01

The invention relates to a process for improving the pyrolytic conversion of waste selected from rubber and plastic to low molecular weight olefinic materials by employing basis salt catalysts in the waste mixture. The salts comprise alkali or alkaline earth compounds, particularly sodium carbonate, in an amount of greater than about 1 weight percent based on the waste feed.

Microemulsion impregnated catalyst composite and use thereof in a synthesis gas conversion process

DOEpatents

Abrevaya, H.; Targos, W.M.

1987-12-22

A catalyst composition is described for synthesis gas conversion comprising a ruthenium metal component deposited on a support carrier wherein the average metal particle size is less than about 100 A. The method of manufacture of the composition via a reverse micelle impregnation technique and the use of the composition in a Fischer-Tropsch conversion process is also disclosed.

Battery and fuel cell electrodes containing stainless steel charging additive

DOEpatents

Zuckerbrod, David; Gibney, Ann

1984-01-01

An electrode for use in electrochemical energy cells is made, comprising a hydrophilic layer and a hydrophobic layer, where the hydrophilic layer comprises a hydrophilic composite which includes: (i) carbon particles; (ii) stainless steel particles; (iii) a nonwetting agent; and (iv) a catalyst, where at least one current collector contacts said composite.

Preparation of .alpha., .beta.-unsaturated carboxylic acids and anhydrides

DOEpatents

Spivey, James Jerry; Gogate, Makarand Ratnakav; Zoeller, Joseph Robert; Tustin, Gerald Charles

1998-01-01

Disclosed is a process for the preparation of .alpha.,.beta.-unsaturated carboxylic acids and anhydrides thereof which comprises contacting formaldehyde or a source of formaldehyde with a carboxylic anhydride in the presence of a catalyst comprising mixed oxides of vanadium, phosphorus and, optionally, a third component selected from titanium, aluminum or, preferably silicon.

Preparation of {alpha}, {beta}-unsaturated carboxylic acids and anhydrides

DOEpatents

Spivey, J.J.; Gogate, M.R.; Zoeller, J.R.; Tustin, G.C.

1998-01-20

Disclosed is a process for the preparation of {alpha},{beta}-unsaturated carboxylic acids and anhydrides thereof which comprises contacting formaldehyde or a source of formaldehyde with a carboxylic anhydride in the presence of a catalyst comprising mixed oxides of vanadium, phosphorus and, optionally, a third component selected from titanium, aluminum or, preferably silicon.

Process for conversion of levulinic acid to ketones

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

Dagle, Vanessa M.; Dagle, Robert A.

A method for generating desired platform chemicals from feedstocks such as cellulosic biomass feedstocks containing levulinic acid by decarboxylating a feed stock comprising levulinic acid to generate ketones. This is done by passing a feed stock comprising levulinic acid in a gas phase over a non-precious metal catalyst on a neutral support.

Solar Powered CO.Sub.2 Conversion

NASA Technical Reports Server (NTRS)

Chen, Bin (Inventor)

2016-01-01

Methods and devices for reducing CO.sub.2 to produce hydrocarbons are disclosed. A device comprises a photoanode capable of splitting H.sub.2O into electrons, protons, and oxygen; an electrochemical cell cathode comprising an electro-catalyst capable of reducing CO.sub.2; H.sub.2O in contact with the surface of the photoanode; CO.sub.2 in contact with the surface of the cathode; and a proton-conducting medium positioned between the photoanode and the cathode. Electrical charges associated with the protons and the electrons move from the photoanode to the cathode, driven in part by a chemical potential difference sufficient to drive the electrochemical reduction of CO.sub.2 at the cathode. A light beam is the sole source of energy used to drive chemical reactions. The photoanode can comprise TiO.sub.2 nanowires or nanotubes, and can also include WO.sub.3 nanowires or nanotubes, quantum dots of CdS or PbS, and Ag or Au nanostructures. The cathode can comprise a conductive gas diffusion layer with nanostructures of an electro-catalyst such as Cu or Co.

Anchored nanostructure materials and method of fabrication

DOEpatents

Seals, Roland D; Menchhofer, Paul A; Howe, Jane Y; Wang, Wei

2012-11-27

Anchored nanostructure materials and methods for their fabrication are described. The anchored nanostructure materials may utilize nano-catalysts that include powder-based or solid-based support materials. The support material may comprise metal, such as NiAl, ceramic, a cermet, or silicon or other metalloid. Typically, nanoparticles are disposed adjacent a surface of the support material. Nanostructures may be formed as anchored to nanoparticles that are adjacent the surface of the support material by heating the nano-catalysts and then exposing the nano-catalysts to an organic vapor. The nanostructures are typically single wall or multi-wall carbon nanotubes.

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

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

Andrew, S.P.S.

1984-09-25

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

Iron catalyst for preparation of polymethylene from synthesis gas and method for producing the catalyst

DOEpatents

Sapienza, R.S.; Slegeir, W.A.

1990-05-15

This invention relates to a process for synthesizing hydrocarbons; more particularly, the invention relates to a process for synthesizing long-chain hydrocarbons known as polymethylene from carbon monoxide and hydrogen or from carbon monoxide and water or mixtures thereof in the presence of a catalyst comprising iron and platinum or palladium or mixtures thereof which may be supported on a solid material, preferably an inorganic refractory oxide. This process may be used to convert a carbon monoxide containing gas to a product which could substitute for high density polyethylene.

Iron catalyst for preparation of polymethylene from synthesis gas and method for producing the catalyst

DOEpatents

Sapienza, Richard S.; Slegeir, William A.

1990-01-01

This invention relates to a process for synthesizing hydrocarbons; more particularly, the invention relates to a process for synthesizing long-chain hydrocarbons known as polymethylene from carbon monoxide and hydrogen or from carbon monoxide and water or mixtures thereof in the presence of a catalyst comprising iron and platinum or palladium or mixtures thereof which may be supported on a solid material, preferably an inorganic refractory oxide. This process may be used to convert a carbon monoxide containing gas to a product which could substitute for high density polyethylene.

Process for the production of ethylidene diacetate from dimethyl ether using a heterogeneous catalyst

DOEpatents

Ramprasad, D.; Waller, F.J.

1998-04-28

This invention relates to a process for producing ethylidene diacetate by the reaction of dimethyl ether, acetic acid, hydrogen and carbon monoxide at elevated temperatures and pressures in the presence of an alkyl halide and a heterogeneous, bifunctional catalyst that is stable to hydrogenation and comprises an insoluble polymer having pendant quaternized heteroatoms, some of which heteroatoms are ionically bonded to anionic Group VIII metal complexes, the remainder of the heteroatoms being bonded to iodide. In contrast to prior art processes, no accelerator (promoter) is necessary to achieve the catalytic reaction and the products are easily separated from the catalyst by filtration. The catalyst can be recycled for 3 consecutive runs without loss in activity.

Contact structure for use in catalytic distillation

DOEpatents

Jones, E.M. Jr.

1984-03-27

A method is described for conducting catalytic chemical reactions and fractionation of the reaction mixture comprising feeding reactants into a distillation column reactor, contracting said reactant in liquid phase with a fixed bed catalyst in the form of a contact catalyst structure consisting of closed porous containers containing the catalyst for the reaction and a clip means to hold and support said containers, which are disposed above, i.e., on the distillation trays in the tower. The trays have weir means to provide a liquid level on the trays to substantially cover the containers. In other words, the trays function in their ordinary manner with the addition thereto of the catalyst. The reaction mixture is concurrently fractionated in the column. 7 figs.

Contact structure for use in catalytic distillation

DOEpatents

Jones, Jr., Edward M.

1985-01-01

A method and apparatus for conducting catalytic chemical reactions and fractionation of the reaction mixture, comprising and feeding reactants into a distillation column reactor contracting said reactant in a liquid phase with a fixed bed catalyst in the form of a contact catalyst structure, consisting of closed porous containers containing the catalyst for the reaction and a clip means to hold and support said containers, which are disposed above, i.e., on the distillation trays in the tower. The trays have weir means to provide a liquid level on the trays to substantially cover the containers. In other words, the trays function in their ordinary manner with the addition thereto of the catalyst. The reaction mixture is concurrently fractionated in the column.

Contact structure for use in catalytic distillation

DOEpatents

Jones, E.M. Jr.

1985-08-20

A method and apparatus are disclosed for conducting catalytic chemical reactions and fractionation of the reaction mixture, comprising and feeding reactants into a distillation column reactor contracting said reactant in a liquid phase with a fixed bed catalyst in the form of a contact catalyst structure, consisting of closed porous containers containing the catalyst for the reaction and a clip means to hold and support said containers, which are disposed above, i.e., on the distillation trays in the tower. The trays have weir means to provide a liquid level on the trays to substantially cover the containers. In other words, the trays function in their ordinary manner with the addition thereto of the catalyst. The reaction mixture is concurrently fractionated in the column. 7 figs.

Method of preparing and utilizing a catalyst system for an oxidation process on a gaseous hydrocarbon stream

DOEpatents

Berry, David A; Shekhawat, Dushyant; Smith, Mark; Haynes, Daniel

2013-07-16

The disclosure relates to a method of utilizing a catalyst system for an oxidation process on a gaseous hydrocarbon stream with a mitigation of carbon accumulation. The system is comprised of a catalytically active phase deposited onto an oxygen conducting phase, with or without supplemental support. The catalytically active phase has a specified crystal structure where at least one catalytically active metal is a cation within the crystal structure and coordinated with oxygen atoms within the crystal structure. The catalyst system employs an optimum coverage ratio for a given set of oxidation conditions, based on a specified hydrocarbon conversion and a carbon deposition limit. Specific embodiments of the catalyst system are disclosed.

Process for the production of ethylidene diacetate from dimethyl ether using a heterogeneous catalyst

DOEpatents

Ramprasad, Dorai; Waller, Francis Joseph

1998-01-01

This invention relates to a process for producing ethylidene diacetate by the reaction of dimethyl ether, acetic acid, hydrogen and carbon monoxide at elevated temperatures and pressures in the presence of an alkyl halide and a heterogeneous, bifunctional catalyst that is stable to hydrogenation and comprises an insoluble polymer having pendant quaternized heteroatoms, some of which heteroatoms are ionically bonded to anionic Group VIII metal complexes, the remainder of the heteroatoms being bonded to iodide. In contrast to prior art processes, no accelerator (promoter) is necessary to achieve the catalytic reaction and the products are easily separated from the catalyst by filtration. The catalyst can be recycled for 3 consecutive runs without loss in activity.

Hydrocarbon reforming catalyst material and configuration of the same

DOEpatents

Singh, Prabhakar; Shockling, Larry A.; George, Raymond A.; Basel, Richard A.

1996-01-01

A hydrocarbon reforming catalyst material comprising a catalyst support impregnated with catalyst is provided for reforming hydrocarbon fuel gases in an electrochemical generator. Elongated electrochemical cells convert the fuel to electrical power in the presence of an oxidant, after which the spent fuel is recirculated and combined with a fresh hydrocarbon feed fuel forming the reformable gas mixture which is fed to a reforming chamber containing a reforming catalyst material, where the reforming catalyst material includes discrete passageways integrally formed along the length of the catalyst support in the direction of reformable gas flow. The spent fuel and/or combusted exhaust gases discharged from the generator chamber transfer heat to the catalyst support, which in turn transfers heat to the reformable gas and to the catalyst, preferably via a number of discrete passageways disposed adjacent one another in the reforming catalyst support. The passageways can be slots extending inwardly from an outer surface of the support body, which slots are partly defined by an exterior confining wall. According to a preferred embodiment, the catalyst support is non-rigid, porous, fibrous alumina, wherein the fibers are substantially unsintered and compressible, and the reforming catalyst support is impregnated, at least in the discrete passageways with Ni and MgO, and has a number of internal slot passageways for reformable gas, the slot passageways being partly closed by a containing outer wall.

Hydrocarbon reforming catalyst material and configuration of the same

DOEpatents

Singh, P.; Shockling, L.A.; George, R.A.; Basel, R.A.

1996-06-18

A hydrocarbon reforming catalyst material comprising a catalyst support impregnated with catalyst is provided for reforming hydrocarbon fuel gases in an electrochemical generator. Elongated electrochemical cells convert the fuel to electrical power in the presence of an oxidant, after which the spent fuel is recirculated and combined with a fresh hydrocarbon feed fuel forming the reformable gas mixture which is fed to a reforming chamber containing a reforming catalyst material, where the reforming catalyst material includes discrete passageways integrally formed along the length of the catalyst support in the direction of reformable gas flow. The spent fuel and/or combusted exhaust gases discharged from the generator chamber transfer heat to the catalyst support, which in turn transfers heat to the reformable gas and to the catalyst, preferably via a number of discrete passageways disposed adjacent one another in the reforming catalyst support. The passageways can be slots extending inwardly from an outer surface of the support body, which slots are partly defined by an exterior confining wall. According to a preferred embodiment, the catalyst support is non-rigid, porous, fibrous alumina, wherein the fibers are substantially unsintered and compressible, and the reforming catalyst support is impregnated, at least in the discrete passageways with Ni and MgO, and has a number of internal slot passageways for reformable gas, the slot passageways being partly closed by a containing outer wall. 5 figs.

Catalyst for the methanation of carbon monoxide in sour gas

DOEpatents

Kustes, William A.; Hausberger, Arthur L.

1985-01-01

The invention involves the synergistic effect of the specific catalytic constituents on a specific series of carriers for the methanation of carbon monoxide in the presence of sulfur at relatively high temperatures and at low steam to gas ratios in the range of 0.2:1 or less. This effect was obtained with catalysts comprising the mixed sulfides and oxides of nickel and chromium supported on carriers comprising magnesium aluminate and magnesium silicate. Conversion of carbon monoxide to methane was in the range of from 40 to 80%. Tests of this combination of metal oxides and sulfides on other carriers and tests of other metal oxides and sulfides on the same carrier produced a much lower level of conversion.

Zeolitic catalytic conversion of alochols to hydrocarbons

DOEpatents

Narula, Chaitanya K.; Davison, Brian H.; Keller, Martin

2017-01-03

A method for converting an alcohol to a hydrocarbon, the method comprising contacting said alcohol with a metal-loaded zeolite catalyst at a temperature of at least 100.degree. C. and up to 550.degree. C., wherein said alcohol can be produced by a fermentation process, said metal is a positively-charged metal ion, and said metal-loaded zeolite catalyst is catalytically active for converting said alcohol to said hydrocarbon.

Zeolitic catalytic conversion of alcohols to hydrocarbons

DOEpatents

Narula, Chaitanya K.; Davison, Brian H.; Keller, Martin

2018-04-10

A method for converting an alcohol to a hydrocarbon, the method comprising contacting said alcohol with a metal-loaded zeolite catalyst at a temperature of at least 100.degree. C. and up to 550.degree. C., wherein said alcohol can be produced by a fermentation process, said metal is a positively-charged metal ion, and said metal-loaded zeolite catalyst is catalytically active for converting said alcohol to said hydrocarbon.

Integrated process and dual-function catalyst for olefin epoxidation

DOEpatents

Zhou, Bing; Rueter, Michael

2003-01-01

The invention discloses a dual-functional catalyst composition and an integrated process for production of olefin epoxides including propylene oxide by catalytic reaction of hydrogen peroxide from hydrogen and oxygen with olefin feeds such as propylene. The epoxides and hydrogen peroxide are preferably produced simultaneously in situ. The dual-functional catalyst comprises noble metal crystallites with dimensions on the nanometer scale (on the order of <1 nm to 10 nm), specially dispersed on titanium silicalite substrate particles. The dual functional catalyst catalyzes both the direct reaction of hydrogen and oxygen to generate hydrogen peroxide intermediate on the noble metal catalyst surface and the reaction of the hydrogen peroxide intermediate with the propylene feed to generate propylene oxide product. Combining both these functions in a single catalyst provides a very efficient integrated process operable below the flammability limits of hydrogen and highly selective for the production of hydrogen peroxide to produce olefin oxides such as propylene oxide without formation of undesired co-products.

Optimization of levulinic acid from lignocellulosic biomass using a new hybrid catalyst.

PubMed

Ya'aini, Nazlina; Amin, Nor Aishah Saidina; Asmadi, Mohd

2012-07-01

Conversion of glucose, empty fruit bunch (efb) and kenaf to levulinic acid over a new hybrid catalyst has been investigated in this study. The characterization and catalytic performance results revealed that the physico-chemical properties of the new hybrid catalyst comprised of chromium chloride and HY zeolite increased the levulinic acid production from glucose compared to the parent catalysts. Optimization of the glucose conversion process using two level full factorial designs (2(3)) with two center points reported 55.2% of levulinic acid yield at 145.2 °C, 146.7 min and 12.0% of reaction temperature, reaction time and catalyst loading, respectively. Subsequently, the potential of efb and kenaf for producing levulinic acid at the optimum conditions was established after 53.2% and 66.1% of efficiencies were reported. The observation suggests that the hybrid catalyst has a potential to be used in biomass conversion to levulinic acid. Copyright © 2012 Elsevier Ltd. All rights reserved.

Nanostructured Perovskite LaCo1-xMnxO3 as Bifunctional Catalysts for Rechargeable Metal-Air Batteries

NASA Astrophysics Data System (ADS)

Ge, Xiaoming; Li, Bing; Wuu, Delvin; Sumboja, Afriyanti; An, Tao; Hor, T. S. Andy; Zong, Yun; Liu, Zhaolin

2015-09-01

Bifunctional catalyst that is active for both oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) is one of the most important components of rechargeable metal-air batteries. Nanostructured perovskite bifunctional catalysts comprising La, Co and Mn(LaCo1-xMnxO3, LCMO) are synthesized by hydrothermal methods. The morphology, structure and electrochemical activity of the perovskite bifunctional catalysts are characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD) and rotating disk electrode (RDE) techniques. Nanorod, nanodisc and nanoparticle are typical morphologies of LCMO. The electrocatalytic activity of LCMO is significantly improved by the addition of conductive materials such as carbon nanotube. To demonstrate the practical utilization, LCMO in the composition of LaCo0.8Mn0.2O3(LCMO82) is used as air cathode catalysts for rechargeable zinc-air batteries. The battery prototype can sustain 470 h or 40 discharge-charge cycles equivalent.

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.

Layered electrode for electrochemical cells

DOEpatents

Swathirajan, Swathy; Mikhail, Youssef M.

2001-01-01

There is provided an electrode structure comprising a current collector sheet and first and second layers of electrode material. Together, the layers improve catalyst utilization and water management.

Ethanol production with dilute acid hydrolysis using partially dried lignocellulosics

DOEpatents

Nguyen, Quang A.; Keller, Fred A.; Tucker, Melvin P.

2003-12-09

A process of converting lignocellulosic biomass to ethanol, comprising hydrolyzing lignocellulosic materials by subjecting dried lignocellulosic material in a reactor to a catalyst comprised of a dilute solution of a strong acid and a metal salt to lower the activation energy (i.e., the temperature) of cellulose hydrolysis and ultimately obtain higher sugar yields.

Extrusion cast explosive

DOEpatents

Scribner, Kenneth J.

1985-01-01

Improved, multiphase, high performance, high energy, extrusion cast explosive compositions, comprising, a crystalline explosive material; an energetic liquid plasticizer; a urethane prepolymer, comprising a blend of polyvinyl formal, and polycaprolactone; a polyfunctional isocyanate; and a catalyst are disclosed. These new explosive compositions exhibit higher explosive content, a smooth detonation front, excellent stability over long periods of storage, and lower sensitivity to mechanical stimulants.

Nature-driven photochemistry for catalytic solar hydrogen production: a Photosystem I-transition metal catalyst hybrid.

PubMed

Utschig, Lisa M; Silver, Sunshine C; Mulfort, Karen L; Tiede, David M

2011-10-19

Solar energy conversion of water into the environmentally clean fuel hydrogen offers one of the best long-term solutions for meeting future energy demands. Nature provides highly evolved, finely tuned molecular machinery for solar energy conversion that exquisitely manages photon capture and conversion processes to drive oxygenic water-splitting and carbon fixation. Herein, we use one of Nature's specialized energy-converters, the Photosystem I (PSI) protein, to drive hydrogen production from a synthetic molecular catalyst comprised of inexpensive, earth-abundant materials. PSI and a cobaloxime catalyst self-assemble, and the resultant complex rapidly produces hydrogen in aqueous solution upon exposure to visible light. This work establishes a strategy for enhancing photosynthetic efficiency for solar fuel production by augmenting natural photosynthetic systems with synthetically tunable abiotic catalysts.

Catalysts for the production of hydrocarbons from carbon monoxide and water

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

Sapienza, Richard S.; Slegeir, William A.; Goldberg, Robert I.

1987-01-01

A method of converting low H.sub.2 /CO ratio syngas to carbonaceous products comprising reacting the syngas with water or steam at 200.degree. to 350.degree. C. in the presence of a metal catalyst supported on zinc oxide. Hydrocarbons are produced with a catalyst selected from cobalt, nickel or ruthenium and alcohols are produced with a catalyst selected from palladium, platinium, ruthenium or copper on the zinc oxide support. The ratio of the reactants are such that for alcohols and saturated hydrocarbons: (2n+1).gtoreq.x.gtoreq.O and for olefinic hydrocarbons: 2n.gtoreq.x.gtoreq.O where n is the number of carbon atoms in the product and x ismore » the molar amount of water in the reaction mixture.« less

Metal phthalocyanine catalysts

DOEpatents

Ellis, Jr., Paul E.; Lyons, James E.

1994-01-01

As a new composition of matter, alkali metal or ammonium or tetraalkylammonium diazidoperfluorophthalocyanatoferrate. Other embodiments of the invention comprise compositions wherein the metal of the coordination complex is cobalt, manganese and chromium.

Copper-containing zeolite catalysts

DOEpatents

Price, G.L.; Kanazirev, V.

1996-12-10

A catalyst useful in the conversion of nitrogen oxides or in the synthesis of nitriles or imines from amines, is formed by preparing an intimate mechanical mixture of a copper (II)-containing species, such as CuO or CuCl{sub 2}, or elemental copper, with a zeolite having a pore mouth comprising 10 oxygen atoms, such as ZSM-5, converting the elemental copper or copper (II) to copper (I), and driving the copper (I) into the zeolite.

Copper-containing zeolite catalysts

DOEpatents

Price, Geoffrey L.; Kanazirev, Vladislav

1996-01-01

A catalyst useful in the conversion of nitrogen oxides or in the synthesis of nitriles or imines from amines, formed by preparing an intimate mechanical mixture of a copper (II)-containing species, such as CuO or CuCl.sub.2, or elemental copper, with a zeolite having a pore mouth comprising 10 oxygen atoms, such as ZSM-5, converting the elemental copper or copper (II) to copper (I), and driving the copper (I) into the zeolite.

Processes for converting biomass-derived feedstocks to chemicals and liquid fuels

DOEpatents

Held, Andrew; Woods, Elizabeth; Cortright, Randy; Gray, Matthew

2017-05-23

The present invention provides processes, methods, and systems for converting biomass-derived feedstocks to liquid fuels and chemicals. The method generally includes the reaction of a hydrolysate from a biomass deconstruction process with hydrogen and a catalyst to produce a reaction product comprising one of more oxygenated compounds. The process also includes reacting the reaction product with a condensation catalyst to produce C.sub.4+ compounds useful as fuels and chemicals.

Processes for converting biomass-derived feedstocks to chemicals and liquid fuels

DOEpatents

Held, Andrew; Woods, Elizabeth; Cortright, Randy; Gray, Matthew

2016-07-05

The present invention provides processes, methods, and systems for converting biomass-derived feedstocks to liquid fuels and chemicals. The method generally includes the reaction of a hydrolysate from a biomass deconstruction process with hydrogen and a catalyst to produce a reaction product comprising one of more oxygenated compounds. The process also includes reacting the reaction product with a condensation catalyst to produce C.sub.4+ compounds useful as fuels and chemicals.

Processes for converting biomass-derived feedstocks to chemicals and liquid fuels

DOEpatents

Held, Andrew; Woods, Elizabeth; Cortright, Randy; Gray, Matthew

2018-04-17

The present invention provides processes, methods, and systems for converting biomass-derived feedstocks to liquid fuels and chemicals. The method generally includes the reaction of a hydrolysate from a biomass deconstruction process with hydrogen and a catalyst to produce a reaction product comprising one of more oxygenated compounds. The process also includes reacting the reaction product with a condensation catalyst to produce C.sub.4+ compounds useful as fuels and chemicals.

Cyclic catalytic upgrading of chemical species using metal oxide materials

NASA Technical Reports Server (NTRS)

White, James H. (Inventor); Schutte, Erick J. (Inventor); Rolfe, Sara L. (Inventor)

2010-01-01

Processes are disclosure which comprise alternately contacting an oxygen-carrying catalyst with a reducing substance, or a lower partial pressure of an oxidizing gas, and then with the oxidizing gas or a higher partial pressure of the oxidizing gas, whereby the catalyst is alternately reduced and then regenerated to an oxygenated state. In certain embodiments, the oxygen-carrying catalyst comprises at least one metal oxide-containing material containing a composition having one of the following formulas: (a) Ce.sub.xB.sub.yB'.sub.zB''O.sub..delta., wherein B=Ba, Sr, Ca, or Zr; B'=Mn, Co, or Fe; B''=Cu; 0.01

Cyclic catalytic upgrading of chemical species using metal oxide materials

DOEpatents

White, James H.; Schutte, Erick J.; Rolfe, Sara L.

2010-11-02

Processes are disclosure which comprise alternately contacting an oxygen-carrying catalyst with a reducing substance, or a lower partial pressure of an oxidizing gas, and then with the oxidizing gas or a higher partial pressure of the oxidizing gas, whereby the catalyst is alternately reduced and then regenerated to an oxygenated state. In certain embodiments, the oxygen-carrying catalyst comprises at least one metal oxide-containing material containing a composition having one of the following formulas: (a) Ce.sub.xB.sub.yB'.sub.zB''O.sub..delta., wherein B=Ba, Sr, Ca, or Zr; B'=Mn, Co, or Fe; B''=Cu; 0.01

Methods of producing porous platinum-based catalysts for oxygen reduction

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

Erlebacher, Jonah D.; Snyder, Joshua D.

A porous metal that comprises platinum and has a specific surface area that is greater than 5 m 2/g and less than 75 m 2/g. A fuel cell includes a first electrode, a second electrode spaced apart from the first electrode, and an electrolyte arranged between the first and the second electrodes. At least one of the first and second electrodes is coated with a porous metal catalyst for oxygen reduction, and the porous metal catalyst comprises platinum and has a specific surface area that is greater than 5 m 2/g and less than 75 m 2/g. A method ofmore » producing a porous metal according to an embodiment of the current invention includes producing an alloy consisting essentially of platinum and nickel according to the formula Pt xNi 1-x, where x is at least 0.01 and less than 0.3; and dealloying the alloy in a substantially pH neutral solution to reduce an amount of nickel in the alloy to produce the porous metal.« less

Hydrothermal alkali metal catalyst recovery process

DOEpatents

Eakman, James M.; Clavenna, LeRoy R.

1979-01-01

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

Porous platinum-based catalysts for oxygen reduction

DOEpatents

Erlebacher, Jonah D; Snyder, Joshua D

2014-11-25

A porous metal that comprises platinum and has a specific surface area that is greater than 5 m.sup.2/g and less than 75 m.sup.2/g. A fuel cell includes a first electrode, a second electrode spaced apart from the first electrode, and an electrolyte arranged between the first and the second electrodes. At least one of the first and second electrodes is coated with a porous metal catalyst for oxygen reduction, and the porous metal catalyst comprises platinum and has a specific surface area that is greater than 5 m.sup.2/g and less than 75 m.sup.2/g. A method of producing a porous metal according to an embodiment of the current invention includes producing an alloy consisting essentially of platinum and nickel according to the formula Pt.sub.xNi.sub.1-x, where x is at least 0.01 and less than 0.3; and dealloying the alloy in a substantially pH neutral solution to reduce an amount of nickel in the alloy to produce the porous metal.

Catalysts for converting syngas into liquid hydrocarbons and methods thereof

DOEpatents

Yu, Fei; Yan, Qiangu; Batchelor, William

2016-03-15

The presently-disclosed subject matter includes methods for producing liquid hydrocarbons from syngas. In some embodiments the syngas is obtained from biomass and/or comprises a relatively high amount of nitrogen and/or carbon dioxide. In some embodiments the present methods can convert syngas into liquid hydrocarbons through a one-stage process. Also provided are catalysts for producing liquid hydrocarbons from syngas, wherein the catalysts include a base material, a transition metal, and a promoter. In some embodiments the base material includes a zeolite-iron material or a cobalt-molybdenum carbide material. In still further embodiments the promoter can include an alkali metal.

Extrusion cast explosive

DOEpatents

Scribner, K.J.

1985-01-29

Improved, multiphase, high performance, high energy, extrusion cast explosive compositions, comprising, a crystalline explosive material; an energetic liquid plasticizer; a urethane prepolymer, comprising a blend of polyvinyl formal, and polycaprolactone; a polyfunctional isocyanate; and a catalyst are disclosed. These new explosive compositions exhibit higher explosive content, a smooth detonation front, excellent stability over long periods of storage, and lower sensitivity to mechanical stimulants. 1 fig.

Extrusion cast explosive

DOEpatents

Scribner, K.J.

1985-11-26

Disclosed is an improved, multiphase, high performance, high energy, extrusion cast explosive compositions, comprising, a crystalline explosive material; an energetic liquid plasticizer; a urethane prepolymer, comprising a blend of polyvinyl formal, and polycaprolactone; a polyfunctional isocyanate; and a catalyst. These new explosive compositions exhibit higher explosive content, a smooth detonation front, excellent stability over long periods of storage, and lower sensitivity to mechanical stimulants. 1 fig.

Hydrogen sulfide-powered solid oxide fuel cells

NASA Astrophysics Data System (ADS)

Liu, Man

2004-12-01

The potential utilization of hydrogen sulfide as fuel in solid oxide fuel cells has been investigated using an oxide-ion conducting YSZ electrolyte and different kinds of anode catalysts at operating temperatures in the range of 700--900°C and at atmospheric pressure. This technology offers an economically attractive alternative to present methods for removing toxic and corrosive H2S gas from sour gas streams and a promising approach for cogenerating electrical energy and useful chemicals. The primary objective of the present research was to find active and stable anode materials. Fuel cell experimental results showed that platinum was a good electrocatalyst for the conversion of H2S, but the Pt/YSZ interface was physically unstable due to the reversible formation and decomposition of PtS in H 2S streams at elevated temperatures. Moreover, instability of the Pt/YSZ interface was accelerated significantly by electrochemical reactions, and ultimately led to the detachment of the Pt anode from the electrolyte. It has been shown that an interlayer of TiO2 stabilized the Pt anode on YSZ electrolyte, thereby prolonging cell lifetime. However, the current output for a fuel cell using Pt/TiO2 as anode was not improved compared to using Pt alone. It was therefore necessary to investigate novel anode systems for H 2S-air SOFCs. New anode catalysts comprising composite metal sulfides were developed. These catalysts exhibited good electrical conductivity and better catalytic activity than Pt. In contrast to MoS2 alone, composite catalysts (M-Mo-S, M = Fe, Co, Ni) were not volatile and had superior stability. However, when used for extended periods of time, detachment of Pt current collecting film from anodes comprising metal sulfides alone resulted in a large increase in contact resistance and reduction in cell performance. Consequently, a systematic investigation was conducted to identify alternative electronic conductors for use with M-Mo-S catalysts. Anode catalysts comprising Co-Mo-S admixed with up to 10% Ag powder were found to have excellent performance and longevity, as well as improved electrical contact when compared with Pt/M-Mo-S anode systems. The highest current density of 450 mA/cm2 and power density of 115 mW/cm2 were achieved with an anode that consisted of 95% (Co-Mo-S) and 5% Ag.

A binary catalyst system of a cationic Ru-CNC pincer complex with an alkali metal salt for selective hydroboration of carbon dioxide.

PubMed

Ng, Chee Koon; Wu, Jie; Hor, T S Andy; Luo, He-Kuan

2016-09-27

Binary catalyst systems comprising a cationic Ru-CNC pincer complex and an alkali metal salt were developed for selective hydroboration of CO 2 utilizing pinacolborane at r.t. and 1 atm CO 2 , with the combination of [Ru(CNC Bn )(CO) 2 (H)][PF 6 ] and KOCO 2 t Bu producing formoxyborane in 76% yield. A bicyclic catalytic mechanism was proposed and discussed.

Gas phase heterogeneous catalytic oxidation of alkanes to aliphatic ketones and/or other oxygenates

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

Lin, Manhua; Wang, Xiang; Yeom, Younghoon

A catalyst, its method of preparation and its use for producing aliphatic ketones by subjecting alkanes C.sub.3 to C.sub.9 to a gas phase catalytic oxidation in the presence of air or oxygen, and, optionally, steam and/or one or more diluting gases. The catalyst comprises a catalytically active mixed metal oxide phase and a suitable support material onto and/or into which the active catalytic phase id dispersed.

Gas phase heterogeneous catalytic oxidation of alkanes to aliphatic ketones and/or other oxygenates

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

Lin, Manhua; Wang, Xiang; Yeom, Younghoon

A catalyst, its method of preparation and its use for producing aliphatic ketones by subjecting alkanes C.sub.3 to C.sub.9 to a gas phase catalytic oxidation in the presence of air or oxygen, and, optionally, steam and/or one or more diluting gases. The catalyst comprises a catalytically active mixed metal oxide phase and a suitable support material onto and/or into which the active catalytic phase is dispersed.

Process and catalyst for carbonylating olefins

DOEpatents

Zoeller, Joseph Robert

1998-06-02

Disclosed is an improved catalyst system and process for preparing aliphatic carbonyl compounds such as aliphatic carboxylic acids, alkyl esters of aliphatic carboxylic acids and anhydrides of aliphatic carboxylic acids by carbonylating olefins in the presence of a catalyst system comprising (1) a first component selected from at least one Group 6 metal, i.e., chromium, molybdenum, and/or tungsten and (2) a second component selected from at least one of certain halides and tertiary and quaternary compounds of a Group 15 element, i.e., nitrogen, phosphorus and/or arsenic, and (3) as a third component, a polar, aprotic solvent. The process employing the improved catalyst system is carried out under carbonylating conditions of pressure and temperature discussed herein. The process constitutes and improvement over known processes since it can be carried out at moderate carbonylation conditions without the necessity of using an expensive noble metal catalyst, volatile, toxic materials such as nickel tetracarbonyl, formic acid or a formate ester. Further, the addition of a polar, aprotic solvent to the catalyst system significantly increases, or accelerates, the rate at which the carbonylation takes place.

Catalysts for the production of hydrocarbons from carbon monoxide and water

DOEpatents

Sapienza, R.S.; Slegeir, W.A.; Goldberg, R.I.

1985-11-06

A method of converting low H/sub 2//CO ratio syngas to carbonaceous products comprising reacting the syngas with water or steam at 200 to 350/sup 0/C in the presence of a metal catalyst supported on zinc oxide. Hydrocarbons are produced with a catalyst selected from cobalt, nickel or ruthenium and alcohols are produced with a catalyst selected from palladium, platinum, ruthenium or copper on the zinc oxide support. The ratio of the reactants are such that for alcohols and saturated hydrocarbons: (2n + 1) greater than or equal to x greater than or equal to O and for olefinic hydrocarbons: 2n greater than or equal to x greater than or equal to O where n is the number of carbon atoms in the product and x is the molar amount of water in the reaction mixture.

Production of hydrogen from alcohols

DOEpatents

Deluga, Gregg A [St. Paul, MN; Schmidt, Lanny D [Minneapolis, MN

2007-08-14

A process for producing hydrogen from ethanol or other alcohols. The alcohol, optionally in combination with water, is contacted with a catalyst comprising rhodium. The overall process is preferably carried out under autothermal conditions.

Metal phthalocyanine catalysts

DOEpatents

Ellis, P.E. Jr.; Lyons, J.E.

1994-10-11

A new composition of matter is described which is an alkali metal or ammonium or tetraalkylammonium diazidoperfluorophthalocyanatoferrate. Other embodiments of the invention comprise compositions wherein the metal of the coordination complex is cobalt, manganese and chromium.

Method of forming catalyst layer by single step infiltration

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

Gerdes, Kirk; Lee, Shiwoo; Dowd, Regis

Provided herein is a method for electrocatalyst infiltration of a porous substrate, of particular use for preparation of a cathode for a solid oxide fuel cell. The method generally comprises preparing an electrocatalyst infiltrate solution comprising an electrocatalyst, surfactant, chelating agent, and a solvent; pretreating a porous mixed ionic-electric conductive substrate; and applying the electrocatalyst infiltration solution to the porous mixed ionic-electric conductive substrate.

Size and weight graded multi-ply laminar electrodes

DOEpatents

Liu, Chia-Tsun; Demczyk, Brian G.; Rittko, Irvin R.

1984-01-01

An electrode is made comprising a porous backing sheet, and attached thereto a catalytically active layer having an electrolyte permeable side and a backing layer contacting side, where the active layer comprises a homogeneous mixture of active hydrophobic and hydrophilic agglomerates with catalyst disposed equally throughout the active layer, and where the agglomerate size increases from the electrolyte permeable side to the backing sheet contacting side.

Interstitial modification of palladium nanoparticles with boron atoms as a green catalyst for selective hydrogenation

NASA Astrophysics Data System (ADS)

Chan, Chun Wong Aaron; Mahadi, Abdul Hanif; Li, Molly Meng-Jung; Corbos, Elena Cristina; Tang, Chiu; Jones, Glenn; Kuo, Winson Chun Hsin; Cookson, James; Brown, Christopher Michael; Bishop, Peter Trenton; Tsang, Shik Chi Edman

2014-12-01

Lindlar catalysts comprising of palladium/calcium carbonate modified with lead acetate and quinoline are widely employed industrially for the partial hydrogenation of alkynes. However, their use is restricted, particularly for food, cosmetic and drug manufacture, due to the extremely toxic nature of lead, and the risk of its leaching from catalyst surface. In addition, the catalysts also exhibit poor selectivities in a number of cases. Here we report that a non-surface modification of palladium gives rise to the formation of an ultra-selective nanocatalyst. Boron atoms are found to take residence in palladium interstitial lattice sites with good chemical and thermal stability. This is favoured due to a strong host-guest electronic interaction when supported palladium nanoparticles are treated with a borane tetrahydrofuran solution. The adsorptive properties of palladium are modified by the subsurface boron atoms and display ultra-selectivity in a number of challenging alkyne hydrogenation reactions, which outclass the performance of Lindlar catalysts.

Synthesis of novel perfluoroalkylglucosides on zeolite and non-zeolite catalysts.

PubMed

Nowicki, Janusz; Mokrzycki, Łukasz; Sulikowski, Bogdan

2015-04-08

Perfluoroalkylglucosides comprise a very important class of fluorine-containing surfactants. These compounds can be synthesized by using the Fisher reaction, starting directly from glucose and the required perfluoroalcohols. We wish to report on the use of zeolite catalysts of different structure and composition for the synthesis of perfluoroalkylglucosides when using glucose and 1-octafluoropentanol as substrates. Zeolites of different pore architecture have been chosen (ZSM-5, ZSM-12, MCM-22 and Beta). Zeolites were characterized by XRD, nitrogen sorption, scanning electron microscopy (SEM) and solid-state 27Al MAS NMR spectroscopy. The activity of the zeolite catalysts in the glycosidation reaction was studied in a batch reactor at 100 °C below atmospheric pressure. The performance of zeolites was compared to other catalysts, an ion-exchange resin (Purolite) and a montmorillonite-type layered aluminosilicate. The catalytic performance of zeolite Beta was the highest among the zeolites studied and the results were comparable to those obtained over Purolite and montmorillonite type catalysts.

Conversion of ammonia into hydrogen and nitrogen by reaction with a sulfided catalyst

DOEpatents

Matthews, Charles W.

1977-01-01

A method is provided for removing ammonia from the sour water stream of a coal gasification process. The basic steps comprise stripping the ammonia from the sour water; heating the stripped ammonia to a temperature from between 400.degree. to 1,000.degree. F; passing the gaseous ammonia through a reactor containing a sulfided catalyst to produce elemental hydrogen and nitrogen; and scrubbing the reaction product to obtain an ammonia-free gas. The residual equilibrium ammonia produced by the reactor is recycled into the stripper. The ammonia-free gas may be advantageously treated in a Claus process to recover elemental sulfur. Iron sulfide or cobalt molybdenum sulfide catalysts are used.

Composition and method for polymer moderated catalytic water formation

DOEpatents

Shepodd, Timothy Jon

1999-01-01

A composition suitable for safely removing hydrogen from gaseous mixtures containing hydrogen and oxygen, particularly those mixtures wherein the hydrogen concentration is within the explosive range. The composition comprises a hydrogenation catalyst, preferably Pd dispersed on carbon, wherein the concentration of Pd is from about 1-10 wt %, dispersed in a polymeric material matrix. As well as serving as a matrix to contain the hydrogenation catalyst, the polymeric material, which is substantially unreactive to hydrogen, provides both a diffusion restriction to hydrogen and oxygen, thereby limiting the rate at which the reactants (hydrogen and oxygen) can diffuse to the catalyst surface and thus, the production of heat from the recombination reaction and as a heat sink.

Contact structure for use in catalytic distillation

DOEpatents

Jones, Jr., Edward M.

1984-01-01

A method for conducting catalytic chemical reactions and fractionation of the reaction mixture comprising feeding reactants into a distillation column reactor contracting said reactant in liquid phase with a fixed bed catalyst in the form of a contact catalyst structure consisting of closed porous containers containing the catatlyst for the reaction and a clip means to hold and support said containers, which are disposed above, i.e., on the distillation trays in the tower. The trays have weir means to provide a liquid level on the trays to substantially cover the containers. In other words, the trays function in their ordinary manner with the addition thereto of the catalyst. The reaction mixture is concurrently fractionated in the column.

Catalysts for conversion of methane to higher hydrocarbons

DOEpatents

Siriwardane, Ranjani V.

1993-01-01

Catalysts for converting methane to higher hydrocarbons such as ethane and ethylene in the presence of oxygen at temperatures in the range of about 700.degree. to 900.degree. C. are described. These catalysts comprise calcium oxide or gadolinium oxide respectively promoted with about 0.025-0.4 mole and about 0.1-0.7 mole sodium pyrophosphate. A preferred reaction temperature in a range of about 800.degree. to 850.degree. C. with a preferred oxygen-to-methane ratio of about 2:1 provides an essentially constant C.sub.2 hydrocarbon yield in the range of about 12 to 19 percent over a period of time greater than about 20 hours.

Liquefaction of black thunder coal with counterflow reactor technology

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

Parker, R.J.; Simpson, P.L.

There is currently a resurgence of interest in the use of carbon monoxide and water to promote the solubilization of low rank coals in liquefaction processes. The mechanism for the water shift gas reaction (WGSR) is well documented and proceeds via a formate ion intermediate at temperatures up to about 400{degrees}C. Coal solubilization is enhanced by CO/H{sub 2}O and by the solvent effect of the supercritical water. The WGSR is catalyzed by bases (alkali metal carbonates, hydroxides, acetates, aluminates). Many inorganic salts which promote catalytic hydrogenation are rendered inactive in CO/H{sub 2}O, although there is positive evidence for the benefitmore » of using pyrite for both the WGSR and as a hydrogenation catalyst. The temperatures at which coal solubilization occurs are insufficient to promote extensive cracking or upgrading of the solubilized coal. Therefore, a two step process might achieve these two reactions sequentially. Alberta Research Council (ARC) has developed a two-stage process for the coprocessing of low rank coals and petroleum resids/bitumens. This process was further advanced by utilizing the counterflow reactor (CFR) concept pioneered by Canadian Energy Developments (CED) and ARC. The technology is currently being applied to coal liquefaction. The two-stage process employs CO/H{sub 2}O at relatively mid temperature and pressure to solubilize the coal, followed by a more severe hydrocracking step. This paper describes the results of an autoclave study conducted to support a bench unit program on the direct liquefaction of coals.« less

Upgrading and Refining of Crude Oils and Petroleum Products by Ionizing Irradiation.

PubMed

Zaikin, Yuriy A; Zaikina, Raissa F

2016-06-01

A general trend in the oil industry is a decrease in the proven reserves of light crude oils so that any increase in future oil exploration is associated with high-viscous sulfuric oils and bitumen. Although the world reserves of heavy oil are much greater than those of sweet light oils, their exploration at present is less than 12 % of the total oil recovery. One of the main constraints is very high expenses for the existing technologies of heavy oil recovery, upgrading, transportation, and refining. Heavy oil processing by conventional methods is difficult and requires high power inputs and capital investments. Effective and economic processing of high viscous oil and oil residues needs not only improvements of the existing methods, such as thermal, catalytic and hydro-cracking, but the development of new technological approaches for upgrading and refining of any type of problem oil feedstock. One of the perspective approaches to this problem is the application of ionizing irradiation for high-viscous oil processing. Radiation methods for upgrading and refining high-viscous crude oils and petroleum products in a wide temperature range, oil desulfurization, radiation technology for refining used oil products, and a perspective method for gasoline radiation isomerization are discussed in this paper. The advantages of radiation technology are simple configuration of radiation facilities, low capital and operational costs, processing at lowered temperatures and nearly atmospheric pressure without the use of any catalysts, high production rates, relatively low energy consumption, and flexibility to the type of oil feedstock.

An economical route to high quality lubricants

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

Andre, J.P.; Hahn, S.K.; Kwon, S.H.

1996-12-01

The current rends in the automotive and industrial markets toward more efficient engines, longer drain intervals, and lower emissions all contribute to placing increasingly stringent performance requirements on lubricants. The demand for higher quality synthetic and non-conventional basestocks is expected to grow at a much faster rate than that of conventional lube basestocks to meet these higher performance standards. Yukong Limited has developed a novel technology (the Yukong UCO Lube Process) for the economic production of high quality, high-viscosity-index lube basestocks from a fuels hydrocracker unconverted oil stream. A pilot plant based on this process has been producing oils formore » testing purposes since May 1994. A commercial facility designed to produce 3,500 BPD of VHVI lube basestocks cane on-stream at Yukong`s Ulsan refinery in October 1995. The Badger Technology Center of Raytheon Engineers and Constructors assisted Yukong during the development of the technology and prepared the basic process design package for the commercial facility. This paper presents process aspects of the technology and comparative data on investment and operating costs. Yukong lube basestock product properties and performance data are compared to basestocks produced by conventional means and by lube hydrocracking.« less

Methods and apparatus for carbon dioxide removal from a fluid stream

DOEpatents

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

2010-01-19

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

Method for forming gold-containing catalyst with porous structure

DOEpatents

Biener, Juergen; Hamza, Alex V; Baeumer, Marcus; Schulz, Christian; Jurgens, Birte; Biener, Monika M.

2014-07-22

A method for forming a gold-containing catalyst with porous structure according to one embodiment of the present invention includes producing a starting alloy by melting together of gold and at least one less noble metal that is selected from the group consisting of silver, copper, rhodium, palladium, and platinum; and a dealloying step comprising at least partial removal of the less noble metal by dissolving the at least one less noble metal out of the starting alloy. Additional methods and products thereof are also presented.

Fluorescence imaging technology (FI) for high-throughput screening of selenide-modified nano-TiO2 catalysts.

PubMed

Wang, Liping; Lee, Jianchao; Zhang, Meijuan; Duan, Qiannan; Zhang, Jiarui; Qi, Hailang

2016-02-18

A high-throughput screening (HTS) method based on fluorescence imaging (FI) was implemented to evaluate the catalytic performance of selenide-modified nano-TiO2. Chemical ink-jet printing (IJP) technology was reformed to fabricate a catalyst library comprising 1405 (Ni(a)Cu(b)Cd(c)Ce(d)In(e)Y(f))Se(x)/TiO2 (M6Se/Ti) composite photocatalysts. Nineteen M6Se/Tis were screened out from the 1405 candidates efficiently.

Nitrogen-doped carbon aerogels for electrical energy storage

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

Campbell, Patrick; Montalvo, Elizabeth; Baumann, Theodore F.

Disclosed here is a method for making a nitrogen-doped carbon aerogel, comprising: preparing a reaction mixture comprising formaldehyde, at least one nitrogen-containing resorcinol analog, at least one catalyst, and at least one solvent; curing the reaction mixture to produce a wet gel; drying the wet gel to produce a dry gel; and thermally annealing the dry gel to produce the nitrogen-doped carbon aerogel. Also disclosed is a nitrogen-doped carbon aerogel obtained according to the method and a supercapacitor comprising the nitrogen-doped carbon aerogel.

Catalytic membranes for fuel cells

DOEpatents

Liu, Di-Jia [Naperville, IL; Yang, Junbing [Bolingbrook, IL; Wang, Xiaoping [Naperville, IL

2011-04-19

A fuel cell of the present invention comprises a cathode and an anode, one or both of the anode and the cathode including a catalyst comprising a bundle of longitudinally aligned graphitic carbon nanotubes including a catalytically active transition metal incorporated longitudinally and atomically distributed throughout the graphitic carbon walls of said nanotubes. The nanotubes also include nitrogen atoms and/or ions chemically bonded to the graphitic carbon and to the transition metal. Preferably, the transition metal comprises at least one metal selected from the group consisting of Fe, Co, Ni, Mn, and Cr.

Process for forming a homogeneous oxide solid phase of catalytically active material

DOEpatents

Perry, Dale L.; Russo, Richard E.; Mao, Xianglei

1995-01-01

A process is disclosed for forming a homogeneous oxide solid phase reaction product of catalytically active material comprising one or more alkali metals, one or more alkaline earth metals, and one or more Group VIII transition metals. The process comprises reacting together one or more alkali metal oxides and/or salts, one or more alkaline earth metal oxides and/or salts, one or more Group VIII transition metal oxides and/or salts, capable of forming a catalytically active reaction product, in the optional presence of an additional source of oxygen, using a laser beam to ablate from a target such metal compound reactants in the form of a vapor in a deposition chamber, resulting in the deposition, on a heated substrate in the chamber, of the desired oxide phase reaction product. The resulting product may be formed in variable, but reproducible, stoichiometric ratios. The homogeneous oxide solid phase product is useful as a catalyst, and can be produced in many physical forms, including thin films, particulate forms, coatings on catalyst support structures, and coatings on structures used in reaction apparatus in which the reaction product of the invention will serve as a catalyst.

Mechanism of soft x-ray continuum radiation from low-energy pinch discharges of hydrogen and ultra-low field ignition of solid fuels

NASA Astrophysics Data System (ADS)

Mills, R.; Lotoski, J.; Lu, Y.

2017-09-01

EUV continuum radiation (10-30 nm) arising only from very low energy pulsed pinch gas discharges comprising some hydrogen was first observed at BlackLight Power, Inc. and reproduced at the Harvard Center for Astrophysics (CfA). The source was determined to be due to the transition of H to the lower-energy hydrogen or hydrino state H(1/4) whose emission matches that observed wherein alternative sources were eliminated. The identity of the catalyst that accepts 3 · 27.2 eV from the H to cause the H to H(1/4) transition was determined to HOH versus 3H. The mechanism was elucidated using different oxide-coated electrodes that were selective in forming HOH versus plasma forming metal atoms as well as from the intensity profile that was a mismatch for the multi-body reaction required during 3H catalysis. The HOH catalyst was further shown to give EUV radiation of the same nature by igniting a solid fuel comprising a source of H and HOH catalyst by passing a low voltage, high current through the fuel to produce explosive plasma. No chemical reaction can release such high-energy light. No high field existed to form highly ionized ions that could give radiation in this EUV region that persisted even without power input. This plasma source serves as strong evidence for the existence of the transition of H to hydrino H(1/4) by HOH as the catalyst and a corresponding new power source wherein initial extraordinarily brilliant light-emitting prototypes are already producing photovoltaic generated electrical power. The hydrino product of a catalyst reaction of atomic hydrogen was analyzed by multiple spectroscopic techniques. Moreover, the mH catalyst was identified to be active in astronomical sources such as the Sun, stars and interstellar medium wherein the characteristics of hydrino match those of the dark matter of the Universe.

Conversion of alkanes to linear alkylsilanes using an iridium-iron-catalysed tandem dehydrogenation-isomerization-hydrosilylation

NASA Astrophysics Data System (ADS)

Jia, Xiangqing; Huang, Zheng

2016-02-01

The conversion of inexpensive, saturated hydrocarbon feedstocks into value-added speciality chemicals using regiospecific, catalytic functionalization of alkanes is a major goal of organometallic chemistry. Linear alkylsilanes represent one such speciality chemical—they have a wide range of applications, including release coatings, silicone rubbers and moulding products. Direct, selective, functionalization of alkanes at primary C-H bonds is difficult and, to date, methods for catalytically converting alkanes into linear alkylsilanes are unknown. Here, we report a well-defined, dual-catalyst system for one-pot, two-step alkane silylations. The system comprises a pincer-ligated Ir catalyst for alkane dehydrogenation and an Fe catalyst that effects a subsequent tandem olefin isomerization-hydrosilylation. This method exhibits exclusive regioselectivity for the production of terminally functionalized alkylsilanes. This dual-catalyst strategy has also been applied to regioselective alkane borylations to form linear alkylboronate esters.

Steam reforming of fast pyrolysis-derived aqueous phase oxygenates over Co, Ni, and Rh metals supported on MgAl 2O 4

DOE PAGES

Xing, Rong; Dagle, Vanessa Lebarbier; Flake, Matthew; ...

2016-02-03

In this paper we examine the feasibility of steam reforming the mixed oxygenate aqueous fraction derived from fast pyrolysis bio-oils. Catalysts selective towards hydrogen formation and resistant to carbon formation utilizing feeds with relatively low steam-to-carbon (S/C) ratios are desired. Rh (5 wt%), Pt (5 wt%), Ru (5 wt%), Ir (5 wt%), Ni (15 wt%), and Co (15 wt%) metals supported on MgAl2O4 were evaluated for catalytic performance at 500 °C and 1 atm using a complex feed mixture comprising acids, polyols, cycloalkanes, and phenolic compounds. The Rh catalyst was found to be the most active and resistant to carbonmore » formation. The Ni and Co catalysts were found to be more active than the other noble metal catalysts investigated (Pt, Ru, and Ir).« less

Pyrochlore-type catalysts for the reforming of hydrocarbon fuels

DOEpatents

Berry, David A [Morgantown, WV; Shekhawat, Dushyant [Morgantown, WV; Haynes, Daniel [Morgantown, WV; Smith, Mark [Morgantown, WV; Spivey, James J [Baton Rouge, LA

2012-03-13

A method of catalytically reforming a reactant gas mixture using a pyrochlore catalyst material comprised of one or more pyrochlores having the composition A.sub.2-w-xA'.sub.wA''.sub.xB.sub.2-y-zB'.sub.yB''.sub.zO.sub.7-.DELTA.. Distribution of catalytically active metals throughout the structure at the B site creates an active and well dispersed metal locked into place in the crystal structure. This greatly reduces the metal sintering that typically occurs on supported catalysts used in reforming reactions, and reduces deactivation by sulfur and carbon. Further, oxygen mobility may also be enhanced by elemental exchange of promoters at sites in the pyrochlore. The pyrochlore catalyst material may be utilized in catalytic reforming reactions for the conversion of hydrocarbon fuels into synthesis gas (H.sub.2+CO) for fuel cells, among other uses.

Pyrochlore catalysts for hydrocarbon fuel reforming

DOEpatents

Berry, David A.; Shekhawat, Dushyant; Haynes, Daniel; Smith, Mark; Spivey, James J.

2012-08-14

A method of catalytically reforming a reactant gas mixture using a pyrochlore catalyst material comprised of one or more pyrochlores having the composition A₂B_2-y-zB'_yB"_zO_7-.DELTA., where y>0 and z.gtoreq.0. Distribution of catalytically active metals throughout the structure at the B site creates an active and well dispersed metal locked into place in the crystal structure. This greatly reduces the metal sintering that typically occurs on supported catalysts used in reforming reactions, and reduces deactivation by sulfur and carbon. Further, oxygen mobility may also be enhanced by elemental exchange of promoters at sites in the pyrochlore. The pyrochlore catalyst material may be utilized in catalytic reforming reactions for the conversion of hydrocarbon fuels into synthesis gas (H₂+CO) for fuel cells, among other uses.

Synthesis and crystal structure of an oxovanadium(IV) complex with a pyrazolone ligand and its use as a heterogeneous catalyst for the oxidation of styrene under mild conditions.

PubMed

Parihar, Sanjay; Pathan, Soyeb; Jadeja, R N; Patel, Anjali; Gupta, Vivek K

2012-01-16

1-Phenyl-3-methyl-4-touloyl-5-pyrazolone (ligand) was synthesized and used to prepare an oxovanadium(IV) complex. The complex was characterized by single-crystal X-ray analysis and various spectroscopic techniques. The single-crystal X-ray analysis of the complex shows that the ligands are coordinated in a syn configuration to each other and create a distorted octahedral environment around the metal ion. A heterogeneous catalyst comprising an oxovanadium(IV) complex and hydrous zirconia was synthesized, characterized by various physicochemical techniques, and successfully used for the solvent-free oxidation of styrene. The influence of the reaction parameters (percent loading, molar ratio of the substrate to H(2)O(2), amount of catalyst, and reaction time) was studied. The catalyst was reused three times without any significant loss in the catalytic activity.

Cyclopentadienyl-containing low-valent early transition metal olefin polymerization catalysts

DOEpatents

Marks, Tobin J.; Luo, Lubin; Yoon, Sung Cheol

2003-04-08

A catalyst system useful to polymerize and co-polymerize polar and non-polar olefin monomers is formed by in situ reduction with a reducing agent of a catalyst precursor comprising {Cp*MRR'.sub.n }.sup.+ {A}.sup.- wherein Cp* is a cyclopentadienyl or substituted cyclopentadienyl moiety; M is an early transition metal; R is a C.sub.1 -C.sub.20 hydrocarbyl; R' are independently selected from hydride, C.sub.1 -C.sub.20 hydrocarbyl, SiR".sub.3, NR".sub.2, OR", SR", GeR".sub.3, and SnR".sub.3 containing groups (R"=C.sub.1 -C.sub.10 hydrocarbyl); n is an integer selected to balance the oxidation state of M; and A is a suitable non-coordinating anionic cocatalyst or precursor. This catalyst system may form stereoregular olefin polymers including syndiotactic polymers of styrene and methylmethacrylate and isotactic copolymers of polar and nonpolar olefin monomers such as methylmethacrylate and styrene.

Cyclopentadienyl-containing low-valent early transition metal olefin polymerization catalysts

DOEpatents

Marks, Tobin J.; Luo, Lubin; Yoon, Sung Cheol

2003-12-30

A catalyst system useful to polymerize and co-polymerize polar and non-polar olefin monomers is formed by in situ reduction with a reducing agent of a catalyst precursor comprising wherein Cp* is a cyclopentadienyl or substituted cyclopentadienyl moiety; M is an early transition metal; R is a C.sub.1 -C.sub.20 hydrocarbyl; R' are independently selected from hydride, C.sub.1 -C.sub.20 hydrocarbyl, SiR".sub.3, NR".sub.2, OR", SR", GeR".sub.3, SnR".sub.3, and C.dbd.C containing groups (R".dbd.C.sub.1 -C.sub.10 hydrocarbyl); n is an integer selected to balance the oxidation state of M; and A is a suitable non-coordinating anionic cocatalyst or precursor. This catalyst system may form stereoregular olefin polymers including syndiotactic polymers of styrene and methylmethacrylate and isotactic copolymers of polar and nonpolar olefin monomers such as methylmethacrylate and styrene.

Catalyst comprising Ir or Ir and Ru for hydrazine decomposition

NASA Technical Reports Server (NTRS)

Armstrong, Warren E. (Inventor); Voge, Hervey H. (Inventor); Ryland, Lloyd B. (Inventor)

1978-01-01

A catalyst for hydrazine decomposition consisting essentially of a carrier having a pore volume of at least 0.1 cubic centimeters per gram and a specific surface area, measured in square meters per gram, equal to 195 (C.sub.p + 0.013 + 0.736 V.sub.p) where C.sub.p is the specific heat capacity of the carrier at about 25.degree. C in calories per gram per degree and V.sub.p is the pore volume of the carrier in cubic centimeters per gram and metal of the group consisting of iridium, and mixtures consisting of iridium and ruthenium deposited on said carrier in an amount between 20% and about 40% by weight of the catalyst and distributed through the pores thereof in discrete particles sufficiently separated from each other so that they do not sinter or fuse together when the catalyst is at hydrazine decomposition temperature.

Low temperature catalyst system for methanol production

DOEpatents

Sapienza, R.S.; Slegeir, W.A.; O'Hare, T.E.

1984-04-20

This patent discloses a catalyst and process useful at low temperatures (150/sup 0/C) and preferably in the range 80 to 120/sup 0/C used in the production of methanol from carbon monoxide and hydrogen. The catalyst components are used in slurry form and comprise (1) a complex reducing agent derived from the component structure NaH-ROH-M(OAc)/sub 2/ where M is selected from the group consisting of Ni, Pd, and Co and R is a lower alkyl group containing 1 to 6 carbon atoms and (2) a metal carbonyl of a group VI (Mo, Cr, W) metal. For the first component, Nic is preferred (where M = Ni and R = tertiary amyl). For the second component, Mo(CO)/sub 6/ is preferred. The mixture is subjected to a conditioning or activating step under temperature and pressure, similar to the parameters given above, to afford the active catalyst.

Selective catalysts and their preparation for catalytic hydrocarbon synthesis

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

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

1991-07-30

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

Effect of Ni Core Structure on the Electrocatalytic Activity of Pt-Ni/C in Methanol Oxidation

PubMed Central

Kang, Jian; Wang, Rongfang; Wang, Hui; Liao, Shijun; Key, Julian; Linkov, Vladimir; Ji, Shan

2013-01-01

Methanol oxidation catalysts comprising an outer Pt-shell with an inner Ni-core supported on carbon, (Pt-Ni/C), were prepared with either crystalline or amorphous Ni core structures. Structural comparisons of the two forms of catalyst were made using transmission electron microscopy (TEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS), and methanol oxidation activity compared using CV and chronoamperometry (CA). While both the amorphous Ni core and crystalline Ni core structures were covered by similar Pt shell thickness and structure, the Pt-Ni(amorphous)/C catalyst had higher methanol oxidation activity. The amorphous Ni core thus offers improved Pt usage efficiency in direct methanol fuel cells. PMID:28811402

Non-precious metal catalysts prepared from precursors comprising cyanamide and polyaniline

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

Chung, Hoon Taek; Zelenay, Piotr

A catalyst for oxygen reduction reaction (ORR) for a fuel cell was prepared by pyrolyzing a mixture of polyaniline, cyanamide, carbon black, and a non-precious metal salt under an inert atmosphere. The pyrolyzed product was treated to remove acid soluble components and then pyrolyzed again. The resulting powder was used to prepare a cathode for a membrane electrode assembly that was used in a fuel cell. When iron(III) chloride was used as the salt, the resulting catalyst was porous with a web-shaped structure. It displayed a maximum power density of 0.79 W/cm at 0.4 V in H.sub.2/O.sub.2 at 1.0 barmore » back pressure.« less

High aspect ratio catalytic reactor and catalyst inserts therefor

DOEpatents

Lin, Jiefeng; Kelly, Sean M.

2018-04-10

The present invention relates to high efficient tubular catalytic steam reforming reactor configured from about 0.2 inch to about 2 inch inside diameter high temperature metal alloy tube or pipe and loaded with a plurality of rolled catalyst inserts comprising metallic monoliths. The catalyst insert substrate is formed from a single metal foil without a central supporting structure in the form of a spiral monolith. The single metal foil is treated to have 3-dimensional surface features that provide mechanical support and establish open gas channels between each of the rolled layers. This unique geometry accelerates gas mixing and heat transfer and provides a high catalytic active surface area. The small diameter, high aspect ratio tubular catalytic steam reforming reactors loaded with rolled catalyst inserts can be arranged in a multi-pass non-vertical parallel configuration thermally coupled with a heat source to carry out steam reforming of hydrocarbon-containing feeds. The rolled catalyst inserts are self-supported on the reactor wall and enable efficient heat transfer from the reactor wall to the reactor interior, and lower pressure drop than known particulate catalysts. The heat source can be oxygen transport membrane reactors.

Solar fuel generator

DOEpatents

Lewis, Nathan S.; West, William C.

2017-01-17

The disclosure provides conductive membranes for water splitting and solar fuel generation. The membranes comprise an embedded semiconductive/photoactive material and an oxygen or hydrogen evolution catalyst. Also provided are chassis and cassettes containing the membranes for use in fuel generation.

Solar Fuel Generator

NASA Technical Reports Server (NTRS)

West, William C. (Inventor); Lewis, Nathan S. (Inventor)

2017-01-01

The disclosure provides conductive membranes for water splitting and solar fuel generation. The membranes comprise an embedded semiconductive/photoactive material and an oxygen or hydrogen evolution catalyst. Also provided are chassis and cassettes containing the membranes for use in fuel generation.

Preparation of olefins from synthesis gas using ruthenium supported on ceric oxide

DOEpatents

Pierantozzi, Ronald

1985-01-01

A catalyst comprising a ruthenium carbonyl compound deposited on a cerium oxide-containing support material provides for the selective synthesis of low molecular weight olefinic hydrocarbons from mixtures of hydrogen and carbon monoxide.

Preparation of olefins from synthesis gas using ruthenium supported on ceric oxide

DOEpatents

Pierantozzi, R.

1985-04-09

A catalyst comprising a ruthenium carbonyl compound deposited on a cerium oxide-containing support material provides for the selective synthesis of low molecular weight olefinic hydrocarbons from mixtures of hydrogen and carbon monoxide.

Apparatuses and methods for deoxygenating biomass-derived pyrolysis oil

DOEpatents

Kalnes, Tom N.

2015-12-29

Apparatuses and methods for deoxygenating a biomass-derived pyrolysis oil are provided herein. In one example, the method comprises of dividing a feedstock stream into first and second feedstock portions. The feedstock stream comprises the biomass-derived pyrolysis oil and has a temperature of about 60.degree. C. or less. The first feedstock portion is combined with a heated organic liquid stream to form a first heated diluted pyoil feed stream. The first heated diluted pyoil feed stream is contacted with a first deoxygenating catalyst in the presence of hydrogen to form an intermediate low-oxygen pyoil effluent. The second feedstock portion is combined with the intermediate low-oxygen pyoil effluent to form a second heated diluted pyoil feed stream. The second heated diluted pyoil feed stream is contacted with a second deoxygenating catalyst in the presence of hydrogen to form additional low-oxygen pyoil effluent.

Method of fabricating electrode catalyst layers with directionally oriented carbon support for proton exchange membrane fuel cell

DOEpatents

Liu, Di-Jia [Naperville, IL; Yang, Junbing [Bolingbrook, IL

2012-03-20

A membrane electrode assembly (MEA) of the invention comprises an anode and a cathode and a proton conductive membrane therebetween, the anode and the cathode each comprising a patterned sheet of longitudinally aligned transition metal-containing carbon nanotubes, wherein the carbon nanotubes are in contact with and are aligned generally perpendicular to the membrane, wherein a catalytically active transition metal is incorporated throughout the nanotubes.

Haloporphyrins and their preparation and use as catalysts

DOEpatents

Ellis, Jr., Paul E.; Lyons, James E.

1997-01-01

The invention provides novel catalyst compositions, useful in the oxidation of hydrocarbons with air or oxygen to form hydroxy-group containing compounds and in the decomposition of hydroperoxides to form hydroxy-group containing compounds. The catalysts comprise transition metal complexes of a porphyrin ring having 1 to 12 halogen substituents on the porphyrin ring, at least one of said halogens being in a meso position and/or the catalyst containing no aryl group in a meso position. The compositions are prepared by halogenating a transition metal complex of a porphyrin. In one embodiment, a complex of a porphyrin with a metal whose porphyrin complexes are not active for oxidation of hydrocarbons is halogenated, thereby to obtain a haloporphyrin complex of that metal, the metal is removed from the haloporphyrin complex to obtain the free base form of the haloporphyrin, and a metal such as iron whose porphyrin complexes are active for oxidation of hydrocarbons and for the decomposition of alkyl hydroperoxides is complexed with the free base to obtain an active catalyst for oxidation of hydrocarbons and decomposition of alkyl hydroperoxides.

Haloporphyrins and their preparation and use as catalysts

DOEpatents

Ellis, P.E. Jr.; Lyons, J.E.

1997-09-02

The invention provides novel catalyst compositions, useful in the oxidation of hydrocarbons with air or oxygen to form hydroxy-group containing compounds and in the decomposition of hydroperoxides to form hydroxy-group containing compounds. The catalysts comprise transition metal complexes of a porphyrin ring having 1 to 12 halogen substituents on the porphyrin ring, at least one of said halogens being in a meso position and/or the catalyst containing no aryl group in a meso position. The compositions are prepared by halogenating a transition metal complex of a porphyrin. In one embodiment, a complex of a porphyrin with a metal whose porphyrin complexes are not active for oxidation of hydrocarbons is halogenated, thereby to obtain a haloporphyrin complex of that metal, the metal is removed from the haloporphyrin complex to obtain the free base form of the haloporphyrin, and a metal such as iron whose porphyrin complexes are active for oxidation of hydrocarbons and for the decomposition of alkyl hydroperoxides is complexed with the free base to obtain an active catalyst for oxidation of hydrocarbons and decomposition of alkyl hydroperoxides.

New iron catalyst for preparation of polymethylene from synthesis gas

DOEpatents

Sapienza, R.S.; Slegeir, W.A.

1988-03-31

This invention relates to a process for synthesizing hydrocarbons; more particularly, the invention relates to a process for synthesizing long-chain hydrocarbons known as polymethylene from carbon monoxide and hydrogen or from carbon monoxide and water or mixtures thereof in the presence of a catalyst comprising iron and platinum or palladium or mixtures thereof which may be supported on a solid material, preferably an inorganic refractory oxide. This process may be used to convert a carbon monoxide containing gas to a product which could substitute for high density polyethylene.

Iron catalyst for preparation of polymethylene from synthesis gas

DOEpatents

Sapienza, Richard S.; Slegeir, William A.

1990-01-01

This invention relates to a process for synthesizing hydrocarbons; more particularly, the invention relates to a process for synthesizing long-chain hydrocarbons known as polymethylene from carbon monoxide and hydrogen or from carbon monoxide and water or mixtures thereof in the presence of a catalyst comprising iron and platinum or palladium or mixtures thereof which may be supported on a solid material, preferably an inorganic refractory oxide. This process may be used to convert a cabon monoxide containing gas to a product which could substitute for high density polyethylene.

Attrition resistant fluidizable reforming catalyst

DOEpatents

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

2011-03-29

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

Mechanically robust, electrically conductive ultralow-density carbon nanotube-based aerogels

DOEpatents

Worsley, Marcus A.; Baumann, Theodore F.; Satcher, Jr., Joe H.

2016-10-04

Disclosed here is a device comprising a porous carbon aerogel or composite thereof as an energy storage material, catalyst support, sensor or adsorbent, wherein the porous carbon aerogel comprises a network of interconnected struts comprising carbon nanotube bundles covalently crosslinked by graphitic carbon nanoparticles, wherein the carbon nanotubes account for 5 to 95 wt. % of the aerogel and the graphitic carbon nanoparticles account for 5 to 95 wt. % of the aerogel, and wherein the aerogel has an electrical conductivity of at least 10 S/m and is capable of withstanding strains of more than 10% before fracture.

Catalytic Reactor For Oxidizing Mercury Vapor

DOEpatents

Helfritch, Dennis J.

1998-07-28

A catalytic reactor (10) for oxidizing elemental mercury contained in flue gas is provided. The catalyst reactor (10) comprises within a flue gas conduit a perforated corona discharge plate (30a, b) having a plurality of through openings (33) and a plurality of projecting corona discharge electrodes (31); a perforated electrode plate (40a, b, c) having a plurality of through openings (43) axially aligned with the through openings (33) of the perforated corona discharge plate (30a, b) displaced from and opposing the tips of the corona discharge electrodes (31); and a catalyst member (60a, b, c, d) overlaying that face of the perforated electrode plate (40a, b, c) opposing the tips of the corona discharge electrodes (31). A uniformly distributed corona discharge plasma (1000) is intermittently generated between the plurality of corona discharge electrode tips (31) and the catalyst member (60a, b, c, d) when a stream of flue gas is passed through the conduit. During those periods when corona discharge (1000) is not being generated, the catalyst molecules of the catalyst member (60a, b, c, d) adsorb mercury vapor contained in the passing flue gas. During those periods when corona discharge (1000) is being generated, ions and active radicals contained in the generated corona discharge plasma (1000) desorb the mercury from the catalyst molecules of the catalyst member (60a, b, c, d), oxidizing the mercury in virtually simultaneous manner. The desorption process regenerates and activates the catalyst member molecules.

Binary ferrihydrite catalysts

DOEpatents

Huffman, Gerald P.; Zhao, Jianmin; Feng, Zhen

1996-01-01

A method of preparing a catalyst precursor comprises dissolving an iron salt and a salt of an oxoanion forming agent, in water so that a solution of the iron salt and oxoanion forming agent salt has a ratio of oxoanion/Fe of between 0.0001:1 to 0.5:1. Next is increasing the pH of the solution to 10 by adding a strong base followed by collecting of precipitate having a binary ferrihydrite structure. A binary ferrihydrite catalyst precursor is also prepared by dissolving an iron salt in water. The solution is brought to a pH of substantially 10 to obtain ferrihydrite precipitate. The precipitate is then filtered and washed with distilled water and subsequently admixed with a hydroxy carboxylic acid solution. The admixture is mixed/agitated and the binary ferrihydrite precipitate is then filtered and recovered.

Method for the continuous production of hydrogen

DOEpatents

Getty, John Paul; Orr, Mark T.; Woodward, Jonathan

2002-01-01

The present invention is a method for the continuous production of hydrogen. The present method comprises reacting a metal catalyst with a degassed aqueous organic acid solution within a reaction vessel under anaerobic conditions at a constant temperature of .ltoreq.80.degree. C. and at a pH ranging from about 4 to about 9. The reaction forms a metal oxide when the metal catalyst reacts with the water component of the organic acid solution while generating hydrogen, then the organic acid solution reduces the metal oxide thereby regenerating the metal catalyst and producing water, thus permitting the oxidation and reduction to reoccur in a continual reaction cycle. The present method also allows the continuous production of hydrogen to be sustained by feeding the reaction with a continuous supply of degassed aqueous organic acid solution.

Bifunctional air electrodes containing elemental iron powder charging additive

DOEpatents

Liu, Chia-tsun; Demczyk, Brian G.; Gongaware, Paul R.

1982-01-01

A bifunctional air electrode for use in electrochemical energy cells is made, comprising a hydrophilic layer and a hydrophobic layer, where the hydrophilic layer essentially comprises a hydrophilic composite which includes: (i) carbon; (ii) elemental iron particles having a particle size of between about 25 microns and about 700 microns diameter; (iii) an oxygen evolution material; (iv) a nonwetting agent; and (v) a catalyst, where at least one current collector is formed into said composite.

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

Lu, Weigang; Yuan, Daqiang; Yakovenko, Andrey A

A super-paddlewheel (comprised of two paddlewheels) metal–organic polyhedron (MOP) containing surface hydroxyl groups was synthesized and characterized. Condensation reactions with linear alkyl anhydrides lead to new MOPs with enhanced solubility. As a result, the surface-modified MOP 4 was demonstrated as a homogeneous Lewis-acid catalyst.

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

Lu, Weigang; Yuan, Daqiang; Yakovenko, Andrey

A super-paddlewheel (comprised of two paddlewheels) metal-organic polyhedron (MOP) containing surface hydroxyl groups was synthesized and characterized. Condensation reactions with linear alkyl anhydrides lead to new MOPs with enhanced solubility. As a result, the surface-modified MOP 4 was demonstrated as a homogeneous Lewis-acid catalyst.

Methanol synthesis using a catalyst combination of alkali or alkaline earth salts and reduced copper chromite

DOEpatents

Tierney, J.W.; Wender, I.; Palekar, V.M.

1995-01-24

The present invention relates to a novel route for the synthesis of methanol, and more specifically to the production of methanol by contacting synthesis gas under relatively mild conditions in a slurry phase with a catalyst combination comprising reduced copper chromite and basic alkali salts or alkaline earth salts. The present invention allows the synthesis of methanol to occur in the temperature range of approximately 100--160 C and the pressure range of 40--65 atm. The process produces methanol with up to 90% syngas conversion per pass and up to 95% methanol selectivity. The only major by-product is a small amount of easily separated methyl formate. Very small amounts of water, carbon dioxide and dimethyl ether are also produced. The present catalyst combination also is capable of tolerating fluctuations in the H[sub 2]/CO ratio without major deleterious effect on the reaction rate. Furthermore, carbon dioxide and water are also tolerated without substantial catalyst deactivation.

Cyclopentadienyl-containing low-valent early transition metal olefin polymerization catalysts

DOEpatents

Marks, Tobin J.; Luo, Lubin; Yoon, Sung Cheol

2006-10-10

A catalyst system useful to polymerize and co-polymerize polar and non-polar olefin monomers is formed by in situ reduction with a reducing agent of a catalyst precursor comprising {Cp*MRR'.sub.n}.sup.+{A}.sup.- wherein Cp* is a cyclopentadienyl or substituted cyclopentadienyl moiety; M is an early transition metal; R is a C.sub.1 C.sub.20 hydrocarbyl; R' are independently selected from hydride, C.sub.1 C.sub.20 hydrocarbyl, SiR''.sub.3, NR''.sub.2, OR'', SR'', GeR''.sub.3, SnR''.sub.3, and C.dbd.C-containing groups (R''=C.sub.1 C.sub.10 hydrocarbyl); n is an integer selected to balance the oxidation state of M; and A is a suitable non-coordinating anionic cocatalyst or precursor. This catalyst system may form stereoregular olefin polymers including syndiotactic polymers of styrene and methylmethacrylate and isotactic copolymers of polar and nonpolar olefin monomers such as methylmethacrylate and styrene.

Cyclopentadienyl-containing low-valent early transition metal olefin polymerization catalysts

DOEpatents

Marks, Tobin J.; Luo, Lubin; Yoon, Sung Cheol

2007-01-09

A catalyst system useful to polymerize and co-polymerize polar and non-polar olefin monomers is formed by in situ reduction with a reducing agent of a catalyst precursor comprising {Cp*MRR'.sub.n}.sup.+{A}.sup.- wherein Cp* is a cyclopentadienyl or substituted cyclopentadienyl moiety; M is an early transition metal; R is a C.sub.1 C.sub.20 hydrocarbyl; R' are independently selected from hydride, C.sub.1 C.sub.20 hydrocarbyl, SiR''.sub.3, NR''.sub.2, OR'', SR'', GeR''.sub.3, SnR''.sub.3, and C.dbd.C-containing groups (R''=C.sub.1 C.sub.10 hydrocarbyl); n is an integer selected to balance the oxidation state of M; and A is a suitable non-coordinating anionic cocatalyst or precursor. This catalyst system may form stereoregular olefin polymers including syndiotactic polymers of styrene and methylmethacrylate and isotactic copolymers of polar and nonpolar olefin monomers such as methylmethacrylate and styrene.

Cyclopentadienyl-Containing Low-Valent Early Transition Metal Olefin Polymerization Catalysts

DOEpatents

Marks, Tobin J.; Luo, Lubin; Yoon, Sung Cheol

2004-06-08

A catalyst system useful to polymerize and co-polymerize polar and non-polar olefin monomers is formed by in situ reduction with a reducing agent of a catalyst precursor comprising {Cp*MRR'.sub.n }.sup.+ {A}.sup.- wherein Cp* is a cyclopentadienyl or substituted cyclopentadienyl moiety; M is an early transition metal; R is a C.sub.1 -C.sub.20 hydrocarbyl; R' are independently selected from hydride, C.sub.1 -C.sub.20 hydrocarbyl, SiR".sub.3, NR".sub.2, OR", SR", GeR".sub.3, SnR".sub.3, and C.dbd.C-containing groups (R"=C.sub.1 -C.sub.10 hydrocarbyl); n is an integer selected to balance the oxidation state of M; and A is a suitable non-coordinating anionic cocatalyst or precursor. This catalyst system may form stereoregular olefin polymers including syndiotactic polymers of styrene and methylmethacrylate and isotactic copolymers of polar and nonpolar olefin monomers such as methylmethacrylate and styrene.

ZnO nanoparticle catalysts for use in biodiesel production and method of making

DOEpatents

Yan, Shuli; Salley, Steven O; Ng, K. Y. Simon

2014-11-25

A method of forming a biodiesel product and a heterogeneous catalyst system used to form said product that has a high tolerance for the presence of water and free fatty acids (FFA) in the oil feedstock is disclosed. This catalyst system may simultaneously catalyze both the esterification of FAA and the transesterification of triglycerides present in the oil feedstock. The catalyst system is comprised of a mixture of zinc oxide and a second metal oxide. The zinc oxide includes a mixture of amorphous zinc oxide and zinc oxide nanocrystals, the zinc nanocrystals having a mean grain size between about 20 and 80 nanometers with at least one of the nanocrystals including a mesopore having a diameter of about 5 to 15 nanometers. Preferably, the second metal oxide is a lanthanum oxide, the lanthanum oxide being selected as one from the group of La.sub.2CO.sub.5, LaOOH, and combinations or mixtures thereof.

Methanol synthesis using a catalyst combination of alkali or alkaline earth salts and reduced copper chromite

DOEpatents

Tierney, John W.; Wender, Irving; Palekar, Vishwesh M.

1995-01-01

The present invention relates to a novel route for the synthesis of methanol, and more specifically to the production of methanol by contacting synthesis gas under relatively mild conditions in a slurry phase with a catalyst combination comprising reduced copper chromite and basic alkali salts or alkaline earth salts. The present invention allows the synthesis of methanol to occur in the temperature range of approximately 100.degree.-160.degree. C. and the pressure range of 40-65 atm. The process produces methanol with up to 90% syngas conversion per pass and up to 95% methanol selectivity. The only major by-product is a small amount of easily separated methyl formate. Very small amounts of water, carbon dioxide and dimethyl ether are also produced. The present catalyst combination also is capable of tolerating fluctuations in the H.sub.2 /CO ratio without major deleterious effect on the reaction rate. Furthermore, carbon dioxide and water are also tolerated without substantial catalyst deactivation.

Methanol synthesis using a catalyst combination of alkali or alkaline earth salts and reduced copper chromite for methanol synthesis

DOEpatents

Tierney, John W.; Wender, Irving; Palekar, Vishwesh M.

1993-01-01

The present invention relates to a novel route for the synthesis of methanol, and more specifically to the production of methanol by contacting synthesis gas under relatively mild conditions in a slurry phase with a catalyst combination comprising reduced copper chromite and basic alkali salts or alkaline earth salts. The present invention allows the synthesis of methanol to occur in the temperature range of approximately 100.degree.-160.degree. C. and the pressure range of 40-65 atm. The process produces methanol with up to 90% syngas conversion per pass and up to 95% methanol selectivity. The only major by-product is a small amount of easily separated methyl formate. Very small amounts of water, carbon dioxide and dimethyl ether are also produced. The present catalyst combination also is capable of tolerating fluctuations in the H.sub.2 /CO ratio without major deleterious effect on the reaction rate. Furthermore, carbon dioxide and water are also tolerated without substantial catalyst deactivation.

Evaluation of Mobil OCTGAIN{trademark} technology for the manufacture of reformulated gasoline via LP modeling

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

Poddar, S.K.; Chum, K.; Ragsdale, R.

1995-09-01

Sulfur and olefins content of gasoline come primarily from the cat-cracked blendstock. Therefore hydrotreating cat cracked naphtha is a straight forward approach to reduce sulfur and olefin contents of gasoline and thereby reduce auto exhaust emission. However, this approach reduces the Octane number of gasoline which requires addition of Octane enhancer like MTBE to meet the stringent requirement of 1990 Clean Air Act Amendments and to produce Reformulated Gasoline (RFG). The paper examines the economic incentives of an innovative process technology which was developed and commercialized by Mobil known as OCTGAIN. The process utilizes fixed bed low pressure hardware andmore » uses a Mobil proprietary catalyst system to produce catalytically cracked (CC) gasoline component with thorough desulfurization and olefin reduction and practically no loss in Octane number. The economic evaluation of the OCTGAIN technology was conducted with Bechtel`s proprietary linear programming software, Process Industry Modeling System by introducing an OCTGAIN process block to a typical PADD-3 refinery configuration for gasoline production and satisfying RFG specifications. The results of the evaluation which involved twenty case studies, show that within the limitations of the study scope, the introduction of OCTGAIN technology creates a definite economic incentive over conventional hydrofinishing of CC naphtha. The profitability of OCTGAIN technology is dependent on the aromatics component of the gasoline pool. The economic advantage of OCTGAIN technology is realized primarily by higher production of premium gasoline and the ability to process lower cost high sulfur crude. The process also allows a better utilization of the FCCU and hydrocracker, if the refinery operation permits.« less

Catalyst cartridge for carbon dioxide reduction unit

NASA Technical Reports Server (NTRS)

Holmes, R. F. (Inventor)

1973-01-01

A catalyst cartridge, for use in a carbon dioxide reducing apparatus in a life support system for space vehicles, is described. The catalyst cartridge includes an inner perforated metal wall, an outer perforated wall space outwardly from the inner wall, a base plate closing one end of the cartridge, and a cover plate closing the other end of the cartridge. The cover plate has a central aperture through which a supply line with a heater feeds a gaseous reaction mixture comprising hydrogen and carbon dioxide at a temperature from about 1000 to about 1400 F. The outer surfaces of the internal wall and the inner surfaces of the outer wall are lined with a ceramic fiber batting material of sufficient thickness to prevent carbon formed in the reaction from passing through it. The portion of the surfaces of the base and cover plates defined within the inner and outer walls are also lined with ceramic batting. The heated reaction mixture passes outwardly through the inner perforated wall and ceramic batting and over the catalyst. The solid carbon product formes is retained within the enclosure containing the catalyst. The solid carbon product formed is retained within the enclosure containing the catalyst. The water vapor and unreacted carbon dioxide and any intermediate products pass through the perforations of the outer wall.

Method and apparatus for forming a carbon-silicon bond in a silane

DOEpatents

Schattenmann, Florian Johannes

2002-01-01

A method for forming at least one product silane, comprising reacting a transition metal hydride with a starting silane in a presence of a catalyst and at a temperature that exceeds a threshold temperature associated with said reacting.

1,2,3-triazolium ionic liquids

DOEpatents

Luebke, David; Nulwala, Hunaid; Tang, Chau

2014-12-09

The present invention relates to compositions of matter that are ionic liquids, the compositions comprising substituted 1,2,3-triazolium cations combined with any anion. Compositions of the invention should be useful in the separation of gases and, perhaps, as catalysts for many reactions.

Highly selective catalytic process for synthesizing 1-hexene from ethylene

DOEpatents

Sen, Ayusman; Murtuza, Shahid; Harkins, Seth B.; Andes, Cecily

2002-01-01

Ethylene is trimerized to form 1-hexene, at a selectivity of up to about 99 mole percent, by contacting ethylene, at an ethylene pressure of from about 200-1500 psig and at a reaction temperature of from about 0.degree. C. to about 100.degree. C., with a catalyst comprising a tantalum compound (e.g., TaCl.sub.5) and a alkylating component comprising a metal hydrocarbyl compound or a metal hydrocarbyl halide compound (e.g., Sn(CH.sub.3).sub.4).

Process for making unsaturated hydrocarbons using microchannel process technology

DOEpatents

Tonkovich, Anna Lee [Dublin, OH; Yuschak, Thomas [Lewis Center, OH; LaPlante, Timothy J [Columbus, OH; Rankin, Scott [Columbus, OH; Perry, Steven T [Galloway, OH; Fitzgerald, Sean Patrick [Columbus, OH; Simmons, Wayne W [Dublin, OH; Mazanec, Terry Daymo, Eric

2011-04-12

The disclosed invention relates to a process for converting a feed composition comprising one or more hydrocarbons to a product comprising one or more unsaturated hydrocarbons, the process comprising: flowing the feed composition and steam in contact with each other in a microchannel reactor at a temperature in the range from about 200.degree. C. to about 1200.degree. C. to convert the feed composition to the product, the process being characterized by the absence of catalyst for converting the one or more hydrocarbons to one or more unsaturated hydrocarbons. Hydrogen and/or oxygen may be combined with the feed composition and steam.

Characteristics of back corona discharge in a honeycomb catalyst and its application for treatment of volatile organic compounds.

PubMed

Feng, Fada; Zheng, Yanyan; Shen, Xinjun; Zheng, Qinzhen; Dai, Shaolong; Zhang, Xuming; Huang, Yifan; Liu, Zhen; Yan, Keping

2015-06-02

The main technical challenges for the treatment of volatile organic compounds (VOCs) with plasma-assisted catalysis in industrial applications are large volume plasma generation under atmospheric pressure, byproduct control, and aerosol collection. To solve these problems, a back corona discharge (BCD) configuration has been designed to evenly generate nonthermal plasma in a honeycomb catalyst. Voltage-current curves, discharge images, and emission spectra have been used to characterize the plasma. Grade particle collection results and flow field visualization in the discharge zones show not only that the particles can be collected efficiently, but also that the pressure drop of the catalyst layer is relatively low. A three-stage plasma-assisted catalysis system, comprising a dielectric barrier discharge (DBD) stage, BCD stage, and catalyst stage, was built to evaluate toluene treatment performance by BCD. The ozone analysis results indicate that BCD enhances the ozone decomposition by collecting aerosols and protecting the Ag-Mn-O catalyst downstream from aerosol contamination. The GC and FTIR results show that BCD contributes to toluene removal, especially when the specific energy input is low, and the total removal efficiency reaches almost 100%. Furthermore, this removal results in the emission of fewer byproducts.

Visible-light photochemical activity of heterostructured core-shell materials composed of selected ternary titanates and ferrites coated by tiO2.

PubMed

Li, Li; Liu, Xuan; Zhang, Yiling; Nuhfer, Noel T; Barmak, Katayun; Salvador, Paul A; Rohrer, Gregory S

2013-06-12

Heterostructured photocatalysts comprised of microcrystalline (mc-) cores and nanostructured (ns-) shells were prepared by the sol-gel method. The ability of titania-coated ATiO3 (A = Fe, Pb) and AFeO3 (A = Bi, La, Y) catalysts to degrade methylene blue in visible light (λ > 420 nm) was compared. The catalysts with the titanate cores had enhanced photocatalytic activities for methylene blue degradation compared to their components alone, whereas the catalysts with ferrite cores did not. The temperature at which the ns-titania shell is crystallized influences the photocatalytic dye degradation. mc-FeTiO3/ns-TiO2 annealed at 500 °C shows the highest reaction rate. Fe-doped TiO2, which absorbs visible light, did not show enhanced photocatalytic activity for methylene blue degradation. This result indicates that iron contamination is not a decisive factor in the reduced reactivity of the titania coated ferrite catalysts. The higher reactivity of materials with the titanate cores suggests that photogenerated charge carriers are more easily transported across the titanate-titanate interface than the ferrite-titanate interface and this provides guidance for materials selection in composite catalyst design.

Binary ferrihydrite catalysts

DOEpatents

Huffman, G.P.; Zhao, J.; Feng, Z.

1996-12-03

A method of preparing a catalyst precursor comprises dissolving an iron salt and a salt of an oxoanion forming agent, in water so that a solution of the iron salt and oxoanion forming agent salt has a ratio of oxoanion/Fe of between 0.0001:1 to 0.5:1. Next is increasing the pH of the solution to 10 by adding a strong base followed by collecting of precipitate having a binary ferrihydrite structure. A binary ferrihydrite catalyst precursor is also prepared by dissolving an iron salt in water. The solution is brought to a pH of substantially 10 to obtain ferrihydrite precipitate. The precipitate is then filtered and washed with distilled water and subsequently admixed with a hydroxy carboxylic acid solution. The admixture is mixed/agitated and the binary ferrihydrite precipitate is then filtered and recovered. 3 figs.

Catalysts for the hydrodenitrogenation of organic materials and process for the preparation of the catalysts

DOEpatents

Laine, Richard M.; Hirschon, Albert S.; Wilson, Jr., Robert B.

1987-01-01

The present invention discloses a process for forming a catalyst for the hydrodenitrogenation of an organic feedstock, which includes (a) obtaining a precatalyst comprising cobalt and molybdenum or nickel and molybdenum; (b) adding in a non-oxidizing an atmosphere selected from hydrogen, helium, nitrogen, neon, argon, carbon monoxide or mixtures thereof to the precatalyst of step (a), a transition met ORIGIN OF THE INVENTION This invention was made in the course of research partially sponsored by the Department of Energy through grants DE-FG22-83P C60781 and DE-FG-85-PC80906, and partially supported by grant CHE82-19541 of the National Science Foundation. The invention is subject to Public Law 96-517 (and amendments), and the United States Government has rights in the present invention.

Visible light photoreduction of CO.sub.2 using heterostructured catalysts

DOEpatents

Matranga, Christopher; Thompson, Robert L; Wang, Congjun

2015-03-24

The method provides for use of sensitized photocatalyst for the photocatalytic reduction of CO.sub.2 under visible light illumination. The photosensitized catalyst is comprised of a wide band gap semiconductor material, a transition metal co-catalyst, and a semiconductor sensitizer. The semiconductor sensitizer is photoexcited by visible light and forms a Type II band alignment with the wide band gap semiconductor material. The wide band gap semiconductor material and the semiconductor sensitizer may be a plurality of particles, and the particle diameters may be selected to accomplish desired band widths and optimize charge injection under visible light illumination by utilizing quantum size effects. In a particular embodiment, CO.sub.2 is reduced under visible light illumination using a CdSe/Pt/TiO2 sensitized photocatalyst with H.sub.2O as a hydrogen source.

Olefin metathesis for effective polymer healing via dynamic exchange of strong carbon-carbon bonds

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

Guan, Zhibin; Lu, Yixuan

A method of preparing a malleable and/or self-healing polymeric or composite material is provided. The method includes providing a polymeric or composite material comprising at least one alkene-containing polymer, combining the polymer with at least one homogeneous or heterogeneous transition metal olefin metathesis catalyst to form a polymeric or composite material, and performing an olefin metathesis reaction on the polymer so as to form reversible carbon-carbon double bonds in the polymer. Also provided is a method of healing a fractured surface of a polymeric material. The method includes bringing a fractured surface of a first polymeric material into contact withmore » a second polymeric material, and performing an olefin metathesis reaction in the presence of a transition metal olefin metathesis catalyst such that the first polymeric material forms reversible carbon-carbon double bonds with the second polymeric material. Compositions comprising malleable and/or self-healing polymeric or composite material are also provided.« less

C-11 cyanide production system

DOEpatents

Kim, Dohyun; Alexoff, David; Kim, Sung Won; Hooker, Jacob; Ferrieri, Richard A

2015-01-13

A method for providing .sup.11C-labeled cyanides from .sup.11C labeled oxides in a target gas stream retrieved from an irradiated high pressure gaseous target containing O.sub.2 is provided, wherein .sup.11C labeled oxides are reduced with H.sub.2 in the presence of a nickel catalyst under a pressure and a temperature sufficient to form a product stream comprising at least about 95% .sup.11CH.sup.4 , the .sup.11CH.sub.4 is then combined with an excess of NH.sub.3 in a carrier/reaction stream flowing at an accelerated velocity and the combined .sup.11CH4 carrier/reaction stream is then contacted with a platinum (Pt) catalyst particulate supported on a substantially-chemically-nonreactive heat-stable support at a temperature of at least about 900 .degree. C., whereby a product stream comprising at least about 60%H.sup.11CN is provided in less than 10 minutes from retrieval of the .sup.11C labeled oxide.

C-11 cyanide production system

DOEpatents

Kim, Dohyun; Alexoff, David; Kim, Sung Won; Hooker, Jacob M.; Ferrieri, Richard A.

2017-11-21

A method for providing .sup.11C-labeled cyanides from .sup.11C labeled oxides in a target gas stream retrieved from an irradiated high pressure gaseous target containing O.sub.2, wherein .sup.11C labeled oxides are reduced with H.sub.2 in the presence of a nickel catalyst under a pressure and a temperature sufficient to form a product stream comprising at least about 95% .sup.11CH.sub.4, the .sup.11CH.sub.4 is then combined with an excess of NH.sub.3 in a carrier/reaction stream flowing at an accelerated velocity and the combined .sup.11CH4 carrier/reaction stream is then contacted with a platinum (Pt) catalyst particulate supported on a substantially-chemically-nonreactive heat-stable support at a temperature of at least about 900.degree. C., whereby a product stream comprising at least about 60% H.sup.11CN is provided in less than 10 minutes from retrieval of the .sup.11C labeled oxide.

Reforming Biomass Derived Pyrolysis Bio-oil Aqueous Phase to Fuels

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

Mukarakate, Calvin; Evans, Robert J.; Deutch, Steve

Fast pyrolysis and catalytic fast pyrolysis (CFP) of biomass produce a liquid product stream comprised of various classes of organic compounds having different molecule size and polarity. This liquid, either spontaneously in the case of catalytic fast pyrolysis or by water addition for the non-catalytic process separates into a non-polar organic-rich fraction and a highly polar water-rich fraction. The organic fraction can be used as a blendstock or feedstock for further processing in a refinery while, in the CFP process design, the aqueous phase is currently sent to wastewater treatment, which results in a loss of residual biogenic carbon presentmore » in this stream. Our work focuses on the catalytic conversion of the biogenic carbon in pyrolysis aqueous phase streams to produce hydrocarbons using a vertical micro-reactor coupled to a molecular beam mass spectrometer (MBMS). Furthermore, the MBMS provides real-time analysis of products while also tracking catalyst deactivation. The catalyst used in this work was HZSM-5, which upgraded the oxygenated organics in the aqueous fraction to fuels comprising small olefins and aromatic hydrocarbons. During processing the aqueous bio-oil fraction the HZSM-5 catalyst exhibited higher activity and coke resistance than those observed in similar experiments using biomass or whole bio-oils. Reduced coking is likely due to ejection of coke precursors from the catalyst pores that was enhanced by excess process water available for steam stripping. The water reacted with coke precursors to form phenol, methylated phenols, naphthol, and methylated naphthols. Conversion data shows that up to 40 wt% of the carbon in the feed stream is recovered as hydrocarbons.« less

Reforming Biomass Derived Pyrolysis Bio-oil Aqueous Phase to Fuels

DOE PAGES

Mukarakate, Calvin; Evans, Robert J.; Deutch, Steve; ...

2017-01-07

Fast pyrolysis and catalytic fast pyrolysis (CFP) of biomass produce a liquid product stream comprised of various classes of organic compounds having different molecule size and polarity. This liquid, either spontaneously in the case of catalytic fast pyrolysis or by water addition for the non-catalytic process separates into a non-polar organic-rich fraction and a highly polar water-rich fraction. The organic fraction can be used as a blendstock or feedstock for further processing in a refinery while, in the CFP process design, the aqueous phase is currently sent to wastewater treatment, which results in a loss of residual biogenic carbon presentmore » in this stream. Our work focuses on the catalytic conversion of the biogenic carbon in pyrolysis aqueous phase streams to produce hydrocarbons using a vertical micro-reactor coupled to a molecular beam mass spectrometer (MBMS). Furthermore, the MBMS provides real-time analysis of products while also tracking catalyst deactivation. The catalyst used in this work was HZSM-5, which upgraded the oxygenated organics in the aqueous fraction to fuels comprising small olefins and aromatic hydrocarbons. During processing the aqueous bio-oil fraction the HZSM-5 catalyst exhibited higher activity and coke resistance than those observed in similar experiments using biomass or whole bio-oils. Reduced coking is likely due to ejection of coke precursors from the catalyst pores that was enhanced by excess process water available for steam stripping. The water reacted with coke precursors to form phenol, methylated phenols, naphthol, and methylated naphthols. Conversion data shows that up to 40 wt% of the carbon in the feed stream is recovered as hydrocarbons.« less

Turbine Fuels from Tar Sands Bitumen and Heavy Oil. Phase I. Preliminary Process Analysis.

DTIC Science & Technology

1985-04-09

OIL RESERVOIRS OF THE UNITED STATES Resource: Oil -in-Place State Field Name (County) (Million Bbls.) Arkansas Smackover Old (Union) 1,6U0 California...Flow Schematic for Gas Oil Feed Hydrotreater 94 14 Summary of Case Studies for Processing Bitumen from New Mexico 95 15 Summary of Case Studies for...Naphtha Hydrotreating Process Estimates 112 14 Gas Oil Hydrocracking Process Estimates 113 l! Gas Oil Hydrotreating Process Estimate 114 16 Fluid

Understanding Interactions between Manganese Oxide and Gold That Lead to Enhanced Activity for Electrocatalytic Water Oxidation

PubMed Central

2015-01-01

To develop active nonprecious metal-based electrocatalysts for the oxygen evolution reaction (OER), a limiting reaction in several emerging renewable energy technologies, a deeper understanding of the activity of the first row transition metal oxides is needed. Previous studies of these catalysts have reported conflicting results on the influence of noble metal supports on the OER activity of the transition metal oxides. Our study aims to clarify the interactions between a transition metal oxide catalyst and its metal support in turning over this reaction. To achieve this goal, we examine a catalytic system comprising nanoparticulate Au, a common electrocatalytic support, and nanoparticulate MnOx, a promising OER catalyst. We conclusively demonstrate that adding Au to MnOx significantly enhances OER activity relative to MnOx in the absence of Au, producing an order of magnitude higher turnover frequency (TOF) than the TOF of the best pure MnOx catalysts reported to date. We also provide evidence that it is a local rather than bulk interaction between Au and MnOx that leads to the observed enhancement in the OER activity. Engineering improvements in nonprecious metal-based catalysts by the addition of Au or other noble metals could still represent a scalable catalyst as even trace amounts of Au are shown to lead a significant enhancement in the OER activity of MnOx. PMID:24661269

Pre-converted nitric oxide gas in catalytic reduction system

DOEpatents

Hsiao, Mark C.; Merritt, Bernard T.; Penetrante, Bernardino M.; Vogtlin, George E.

1999-01-01

A two-stage catalyst comprises an oxidative first stage and a reductive second stage. The first stage is intended to convert NO to NO.sub.2 in the presence of O.sub.2. The second stage serves to convert NO.sub.2 to environmentally benign gases that include N2, CO2, and H.sub.2 O. By preconverting NO to NO.sub.2 in the first stage, the efficiency of the second stage for NO.sub.x reduction is enhanced. For example, an internal combustion engine exhaust is connected by a pipe to a first chamber. An oxidizing first catalyst converts NO to NO.sub.2 in the presence of O.sub.2 and includes platinum/alumina, e.g., Pt/Al.sub.2 O.sub.3 catalyst. A flow of hydrocarbons (C.sub.x H.sub.y) is input from a pipe into a second chamber. For example, propene can be used as a source of hydrocarbons. The NO.sub.2 from the first catalyst mixes with the hydrocarbons in the second chamber. The mixture proceeds to a second reduction catalyst that converts NO.sub.2 to N2, CO2, and H.sub.2 O, and includes a gamma-alumina .gamma.-Al.sub.2 O.sub.3. The hydrocarbons and NO.sub.x are simultaneously reduced while passing through the second catalyst.

Understanding interactions between manganese oxide and gold that lead to enhanced activity for electrocatalytic water oxidation.

PubMed

Gorlin, Yelena; Chung, Chia-Jung; Benck, Jesse D; Nordlund, Dennis; Seitz, Linsey; Weng, Tsu-Chien; Sokaras, Dimosthenis; Clemens, Bruce M; Jaramillo, Thomas F

2014-04-02

To develop active nonprecious metal-based electrocatalysts for the oxygen evolution reaction (OER), a limiting reaction in several emerging renewable energy technologies, a deeper understanding of the activity of the first row transition metal oxides is needed. Previous studies of these catalysts have reported conflicting results on the influence of noble metal supports on the OER activity of the transition metal oxides. Our study aims to clarify the interactions between a transition metal oxide catalyst and its metal support in turning over this reaction. To achieve this goal, we examine a catalytic system comprising nanoparticulate Au, a common electrocatalytic support, and nanoparticulate MnO(x), a promising OER catalyst. We conclusively demonstrate that adding Au to MnO(x) significantly enhances OER activity relative to MnO(x) in the absence of Au, producing an order of magnitude higher turnover frequency (TOF) than the TOF of the best pure MnO(x) catalysts reported to date. We also provide evidence that it is a local rather than bulk interaction between Au and MnO(x) that leads to the observed enhancement in the OER activity. Engineering improvements in nonprecious metal-based catalysts by the addition of Au or other noble metals could still represent a scalable catalyst as even trace amounts of Au are shown to lead a significant enhancement in the OER activity of MnO(x).

Pre-converted nitric oxide gas in catalytic reduction system

DOEpatents

Hsiao, M.C.; Merritt, B.T.; Penetrante, B.M.; Vogtlin, G.E.

1999-04-06

A two-stage catalyst comprises an oxidative first stage and a reductive second stage. The first stage is intended to convert NO to NO{sub 2} in the presence of O{sub 2}. The second stage serves to convert NO{sub 2} to environmentally benign gases that include N{sub 2}, CO{sub 2}, and H{sub 2}O. By preconverting NO to NO{sub 2} in the first stage, the efficiency of the second stage for NO{sub x} reduction is enhanced. For example, an internal combustion engine exhaust is connected by a pipe to a first chamber. An oxidizing first catalyst converts NO to NO{sub 2} in the presence of O{sub 2} and includes platinum/alumina, e.g., Pt/Al{sub 2}O{sub 3} catalyst. A flow of hydrocarbons (C{sub x}H{sub y}) is input from a pipe into a second chamber. For example, propene can be used as a source of hydrocarbons. The NO{sub 2} from the first catalyst mixes with the hydrocarbons in the second chamber. The mixture proceeds to a second reduction catalyst that converts NO{sub 2} to N{sub 2}, CO{sub 2}, and H{sub 2}O, and includes a {gamma}-Al{sub 2}O{sub 3}. The hydrocarbons and NO{sub x} are simultaneously reduced while passing through the second catalyst. 9 figs.

High-density 3D graphene-based monolith and related materials, methods, and devices

DOEpatents

Worsley, Marcus A.; Baumann, Theodore F.; Biener, Juergen; Charnvanichborikarn, Supakit; Kucheyev, Sergei; Montalvo, Elizabeth; Shin, Swanee; Tylski, Elijah

2017-03-21

A composition comprising at least one high-density graphene-based monolith, said monolith comprising a three-dimensional structure of graphene sheets crosslinked by covalent carbon bonds and having a density of at least 0.1 g/cm.sup.3. Also provided is a method comprising: preparing a reaction mixture comprising a suspension and at least one catalyst, said suspension selected from a graphene oxide (GO) suspension and a carbon nanotube suspension; curing the reaction mixture to produce a wet gel; drying the wet gel to produce a dry gel, said drying step is substantially free of supercritical drying and freeze drying; and pyrolyzing the dry gel to produce a high-density graphene-based monolith. Exceptional combinations of properties are achieved including high conductive and mechanical properties.

Alkali or alkaline earth metal promoted catalyst and a process for methanol synthesis using alkali or alkaline earth metals as promoters

DOEpatents

Tierney, J.W.; Wender, I.; Palekar, V.M.

1995-01-31

The present invention relates to a novel route for the synthesis of methanol, and more specifically to the production of methanol by contacting synthesis gas under relatively mild conditions in a slurry phase with a heterogeneous catalyst comprising reduced copper chromite impregnated with an alkali or alkaline earth metal. There is thus no need to add a separate alkali or alkaline earth compound. The present invention allows the synthesis of methanol to occur in the temperature range of approximately 100--160 C and the pressure range of 40--65 atm. The process produces methanol with up to 90% syngas conversion per pass and up to 95% methanol selectivity. The only major by-product is a small amount of easily separated methyl formate. Very small amounts of water, carbon dioxide and dimethyl ether are also produced. The present catalyst combination also is capable of tolerating fluctuations in the H[sub 2]/CO ratio without major deleterious effect on the reaction rate. Furthermore, carbon dioxide and water are also tolerated without substantial catalyst deactivation.

Reactions catalyzed by haloporphyrins

DOEpatents

Ellis, P.E. Jr.; Lyons, J.E.

1996-02-06

The invention provides novel methods for the oxidation of hydrocarbons with oxygen-containing gas to form hydroxy-group containing compounds and for the decomposition of hydroperoxides to form hydroxy-group containing compounds. The catalysts used in the methods of the invention comprise transition metal complexes of a porphyrin ring having 1 to 12 halogen substituents on the porphyrin ring, at least one of said halogens being in a meso position and/or the catalyst containing no aryl group in a meso position. The catalyst compositions are prepared by halogenating a transition metal complex of a porphyrin. In one embodiment, a complex of a porphyrin with a metal whose porphyrin complexes are not active for oxidation of alkanes is halogenated, thereby to obtain a haloporphyrin complex of that metal, the metal is removed from the haloporphyrin complex to obtain the free base form of the haloporphyrin, and a metal such as iron whose porphyrin complexes are active for oxidation of alkanes and for the decomposition of alkyl hydroperoxides is complexed with the free base to obtain an active catalyst for oxidation of alkanes and decomposition of alkyl hydroperoxides.

Reactions catalyzed by haloporphyrins

DOEpatents

Ellis, Jr., Paul E.; Lyons, James E.

1996-01-01

The invention provides novel methods for the oxidation of hydrocarbons with oxygen-containing gas to form hydroxy-group containing compounds and for the decomposition of hydroperoxides to form hydroxygroup containing compounds. The catalysts used in the methods of the invention comprise transition metal complexes of a porphyrin ring having 1 to 12 halogen substituents on the porphyrin ring, at least one of said halogens being in a meso position and/or the catalyst containing no aryl group in a meso position. The catalyst compositions are prepared by halogenating a transition metal complex of a porphyrin. In one embodiment, a complex of a porphyrin with a metal whose porphyrin complexes are not active for oxidation of alkanes is halogenated, thereby to obtain a haloporphyrin complex of that metal, the metal is removed from the haloporphyrin complex to obtain the free base form of the haloporphyrin, and a metal such as iron whose porphyrin complexes are active for oxidation of alkanes and for the decomposition of alkyl hydroperoxides is complexed with the free base to obtain an active catalyst for oxidation of alkanes and decomposition of alkyl hydroperoxides.

anti-Selective catalytic asymmetric nitroaldol reaction via a heterobimetallic heterogeneous catalyst.

PubMed

Nitabaru, Tatsuya; Nojiri, Akihiro; Kobayashi, Makoto; Kumagai, Naoya; Shibasaki, Masakatsu

2009-09-30

Full details of an anti-selective catalytic asymmetric nitroaldol reaction promoted by a heterobimetallic catalyst comprised of Nd(5)O(O(i)Pr)(13), an amide-based ligand, and NaHMDS (sodium hexamethyldisilazide) are described. A systematic synthesis and evaluation of amide-based ligands led to the identification of optimum ligand 1m, which provided a suitable platform for the Nd/Na heterobimetallic complex. During the catalyst preparation in THF, a heterogeneous mixture developed and centrifugation of the suspension allowed for separation of the precipitate, which contained the active catalyst and which could be stored for at least 1 month without any loss of catalytic performance. The precipitate promoted a nitroaldol (Henry) reaction for a broad range of nitroalkanes and aldehydes under heterogeneous conditions, affording the corresponding 1,2-nitroalkanol in a highly anti-selective (up to anti/syn = >40/1) and enantioselective manner (up to 98% ee). Inductively coupled plasma (ICP) and X-ray fluorescence (XRF) analyses revealed that the precipitate indeed included both neodymium and sodium, which was further supported by high-resolution ESI TOF MS spectrometry.

Alkali or alkaline earth metal promoted catalyst and a process for methanol synthesis using alkali or alkaline earth metals as promoters

DOEpatents

Tierney, John W.; Wender, Irving; Palekar, Vishwesh M.

1995-01-01

The present invention relates to a novel route for the synthesis of methanol, and more specifically to the production of methanol by contacting synthesis gas under relatively mild conditions in a slurry phase with a heterogeneous catalyst comprising reduced copper chromite impregnated with an alkali or alkaline earth metal. There is thus no need to add a separate alkali or alkaline earth compound. The present invention allows the synthesis of methanol to occur in the temperature range of approximately 100.degree.-160.degree. C. and the pressure range of 40-65 atm. The process produces methanol with up to 90% syngas conversion per pass and up to 95% methanol selectivity. The only major by-product is a small amount of easily separated methyl formate. Very small amounts of water, carbon dioxide and dimethyl ether are also produced. The present catalyst combination also is capable of tolerating fluctuations in the H.sub.2 /CO ratio without major deleterious effect on the reaction rate. Furthermore, carbon dioxide and water are also tolerated without substantial catalyst deactivation.

Fine-Grained Targets for Laser Synthesis of Carbon Nanotubes

NASA Technical Reports Server (NTRS)

Smith, Michael W. (Inventor); Park, Cheol (Inventor)

2017-01-01

A mechanically robust, binder-free, inexpensive target for laser synthesis of carbon nanotubes and a method for making same, comprising the steps of mixing prismatic edge natural flake graphite with a metal powder catalyst and pressing the graphite and metal powder mixture into a mold having a desired target shape.

Fine-Grained Targets for Laser Synthesis of Carbon Nanotubes

NASA Technical Reports Server (NTRS)

Smith, Michael W. (Inventor); Park, Cheol (Inventor)

2015-01-01

A mechanically robust, binder-free, inexpensive target for laser synthesis of carbon nanotubes and a method for making same, comprising the steps of mixing prismatic edge natural flake graphite with a metal powder catalyst and pressing the graphite and metal powder mixture into a mold having a desired target shape.

High ethylene to ethane processes for oxidative coupling

DOEpatents

Chafin, R.B.; Warren, B.K.

1991-12-17

Oxidative coupling of lower alkane to higher hydrocarbon is conducted using a catalyst comprising barium and/or strontium component and a metal oxide combustion promoter in the presence of vapor phase halogen component. High ethylene to ethane mole ratios in the product can be obtained over extended operating periods.

High ethylene to ethane processes for oxidative coupling

DOEpatents

Chafin, Richard B.; Warren, Barbara K.

1991-01-01

Oxidative coupling of lower alkane to higher hydrocarbon is conducted using catalyst comprising barium and/or strontium component and a metal oxide combustion promoter in the presence of vapor phase halogen component. High ethylene to ethane mole ratios in the product can be obtained over extended operating periods.

Metal nanoparticle deposited inorganic nanostructure hybrids, uses thereof and processes for their preparation

DOEpatents

Tenne, Reshef; Tsverin, Yulia; Burghaus, Uwe; Komarneni, Mallikharjuna Rao

2016-01-26

This invention relates to a hybrid component comprising at least one nanoparticle of inorganic layered compound (in the form of fullerene-like structure or nanotube), and at least one metal nanoparticle, uses thereof as a catalyst, (e.g. photocatalysis) and processes for its preparation.

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

DOEpatents

Sharp, David W.

1980-01-01

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

Gas diffusion electrode setup for catalyst testing in concentrated phosphoric acid at elevated temperatures

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

Wiberg, Gustav K. H., E-mail: gustav.wiberg@gmail.com, E-mail: m.arenz@chem.ku.dk; Fleige, Michael; Arenz, Matthias, E-mail: gustav.wiberg@gmail.com, E-mail: m.arenz@chem.ku.dk

2015-02-15

We present a detailed description of the construction and testing of an electrochemical cell setup allowing the investigation of a gas diffusion electrode containing carbon supported high surface area catalysts. The setup is designed for measurements in concentrated phosphoric acid at elevated temperature, i.e., very close to the actual conditions in high temperature proton exchange membrane fuel cells (HT-PEMFCs). The cell consists of a stainless steel flow field and a PEEK plastic cell body comprising the electrochemical cell, which exhibits a three electrode configuration. The cell body and flow field are braced using a KF-25 vacuum flange clamp, which allowsmore » an easy assembly of the setup. As demonstrated, the setup can be used to investigate temperature dependent electrochemical processes on high surface area type electrocatalysts, but it also enables quick screening tests of HT-PEMFC catalysts under realistic conditions.« less

Acid-functionalized polyolefin materials and their use in acid-promoted chemical reactions

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

Oyola, Yatsandra; Tian, Chengcheng; Bauer, John Christopher

An acid-functionalized polyolefin material that can be used as an acid catalyst in a wide range of acid-promoted chemical reactions, wherein the acid-functionalized polyolefin material includes a polyolefin backbone on which acid groups are appended. Also described is a method for the preparation of the acid catalyst in which a precursor polyolefin is subjected to ionizing radiation (e.g., electron beam irradiation) of sufficient power and the irradiated precursor polyolefin reacted with at least one vinyl monomer having an acid group thereon. Further described is a method for conducting an acid-promoted chemical reaction, wherein an acid-reactive organic precursor is contacted inmore » liquid form with a solid heterogeneous acid catalyst comprising a polyolefin backbone of at least 1 micron in one dimension and having carboxylic acid groups and either sulfonic acid or phosphoric acid groups appended thereto.« less

Gas diffusion electrode setup for catalyst testing in concentrated phosphoric acid at elevated temperatures

NASA Astrophysics Data System (ADS)

Wiberg, Gustav K. H.; Fleige, Michael; Arenz, Matthias

2015-02-01

We present a detailed description of the construction and testing of an electrochemical cell setup allowing the investigation of a gas diffusion electrode containing carbon supported high surface area catalysts. The setup is designed for measurements in concentrated phosphoric acid at elevated temperature, i.e., very close to the actual conditions in high temperature proton exchange membrane fuel cells (HT-PEMFCs). The cell consists of a stainless steel flow field and a PEEK plastic cell body comprising the electrochemical cell, which exhibits a three electrode configuration. The cell body and flow field are braced using a KF-25 vacuum flange clamp, which allows an easy assembly of the setup. As demonstrated, the setup can be used to investigate temperature dependent electrochemical processes on high surface area type electrocatalysts, but it also enables quick screening tests of HT-PEMFC catalysts under realistic conditions.

Value recovery from spent alumina-base catalyst

DOEpatents

Hyatt, David E.

1987-01-01

A process for the recovery of aluminum and at least one other metal selected from the group consisting of molybdenum, nickel and cobalt from a spent hydrogenation catalyst comprising (1) adding about 1 to 3 parts H.sub.2 SO.sub.4 to each part of spent catalyst in a reaction zone of about 20.degree. to 200.degree. C. under sulfide gas pressure between about 1 and about 35 atmospheres, (2) separating the resultant Al.sub.2 (SO.sub.4).sub.3 solution from the sulfide precipitate in the mixture, (3) oxidizing the remaining sulfide precipitate as an aqueous slurry at about 20.degree. to 200.degree. C. in an oxygen-containing atmosphere at a pressure between about 1 and about 35 atmospheres, (4) separating the slurry to obtain solid molybdic acid and a sulfate liquor containing said at least one metal, and (5) recovering said at least one metal from the sulfate liquor in marketable form.

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

Lilga, Michael A.; Padmaperuma, Asanga B.; Auberry, Deanna L.

We studied a new process for direct conversion of either levulinic acid (LA) or γ-valerolactone (GVL) to hydrocarbon fuel precursors. The process involves passing an aqueous solution of LA or GVL containing a reducing agent, such as ethylene glycol or formic acid, over a ketonization catalyst at 380–400 °C and atmospheric pressure to form a biphasic liquid product. The organic phase is significantly oligomerized and deoxygenated and comprises a complex mixture of open-chain alkanes and olefins, aromatics, and low concentrations of ketones, alcohols, ethers, and carboxylates or lactones. Carbon content in the aqueous phase decreases with decreasing feed rate; themore » aqueous phase can be reprocessed through the same catalyst to form additional organic oils to improve carbon yield. Catalysts are readily regenerated to restore initial activity. Furthermore, the process might be valuable in converting cellulosics to biorenewable gasoline, jet, and diesel fuels as a means to decrease petroleum use and decrease greenhouse gas emissions.« less

Palladium on Nitrogen-Doped Mesoporous Carbon: A Bifunctional Catalyst for Formate-Based, Carbon-Neutral Hydrogen Storage.

PubMed

Wang, Fanan; Xu, Jinming; Shao, Xianzhao; Su, Xiong; Huang, Yanqiang; Zhang, Tao

2016-02-08

The lack of safe, efficient, and economical hydrogen storage technologies is a hindrance to the realization of the hydrogen economy. Reported herein is a reversible formate-based carbon-neutral hydrogen storage system that is established over a novel catalyst comprising palladium nanoparticles supported on nitrogen-doped mesoporous carbon. The support was fabricated by a hard template method and nitridated under a flow of ammonia. Detailed analyses demonstrate that this bicarbonate/formate redox equilibrium is promoted by the cooperative role of the doped nitrogen functionalities and the well-dispersed, electron-enriched palladium nanoparticles. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Catalyst for cracking kerosene

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

Hsie, C. H.

1985-06-04

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

Submergible torch for treating waste solutions and method thereof

DOEpatents

Mattus, Alfred J.

1995-01-01

A submergible torch for removing nitrate and/or nitrite ions from a waste solution containing nitrate and/or nitrite ions comprises: a torch tip, a fuel delivery mechanism, a fuel flow control mechanism, a catalyst, and a combustion chamber. The submergible torch is ignited to form a flame within the combustion chamber of the submergible torch. The torch is submerged in a waste solution containing nitrate and/or nitrite ions in such a manner that the flame is in contact with the waste solution and the catalyst and is maintained submerged for a period of time sufficient to decompose the nitrate and/or nitrite ions present in the waste solution.

Method of inducing surface ensembles on a metal catalyst

DOEpatents

Miller, Steven S.

1989-01-01

A method of inducing surface ensembles on a transition metal catalyst used in the conversion of a reactant gas or gas mixture, such as carbon monoxide and hydrogen into hydrocarbons (the Fischer-Tropsch reaction) is disclosed which comprises adding a Lewis base to the syngas (CO+H.sub.2) mixture before reaction takes place. The formation of surface ensembles in this manner restricts the number and types of reaction pathways which will be utilized, thus greatly narrowing the product distribution and maximizing the efficiency of the Fischer-Tropsch reaction. Similarly, amines may also be produced by the conversion of reactant gas or gases, such as nitrogen, hydrogen, or hydrocarbon constituents.

Method of inducing surface ensembles on a metal catalyst

DOEpatents

Miller, S.S.

1987-10-02

A method of inducing surface ensembles on a transition metal catalyst used in the conversion of a reactant gas or gas mixture, such as carbon monoxide and hydrogen into hydrocarbons (the Fischer-Tropsch reaction) is disclosed which comprises adding a Lewis base to the syngas (CO + H/sub 2/) mixture before reaction takes place. The formation of surface ensembles in this manner restricts the number and types of reaction pathways which will be utilized, thus greatly narrowing the product distribution and maximizing the efficiency of the Fischer-Tropsch reaction. Similarly, amines may also be produced by the conversion of reactant gas or gases, such as nitrogen, hydrogen, or hydrocarbon constituents.

Lithium-air batteries, method for making lithium-air batteries

DOEpatents

Vajda, Stefan; Curtiss, Larry A.; Lu, Jun; Amine, Khalil; Tyo, Eric C.

2016-11-15

The invention provides a method for generating Li.sub.2O.sub.2 or composites of it, the method uses mixing lithium ions with oxygen ions in the presence of a catalyst. The catalyst comprises a plurality of metal clusters, their alloys and mixtures, each cluster consisting of between 3 and 18 metal atoms. The invention also describes a lithium-air battery which uses a lithium metal anode, and a cathode opposing the anode. The cathode supports metal clusters, each cluster consisting of size selected clusters, taken from a range of between approximately 3 and approximately 18 metal atoms, and an electrolyte positioned between the anode and the cathode.

Submergible torch for treating waste solutions and method thereof

DOEpatents

Mattus, Alfred J.

1994-01-01

A submergible torch for removing nitrate and/or nitrite ions from a waste solution containing nitrate and/or nitrite ions comprises: a torch tip, a fuel delivery mechanism, a fuel flow control mechanism, a catalyst, and a combustion chamber. The submergible torch is ignited to form a flame within the combustion chamber of the submergible torch. The torch is submerged in a waste solution containing nitrate and/or nitrite ions in such a manner that the flame is in contact with the waste solution and the catalyst and is maintained submerged for a period of time sufficient to decompose the nitrate and/or nitrite ions present in the waste solution.

High-Selectivity Electrochemical Conversion of CO 2 to Ethanol using a Copper Nanoparticle/N-Doped Graphene Electrode

DOE PAGES

Song, Yang; Peng, Rui; Hensley, Dale K.; ...

2016-09-28

Carbon dioxide is a pollutant, but also a potential carbon source provided an efficient means to convert it to useful products. Herein we report a nanostructured catalyst for the direct electrochemical reduction of dissolved CO 2 to ethanol with high Faradaic efficiency (63%) and high selectivity (84%). The catalyst is comprised of Cu nanoparticle on a highly textured, N-doped graphene film. Detailed electrochemical analysis and complementary DFT calculations indicate a novel mechanism in which multiple active sites, working sequentially, control the coupling of carbon monoxide radicals and mediate the subsequent electrochemical reduction to alcohol.

Catalytic conversion of alcohols having at least three carbon atoms to hydrocarbon blendstock

DOEpatents

Narula, Chaitanya K.; Davison, Brian H.

2018-04-17

A method for producing a hydrocarbon blendstock, the method comprising contacting at least one saturated acyclic alcohol having at least three and up to ten carbon atoms with a metal-loaded zeolite catalyst at a temperature of at least 100.degree. C. and up to 550.degree. C., wherein the metal is a positively-charged metal ion, and the metal-loaded zeolite catalyst is catalytically active for converting the alcohol to the hydrocarbon blendstock, wherein the method directly produces a hydrocarbon blendstock having less than 1 vol % ethylene and at least 35 vol % of hydrocarbon compounds containing at least eight carbon atoms.

Catalytic conversion of alcohols having at least three carbon atoms to hydrocarbon blendstock

DOEpatents

Narula, Chaitanya K.; Davison, Brian H.

2015-11-13

A method for producing a hydrocarbon blendstock, the method comprising contacting at least one saturated acyclic alcohol having at least three and up to ten carbon atoms with a metal-loaded zeolite catalyst at a temperature of at least 100°C and up to 550°C, wherein the metal is a positively-charged metal ion, and the metal-loaded zeolite catalyst is catalytically active for converting the alcohol to the hydrocarbon blendstock, wherein the method directly produces a hydrocarbon blendstock having less than 1 vol % ethylene and at least 35 vol % of hydrocarbon compounds containing at least eight carbon atoms.

Dilute acid/metal salt hydrolysis of lignocellulosics

DOEpatents

Nguyen, Quang A.; Tucker, Melvin P.

2002-01-01

A modified dilute acid method of hydrolyzing the cellulose and hemicellulose in lignocellulosic material under conditions to obtain higher overall fermentable sugar yields than is obtainable using dilute acid alone, comprising: impregnating a lignocellulosic feedstock with a mixture of an amount of aqueous solution of a dilute acid catalyst and a metal salt catalyst sufficient to provide higher overall fermentable sugar yields than is obtainable when hydrolyzing with dilute acid alone; loading the impregnated lignocellulosic feedstock into a reactor and heating for a sufficient period of time to hydrolyze substantially all of the hemicellulose and greater than 45% of the cellulose to water soluble sugars; and recovering the water soluble sugars.

W-containing oxide layers obtained on aluminum and titanium by PEO as catalysts in thiophene oxidation

NASA Astrophysics Data System (ADS)

Rudnev, V. S.; Lukiyanchuk, I. V.; Vasilyeva, M. S.; Morozova, V. P.; Zelikman, V. M.; Tarkhanova, I. G.

2017-11-01

W-containing oxide layers fabricated on titanium and aluminum alloys by Plasma electrolytic oxidation (PEO) have been tested in the reaction of the peroxide oxidation of thiophene. Samples with two types of coatings have been investigated. Coatings I contained tungsten oxide in the matrix and on the surface of amorphous silica-titania or silica-alumina layers, while coatings II comprised crystalline WO3 and/or Al2(WO4)3. Aluminum-supported catalyst containing a smallest amount of transition metals in the form of tungsten oxides and manganese oxides in low oxidation levels showed high activity and stability.

Esterification of fermentation-derived acids via pervaporation

DOEpatents

Datta, R.; Tsai, S.P.

1998-03-03

A low temperature method for esterifying ammonium- and amine-containing salts is provided whereby the salt is reacted with an alcohol in the presence of heat and a catalyst and then subjected to a dehydration and deamination process using pervaporation. The invention also provides for a method for producing esters of fermentation derived, organic acid salt comprising first cleaving the salt into its cationic part and anionic part, mixing the anionic part with an alcohol to create a mixture; heating the mixture in the presence of a catalyst to create an ester; dehydrating the now heated mixture; and separating the ester from the now-dehydrated mixture. 2 figs.

Esterification of fermentation-derived acids via pervaporation

DOEpatents

Datta, Rathin; Tsai, Shih-Perng

1998-01-01

A low temperature method for esterifying ammonium- and amine-containing salts is provided whereby the salt is reacted with an alcohol in the presence of heat and a catalyst and then subjected to a dehydration and deamination process using pervaporation. The invention also provides for a method for producing esters of fermentation derived, organic acid salt comprising first cleaving the salt into its cationic part and anionic part, mixing the anionic part with an alcohol to create a mixture; heating the mixture in the presence of a catalyst to create an ester; dehydrating the now heated mixture; and separating the ester from the now-dehydrated mixture.

System for rapid biohydrogen phenotypic screening of microorganisms using a chemochromic sensor

DOEpatents

Seibert, Michael; Benson, David K.; Flynn, Timothy Michael

2002-01-01

Provided is a system for identifying a hydrogen gas producing organism. The system includes a sensor film having a first layer comprising a transition metal oxide or oxysalt and a second layer comprising a hydrogen-dissociative catalyst metal, the first and second layers having an inner and an outer surface wherein the inner surface of the second layer is deposited on the outer surface of the first layer, and a substrate adjacent to the outer surface of the second layer, the organism isolated on the substrate.

Method and apparatus for rapid biohydrogen phenotypic screening of microorganisms using a chemochromic sensor

DOEpatents

Seibert, Michael; Benson, David K.; Flynn, Timothy Michael

2001-01-01

The invention provides an assay system for identifying a hydrogen-gas-producing organism, including a sensor film having a first layer comprising a transition metal oxide or oxysalt and a second layer comprising hydrogen-dissociative catalyst metal, the first and second layers having an inner and an outer surface wherein the inner surface of the second layer is deposited on the outer surface of the first layer, and a substrate disposed proximally to the outer surface of the second layer, the organism being isolated on the substrate.

Method for improving product yields in an anionic metalloporphyrin-based artificial photosynthesis system

DOEpatents

Shelnutt, John A.

1986-01-01

A method for improving product yields in an anionic metalloporphyrin-based artificial photosynthesis system for hydrogen generation which comprises forming an aqueous solution comprising an electron donor, methylviologen, and certain metalloporphyrins and metallochlorins, and irradiating said aqueous solution with light in the presence of a catalyst. In the photosynthesis process, solar energy is collected and stored in the form of a gas hydrogen. Ligands attached above and below the metalloporphyrin and metallochlorin plane are capable of sterically blocking photochemically inactive electrostatically bound .pi.--.pi. complexes which can develop.

Method for improving product yields in an anionic metalloporphyrin-based artificial photosynthesis system

DOEpatents

Shelnutt, J.A.

1984-11-29

A method is disclosed improving product yields in an anionic metalloporphyrin-based artificial photosynthesis system for hydrogen generation. The method comprises forming an aqueous solution comprising an electron donor, methylviologen, and certain metalloporphyrins and metallochlorins, and irradiating said aqueous solution with light in the presence of a catalyst. In the photosynthesis process, solar energy is collected and stored in the form of a hydrogen. Ligands attached above and below the metalloporphyrin and metallochlorin plane are capable of sterically blocking photochemically inactive electrostatically bound ..pi..-..pi.. complexes which can develop.

Spin conversion of positronium in NiO/Al2O3 catalysts observed by coincidence Doppler broadening technique

NASA Astrophysics Data System (ADS)

Zhang, H. J.; Chen, Z. Q.; Wang, S. J.; Kawasuso, A.; Morishita, N.

2010-07-01

High-purity NiO/Al2O3 catalysts were prepared by mixing NiO and γ-Al2O3 nanopowders. X-ray diffraction patterns were measured to characterize the grain size and crystalline phase of the nanopowders. Positron-annihilation spectroscopy was used to study the microstructure and surface properties of the pores inside the NiO/Al2O3 catalysts. The positron lifetime spectrum comprises two short and two long lifetime components. The two long lifetimes τ3 and τ4 correspond to ortho-positronium (o-Ps) annihilated in microvoids and large pores, respectively. With increasing NiO content in the NiO/Al2O3 catalysts, both τ4 and its intensity I4 show continuous decrease. Meanwhile, the para-positronium (p-Ps) intensity, obtained from coincidence Doppler broadening spectra, increases gradually with NiO content. The different variation in o-Ps and p-Ps intensity suggests the ortho-para conversion of positronium in NiO/Al2O3 catalysts. X-ray photoelectron spectroscopy shows that Ni mainly exists in the form of NiO. The electron-spin-resonance measurements reveal that the ortho-para conversion of Ps is induced by the unpaired electrons of the paramagnetic centers of NiO.

Literature survey of properties of synfuels derived from coal

NASA Technical Reports Server (NTRS)

Reynolds, T. W.; Niedzwiecki, R. W.; Clark, J. S.

1980-01-01

A literature survey of the properties of synfuels for ground-based gas turbine applications is presented. Four major concepts for converting coal into liquid fuels are described: solvent extraction, catalytic liquefaction, pyrolysis, and indirect liquefaction. Data on full range syncrudes, various distillate cuts, and upgraded products are presented for fuels derived from various processes, including H-coal, synthoil, solvent-refined coal, donor solvent, zinc chloride hydrocracking, co-steam, and flash pyrolysis. Some typical ranges of data for coal-derived low Btu gases are also presented.

A Simple and Efficient Synthesis of 4-Arylacridinediones and 6-Aryldiindeno[1,2-b:2,1-e]pyridinediones using CuI Nanoparticles as Catalyst under Solvent-Free Conditions.

PubMed

Abdolmohammadi, Shahrzad; Dahi-Azar, Saman; Mohammadnejad, Mahdieh; Hosseinian, Akram

2017-01-01

The importance of acridine core structure and other heterocycles containing its framework is well known, as they are found in numerous compounds with a variety of biological effects. Pyridine is also an important solvent and heterocyclic nucleus for the design and synthesis of novel molecules with biological properties. It occurs in several natural compounds which are used as a precursor in agrochemicals and pharmaceuticals. The utility of nanostructured metal salts because of their small size and high surface area as catalysts in organic synthesis has drawn special attention due to their better properties such as slower reaction rate, reusability of the catalyst, and higher yields of products compared to the bulk size. Nanosized copper iodide is one reusable Lewis acid catalyst which has revealed several catalytic activities for the synthesis of organic compounds and others. As part of our recent study to develop heterocyclic syntheses using nanostructured catalysts, we now report an efficient and clean synthetic route to 4-arylacridinediones and 6-aryldiindeno[1,2-b:2,1-e]pyridinediones via a condensation reaction catalyzed by CuI nanoparticles under solvent-free conditions. The present work deals with the condensation reaction of aromatic aldehydes, ammonium acetate and active methylene compounds comprising dimedone or 1,3- indanedione in the presence of a catalytic amount of the synthesized CuI nanoparticles could be applied for the solvent-free preparation of 4-arylacridinediones and 6-aryldiindeno[1,2-b:2,1- e]pyridinediones at 70 °C within 60 min. A series of 9-aryl-3,3,6,6-tetramethyl-3,4,6,7,9,10-hexahydro-1,8(2H,5H)-acridinediones and 6-aryldiindeno[1,2-b:2,1-e]pyridine-5,7-diones were synthesized in high to excellent yields via a simple one-pot three-component coupling reaction using the synthesized CuI nanoparticles as an efficient and recyclable catalyst. All synthesized compounds were well characterized by their satisfactory elemental analyses, IR, 1 H and 13 C NMR spectroscopy. The synthesized catalyst was fully characterized by XRD, TEM and SEM techniques. A solvent-free condensation between aromatic aldehydes, ammonium acetate and active methylene compounds comprising dimedone or 1,3-indanedione, in the presence of CuI nanoparticles as an efficient and recyclable catalyst leads to the formation of 4-arylacridinediones and 6-aryldiindeno[1,2-b:2,1-e]pyridinediones. This novel and practical approach has a number of advantages for instance, the condensation itself is solvent-free, the total amount of solvent used in the whole process is significantly decreased, the yields of pure products are high to excellent without any by-products, the catalyst is reusable, and the work-up is very simple. Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.org.

Structure-activity correlations in a nickel-borate oxygen evolution catalyst.

PubMed

Bediako, D Kwabena; Lassalle-Kaiser, Benedikt; Surendranath, Yogesh; Yano, Junko; Yachandra, Vittal K; Nocera, Daniel G

2012-04-18

An oxygen evolution catalyst that forms as a thin film from Ni(aq)(2+) solutions containing borate electrolyte (Ni-B(i)) has been studied by in situ X-ray absorption spectroscopy. A dramatic increase in catalytic rate, induced by anodic activation of the electrodeposited films, is accompanied by structure and oxidation state changes. Coulometric measurements correlated with X-ray absorption near-edge structure spectra of the active catalyst show that the nickel centers in activated films possess an average oxidation state of +3.6, indicating that a substantial proportion of nickel centers exist in a formal oxidation state of Ni(IV). In contrast, nickel centers in nonactivated films exist predominantly as Ni(III). Extended X-ray absorption fine structure reveals that activated catalyst films comprise bis-oxo/hydroxo-bridged nickel centers organized into sheets of edge-sharing NiO(6) octahedra. Diminished long-range ordering in catalyst films is due to their ostensibly amorphous nature. Nonactivated films display a similar oxidic nature but exhibit a distortion in the local coordination geometry about nickel centers, characteristic of Jahn-Teller distorted Ni(III) centers. Our findings indicate that the increase in catalytic activity of films is accompanied by changes in oxidation state and structure that are reminiscent of those observed for conversion of β-NiOOH to γ-NiOOH and consequently challenge the long-held notion that the β-NiOOH phase is a more efficient oxygen-evolving catalyst. © 2012 American Chemical Society

Two-dimensional porous anodic alumina for optoelectronics and photocatalytic application

NASA Astrophysics Data System (ADS)

Khoroshko, L. S.

2015-11-01

Fabrication of porous anodic alumina film structures using anodizing, sol-gel synthesis and photolithography is reported. The structures receive interest as planar waveguides due to strong photoluminescence of the embedded trivalent lanthanides. Mesoporous structures comprising sol-gel derived titania in porous anodic alumina play a role of effective catalyst for water purification.

Preparation of catalysts via ion-exchangeable coatings on supports

DOEpatents

Dosch, R.G.; Stephens, H.P.

1986-04-09

Disclosed are: new catalytic compositions which comprise an inert support coated with a hydrous alkali metal, alkaline earth metal, or quaternary ammonium titanate, niobate, zirconate, or tantalate, in which the alkali or alkaline earth metal or quaternary ammonium cations have been exchanged for a catalytically effective quantity of a catalytically effective metal.

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.

Porous substrates filled with nanomaterials

DOEpatents

Worsley, Marcus A.; Baumann, Theodore F.; Satcher, Jr., Joe H.; Stadermann, Michael

2018-04-03

A composition comprising: at least one porous carbon monolith, such as a carbon aerogel, comprising internal pores, and at least one nanomaterial, such as carbon nanotubes, disposed uniformly throughout the internal pores. The nanomaterial can be disposed in the middle of the monolith. In addition, a method for making a monolithic solid with both high surface area and good bulk electrical conductivity is provided. A porous substrate having a thickness of 100 microns or more and comprising macropores throughout its thickness is prepared. At least one catalyst is deposited inside the porous substrate. Subsequently, chemical vapor deposition is used to uniformly deposit a nanomaterial in the macropores throughout the thickness of the porous substrate. Applications include electrical energy storage, such as batteries and capacitors, and hydrogen storage.

Porous substrates filled with nanomaterials

DOEpatents

Worsley, Marcus A.; Baumann, Theodore F.; Satcher, Jr., Joe H.; Stadermann, Michael

2014-08-19

A composition comprising: at least one porous carbon monolith, such as a carbon aerogel, comprising internal pores, and at least one nanomaterial, such as carbon nanotubes, disposed uniformly throughout the internal pores. The nanomaterial can be disposed in the middle of the monolith. In addition, a method for making a monolithic solid with both high surface area and good bulk electrical conductivity is provided. A porous substrate having a thickness of 100 microns or more and comprising macropores throughout its thickness is prepared. At least one catalyst is deposited inside the porous substrate. Subsequently, chemical vapor deposition is used to uniformly deposit a nanomaterial in the macropores throughout the thickness of the porous substrate. Applications include electrical energy storage, such as batteries and capacitors, and hydrogen storage.

Method and apparatus for synthesizing hydrocarbons

DOEpatents

Colmenares, C.A.; Somorjai, G.A.; Maj, J.J.

1983-06-21

A method and apparatus for synthesizing a mixture of hydrocarbons having five carbons or less is disclosed. An equal molar ratio of CO and H/sub 2/ gases is caused to pass through a ThO/sub 2/ catalyst having a surface area of about 80 to 125 m/sup 2//g. The catalyst further includes Na present as a substitutional cation in an amount of about 5 to 10 atom %. At a temperature of about 340 to 360/sup 0/C, and at pressures of about 20 to 50 atm, CH/sub 3/OH is produced in an amount of about 90 wt % of the total hydrocarbon mixture, and comprised 1 mole % of the effluent gas.

Methods of refining natural oils, and methods of producing fuel compositions

DOEpatents

Firth, Bruce E.; Kirk, Sharon E.

2015-10-27

A method of refining a natural oil includes: (a) providing a feedstock that includes a natural oil; (b) reacting the feedstock in the presence of a metathesis catalyst to form a metathesized product that includes olefins and esters; (c) passivating residual metathesis catalyst with an agent that comprises nitric acid; (d) separating the olefins in the metathesized product from the esters in the metathesized product; and (e) transesterifying the esters in the presence of an alcohol to form a transesterified product and/or hydrogenating the olefins to form a fully or partially saturated hydrogenated product. Methods for suppressing isomerization of olefin metathesis products produced in a metathesis reaction, and methods of producing fuel compositions are described.

Microcombustor

DOEpatents

Gardner, Timothy J.; Manginelli, Ronald P.; Lewis, Patrick R.; Frye-Mason, Gregory C.; Colburn, Chris

2004-09-07

A microcombustor comprises a microhotplate and a catalyst for sustained combustion on the microscale. The microhotplate has very low heat capacity and thermal conductivity that mitigate large heat losses arising from large surface-to-volume ratios typical of the microdomain. The heated catalyst enables flame ignition and stabilization, permits combustion with lean fuel/air mixtures, extends a hydrocarbon's limits of flammability, and lowers the combustion temperature. The reduced operating temperatures enable a longer microcombustor lifetime and the reduced fuel consumption enables smaller fuel supplies, both of which are especially important for portable microsystems applications. The microcombustor can be used for on-chip thermal management and for sensor applications, such as heating of a micro gas chromatography column and for use as a micro flame ionization detector.

Nanocrystal assembly for tandem catalysis

DOEpatents

Yang, Peidong; Somorjai, Gabor; Yamada, Yusuke; Tsung, Chia-Kuang; Huang, Wenyu

2014-10-14

The present invention provides a nanocrystal tandem catalyst comprising at least two metal-metal oxide interfaces for the catalysis of sequential reactions. One embodiment utilizes a nanocrystal bilayer structure formed by assembling sub-10 nm platinum and cerium oxide nanocube monolayers on a silica substrate. The two distinct metal-metal oxide interfaces, CeO.sub.2--Pt and Pt--SiO.sub.2, can be used to catalyze two distinct sequential reactions. The CeO.sub.2--Pt interface catalyzed methanol decomposition to produce CO and H.sub.2, which were then subsequently used for ethylene hydroformylation catalyzed by the nearby Pt--SiO.sub.2 interface. Consequently, propanal was selectively produced on this nanocrystal bilayer tandem catalyst.

Submergible torch for treating waste solutions and method thereof

DOEpatents

Mattus, A.J.

1994-12-06

A submergible torch is described for removing nitrate and/or nitrite ions from a waste solution containing nitrate and/or nitrite ions comprises: a torch tip, a fuel delivery mechanism, a fuel flow control mechanism, a catalyst, and a combustion chamber. The submergible torch is ignited to form a flame within the combustion chamber of the submergible torch. The torch is submerged in a waste solution containing nitrate and/or nitrite ions in such a manner that the flame is in contact with the waste solution and the catalyst and is maintained submerged for a period of time sufficient to decompose the nitrate and/or nitrite ions present in the waste solution. 2 figures.

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

Xing, Rong; Dagle, Vanessa Lebarbier; Flake, Matthew

In this study we examine feasibility for steam reforming the mixed oxygenate aqueous fraction derived from mildly hydrotreated fast pyrolysis bio-oils. Catalysts selective towards hydrogen formation and resistant to carbon formation utilizing feeds with relatively low steam-to-carbon (S/C) ratios are desired. Rh (5 wt%), Pt (5 wt%), Ru (5 wt%), Ir (5 wt%), Ni (15 wt%), and Co (15 wt%) metals supported on MgAl 2O 4 were evaluated for catalytic performance at 500°C and 1 atm using a complex feed mixture comprising of acids, polyols, cycloalkanes, and phenolic compounds. The Rh catalyst was found to be the most active andmore » resistant to carbon formation. The Ni and Co catalysts were found to be more active than the other noble metal catalysts investigated (Pt, Ru, and Ir). However, Ni was found to form significantly more carbon (coke) on the catalyst surface. Furthermore, Co was found to be the most selective towards H 2 formation. Evaluating the effect of temperature on stability for the Rh catalyst we found that catalyst stability was best when operated at 500°C as compared to the higher temperatures investigated (700, 800°C). When operating at 700°C significantly more graphitic formation was observed on the spent catalyst surface. Operating at 800°C resulted in reactor plugging as a result of thermal decomposition of the reactants. Thus, a concept analogous to the petroleum industries’ use of a pre-reformer, operated at approximately 500°C for steam reforming of the heavier naphtha components, followed by a high temperature methane reforming operated in the 600-850°C temperature range, could be applied in the case of steam reforming biomass derived oxygenates. Moreover, stability evaluations were performed over the Rh, Ni, and Co catalysts at 500°C and 1 atm, under similar initial conversions, reveal the Co catalyst to be the most stable and selective towards H 2 production. Conversion and selectivity to CH 4 over Co remained relatively stable at approximately 80% and 1.2%, respectively. By contrast, the Rh and Ni catalysts CH 4 selectivity’s were approximately 7-8%. Thus suggesting that a Co type catalyst may be more suitable for the steam reforming of biomass derived oxygenates as compared to the more conventional Ni and Rh type steam reforming catalysts. However, deposition of carbon on the surface was observed. High resolution TEM on the spent catalysts revealed the formation of graphitic carbon on the Rh catalyst, and filamentous carbon formation was observed on both the Ni and Co catalysts, albeit less pronounced on Co. Thus there is certainly opportunity for improvement in Co catalyst design and/or with process optimization.« less

Calorimetric Thermoelectric Gas Sensor for the Detection of Hydrogen, Methane and Mixed Gases

PubMed Central

Park, Nam-Hee; Akamatsu, Takafumi; Itoh, Toshio; Izu, Noriya; Shin, Woosuck

2014-01-01

A novel miniaturized calorimeter-type sensor device with a dual-catalyst structure was fabricated by integrating different catalysts on the hot (Pd/θ-Al2O3) and cold (Pt/α-Al2O3) ends of the device. The device comprises a calorimeter with a thermoelectric gas sensor (calorimetric-TGS), combining catalytic combustion and thermoelectric technologies. Its response for a model fuel gas of hydrogen and methane was investigated with various combustor catalyst compositions. The calorimetric-TGS devices detected H2, CH4, and a mixture of the two with concentrations ranging between 200 and 2000 ppm at temperatures of 100–400 °C, in terms of the calorie content of the gases. It was necessary to reduce the much higher response voltage of the TGS to H2 compared to CH4. We enhanced the H2 combustion on the cold side so that the temperature differences and response voltages to H2 were reduced. The device response to H2 combustion was reduced by 50% by controlling the Pt concentration in the Pt/α-Al2O3 catalyst on the cold side to 3 wt%. PMID:24818660

A Systematic Investigation of Quaternary Ammonium Ions as Asymmetric Phase Transfer Catalysts. Synthesis of Catalyst Libraries and Evaluation of Catalyst Activity

PubMed Central

Denmark, Scott E.; Gould, Nathan D.; Wolf, Larry M.

2011-01-01

Despite over three decades of research into asymmetric phase transfer catalysis (APTC), a fundamental understanding of the factors that affect the rate and stereoselectivity of this important process are still obscure. This paper describes the initial stages of a long-term program aimed at elucidating the physical organic foundations of APTC employing a chemoinformatic analysis of the alkylation of a protected glycine imine with a libraries of enantiomerically enriched quaternary ammonium ions. The synthesis of the quaternary ammonium ions follows a diversity oriented approach wherein the tandem inter[4+2]/intra[3+2] cycloaddition of nitroalkenes serves as the key transformation. A two part synthetic strategy comprised of: (1) preparation of enantioenriched scaffolds and (2) development of parallel synthesis procedures is described. The strategy allows for the facile introduction of four variable groups in the vicinity of a stereogenic quaternary ammonium ion. The quaternary ammonium ions exhibited a wide range of activity and to a lesser degree enantioselectivity. Catalyst activity and selectivity are rationalized in a qualitative way based on the effective positive potential of the ammonium ion. PMID:21446721

Method of making alkyl esters

DOEpatents

Elliott, Brian

2010-09-14

Methods of making alkyl esters are described herein. The methods are capable of using raw, unprocessed, low-cost feedstocks and waste grease. Generally, the method involves converting a glyceride source to a fatty acid composition and esterifying the fatty acid composition to make alkyl esters. In an embodiment, a method of making alkyl esters comprises providing a glyceride source. The method further comprises converting the glyceride source to a fatty acid composition comprising free fatty acids and less than about 1% glyceride by mass. Moreover, the method comprises esterifying the fatty acid composition in the presence of a solid acid catalyst at a temperature ranging firm about 70.degree. C. to about 120.degree. C. to produce alkyl esters, such that at least 85% of the free fatty acids are converted to alkyl esters. The method also incorporates the use of packed bed reactors for glyceride conversion and/or fatty acid esterification to make alkyl esters.

Method and system for capturing carbon dioxide and/or sulfur dioxide from gas stream

DOEpatents

Chang, Shih-Ger; Li, Yang; Zhao, Xinglei

2014-07-08

The present invention provides a system for capturing CO.sub.2 and/or SO.sub.2, comprising: (a) a CO.sub.2 and/or SO.sub.2 absorber comprising an amine and/or amino acid salt capable of absorbing the CO.sub.2 and/or SO.sub.2 to produce a CO.sub.2- and/or SO.sub.2-containing solution; (b) an amine regenerator to regenerate the amine and/or amino acid salt; and, when the system captures CO.sub.2, (c) an alkali metal carbonate regenerator comprising an ammonium catalyst capable catalyzing the aqueous alkali metal bicarbonate into the alkali metal carbonate and CO.sub.2 gas. The present invention also provides for a system for capturing SO.sub.2, comprising: (a) a SO.sub.2 absorber comprising aqueous alkali metal carbonate, wherein the alkali metal carbonate is capable of absorbing the SO.sub.2 to produce an alkali metal sulfite/sulfate precipitate and CO.sub.2.

Methods of making membrane electrode assemblies

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

Kim, Yu Seung; Lee, Kwan -Soo; Rockward, Tommy Q. T.

Method of making a membrane electrode assembly comprising: providing a membrane comprising a perfluorinated sulfonic acid; providing a first transfer substrate; applying to a surface of the first transfer substrate a first ink, said first ink comprising an ionomer and a catalyst; applying to the first ink a suitable non-aqueous swelling agent; forming an assembly comprising: the membrane; and the first transfer substrate, wherein the surface of the first transfer substrate comprising the first ink and the non-aqueous swelling agent is disposed upon one surface of the membrane; and heating the assembly at a temperature of 150.degree. C. or lessmore » and at a pressure of from about 250 kPa to about 3000 kPa or less for a time suitable to allow substantially complete transfer of the first ink and the second ink to the membrane; and cooling the assembly to room temperature and removing the first transfer substrate and the second transfer substrate.« less

Catalysts and methods for ring opening metathesis polymerization

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

Schrock, Richard Royce; Autenrieth, Benjamin

The present invention, among other things, provides highly syndiotactic poly(dicyclopentadiene) and/or hydrogenated poly(dicyclopentadiene), compositions thereof, and compounds and methods for preparing the same. In some embodiments, a provided compound is a compound of formula I, II or III. In some embodiments, a provided method comprises providing a compound of formula I, II or III.

Surface functionalization of metal-organic polyhedron for homogeneous cyclopropanation catalysis.

PubMed

Lu, Weigang; Yuan, Daqiang; Yakovenko, Andrey; Zhou, Hong-Cai

2011-05-07

A super-paddlewheel (comprised of two paddlewheels) metal-organic polyhedron (MOP) containing surface hydroxyl groups was synthesized and characterized. Condensation reactions with linear alkyl anhydrides lead to new MOPs with enhanced solubility. As a result, the surface-modified MOP 4 was demonstrated as a homogeneous Lewis-acid catalyst. © The Royal Society of Chemistry 2011

Pursuing the Human Side of Driving. A Senior Grade Level Driver Education Refresher Course Curriculum.

ERIC Educational Resources Information Center

Bradley, David L.; Sorte, Bruce M.

Designed for high school seniors, this supplemental traffic safety program serves as a catalyst for discussion and learning in the area of affective education and safe and responsible driving. The guide is comprised of seven instructional units: (1) Orientation; (2) Communication Skills; (3) Skillful Decision Maker and Why; (4) Recognizing…

Catalyst support of mixed cerium zirconium titanium oxide, including use and method of making

DOEpatents

Willigan, Rhonda R [Manchester, CT; Vanderspurt, Thomas Henry [Glastonbury, CT; Tulyani, Sonia [Manchester, CT; Radhakrishnan, Rakesh [Vernon, CT; Opalka, Susanne Marie [Glastonbury, CT; Emerson, Sean C [Broad Brook, CT

2011-01-18

A durable catalyst support/catalyst is capable of extended water gas shift operation under conditions of high temperature, pressure, and sulfur levels. The support is a homogeneous, nanocrystalline, mixed metal oxide of at least three metals, the first being cerium, the second being Zr, and/or Hf, and the third importantly being Ti, the three metals comprising at least 80% of the metal constituents of the mixed metal oxide and the Ti being present in a range of 5% to 45% by metals-only atomic percent of the mixed metal oxide. The mixed metal oxide has an average crystallite size less than 6 nm and forms a skeletal structure with pores whose diameters are in the range of 4-9 nm and normally greater than the average crystallite size. The surface area of the skeletal structure per volume of the material of the structure is greater than about 240 m.sup.2/cm.sup.3. The method of making and use are also described.

Ketonization of levulinic acid and γ-valerolactone to hydrocarbon fuel precursors

DOE PAGES

Lilga, Michael A.; Padmaperuma, Asanga B.; Auberry, Deanna L.; ...

2017-06-21

We studied a new process for direct conversion of either levulinic acid (LA) or γ-valerolactone (GVL) to hydrocarbon fuel precursors. The process involves passing an aqueous solution of LA or GVL containing a reducing agent, such as ethylene glycol or formic acid, over a ketonization catalyst at 380–400 °C and atmospheric pressure to form a biphasic liquid product. The organic phase is significantly oligomerized and deoxygenated and comprises a complex mixture of open-chain alkanes and olefins, aromatics, and low concentrations of ketones, alcohols, ethers, and carboxylates or lactones. Carbon content in the aqueous phase decreases with decreasing feed rate; themore » aqueous phase can be reprocessed through the same catalyst to form additional organic oils to improve carbon yield. Catalysts are readily regenerated to restore initial activity. Furthermore, the process might be valuable in converting cellulosics to biorenewable gasoline, jet, and diesel fuels as a means to decrease petroleum use and decrease greenhouse gas emissions.« less

Electrode kinetics of ethanol oxidation on novel CuNi alloy supported catalysts synthesized from PTFE suspension

NASA Astrophysics Data System (ADS)

Sen Gupta, S.; Datta, J.

An understanding of the kinetics and mechanism of the electrochemical oxidation of ethanol is of considerable interest for the optimization of the direct ethanol fuel cell. In this paper, the electro-oxidation of ethanol in sodium hydroxide solution has been studied over 70:30 CuNi alloy supported binary platinum electrocatalysts. These comprised mixed deposits of Pt with Ru or Mo. The electrodepositions were carried out under galvanostatic condition from a dilute suspension of polytetrafluoroethylene (PTFE) containing the respective metal salts. Characterization of the catalyst layers by scanning electron microscope (SEM)-energy dispersive X-ray (EDX) indicated that this preparation technique yields well-dispersed catalyst particles on the CuNi alloy substrate. Cyclic voltammetry, polarization study and electrochemical impedance spectroscopy were used to investigate the kinetics and mechanism of ethanol electro-oxidation over a range of NaOH and ethanol concentrations. The relevant parameters such as Tafel slope, charge transfer resistance and the reaction orders in respect of OH - ions and ethanol were determined.

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.

Atomic level study of water-gas shift catalysts via transmission electron microscopy and x-ray spectroscopy

NASA Astrophysics Data System (ADS)

Akatay, Mehmed Cem

Water-gas shift (WGS), CO + H2O ⇆ CO2 + H2 (DeltaH° = -41 kJ mol -1), is an industrially important reaction for the production of high purity hydrogen. Commercial Cu/ZnO/Al2O3 catalysts are employed to accelerate this reaction, yet these catalysts suffer from certain drawbacks, including costly regeneration processes and sulfur poisoning. Extensive research is focused on developing new catalysts to replace the current technology. Supported noble metals stand out as promising candidates, yet comprise intricate nanostructures complicating the understanding of their working mechanism. In this study, the structure of the supported Pt catalysts is explored by transmission electron microscopy and X-ray spectroscopy. The effect of the supporting phase and the use of secondary metals on the reaction kinetics is investigated. Structural heterogeneities are quantified and correlated with the kinetic descriptors of the catalysts to develop a fundamental understanding of the catalytic mechanism. The effect of the reaction environment on catalyst structure is examined by in-situ techniques. This study benefitted greatly from the use of model catalysts that provide a convenient medium for the atomic level characterization of nanostructures. Based on these studies, Pt supported on iron oxide nano islands deposited on inert spherical alumina exhibited 48 times higher WGS turnover rate (normalized by the total Pt surface area) than Pt supported on bulk iron oxide. The rate of aqueous phase glycerol reforming reaction of Pt supported on multiwall carbon nanotubes (MWCNT) is promoted by co-impregnating with cobalt. The synthesis resulted in a variety of nanostructures among which Pt-Co bimetallic nanoparticles are found to be responsible for the observed promotion. The unprecedented WGS rate of Pt supported on Mo2C is explored by forming Mo 2C patches on top of MWCNTs and the rate promotion is found to be caused by the Pt-Mo bimetallic entities.

Oxidation resistant organic hydrogen getters

DOEpatents

Shepodd, Timothy J [Livermore, CA; Buffleben, George M [Tracy, CA

2008-09-09

A composition for removing hydrogen from an atmosphere, comprising a mixture of a polyphenyl ether and a hydrogenation catalyst, preferably a precious metal catalyst, and most preferably Pt. This composition is stable in the presence of oxygen, will not polymerize or degrade upon exposure to temperatures in excess of 200.degree. C., or prolonged exposure to temperatures in the range of 100-300.degree. C. Moreover, these novel hydrogen getter materials can be used to efficiently removing hydrogen from mixtures of hydrogen/inert gas (e.g., He, Ar, N.sub.2), hydrogen/ammonia atmospheres, such as may be encountered in heat exchangers, and hydrogen/carbon dioxide atmospheres. Water vapor and common atmospheric gases have no adverse effect on the ability of these getter materials to absorb hydrogen.

Ruthenium-Catalyzed Aerobic Oxidation of Amines.

PubMed

Ray, Ritwika; Hazari, Arijit Singha; Lahiri, Goutam Kumar; Maiti, Debabrata

2018-01-18

Amine oxidation is one of the fundamental reactions in organic synthesis as it leads to a variety of value-added products such as oximes, nitriles, imines, and amides among many others. These products comprise the key N-containing building blocks in the modern chemical industry, and such transformations, when achieved in the presence of molecular oxygen without using stoichiometric oxidants, are much preferred as they circumvent the production of unwanted wastes. In parallel, the versatility of ruthenium catalysts in various oxidative transformations is well-documented. Herein, this review focuses on aerobic oxidation of amines specifically by using ruthenium catalysts and highlights the major achievements in this direction and challenges that still need to be addressed. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Method to convert biomass to 5-(hydroxymethyl)-furfural (HMF) and furfural using lactones, furans, and pyrans as solvents

DOEpatents

Dumesic, James A.; Ribeiro Gallo, Jean Marcel; Alonso, David

2014-07-08

Described is a process to produce hydroxymethyl furfural (HMF) from biomass-derived sugars. The process includes the steps of reacting a C5 and/or C6 sugar-containing reactant derived from biomass in a monophasic or biphasic reaction solution comprising water and a co-solvent. The co-solvent can be beta-, gamma-, and/or delta-lactones derived from biomass, tetrahydrofuran (THF) derived from biomass, and/or methyltetrahydrofuran (MTHF) derived from biomass. The reaction takes place in the presence of an acid catalyst and a dehydration catalyst for a time and under conditions such that at least a portion of glucose or fructose present in the reactant is converted to HMF.

Simultaneous removal of nitrogen oxides and sulfur oxides from combustion gases

DOEpatents

Clay, David T.; Lynn, Scott

1976-10-19

A process for the simultaneous removal of sulfur oxides and nitrogen oxides from power plant stack gases comprising contacting the stack gases with a supported iron oxide catalyst/absorbent in the presence of sufficient reducing agent selected from the group consisting of carbon monoxide, hydrogen, and mixtures thereof, to provide a net reducing atmosphere in the SO.sub.x /NO.sub.x removal zone. The sulfur oxides are removed by absorption substantially as iron sulfide, and nitrogen oxides are removed by catalytic reduction to nitrogen and ammonia. The spent iron oxide catalyst/absorbent is regenerated by oxidation and is recycled to the contacting zone. Sulfur dioxide is also produced during regeneration and can be utilized in the production of sulfuric acid and/or sulfur.

Process for hydrogen isotope concentration between liquid water and hydrogen gas

DOEpatents

Stevens, William H.

1976-09-21

A process for hydrogen isotope exchange and concentration between liquid water and hydrogen gas, wherein liquid water and hydrogen gas are contacted, in an exchange section, with one another and with at least one catalyst body comprising at least one metal selected from Group VIII of the Periodic Table and preferably a support therefor, the catalyst body has a liquid-water-repellent, gas permeable polymer or organic resin coating, preferably a fluorinated olefin polymer or silicone coating, so that the isotope concentration takes place by two simultaneously occurring steps, namely, ##EQU1## WHILE THE HYDROGEN GAS FED TO THE EXCHANGE SECTION IS DERIVED IN A REACTOR VESSEL FROM LIQUID WATER THAT HAS PASSED THROUGH THE EXCHANGE SECTION.

Deepening Understanding of "Pedagogical Outcomes" through Video Data Collection: A Catalyst for Guided Reflective Learning Conversations

ERIC Educational Resources Information Center

Dann, Chris; Richardson, Tony

2015-01-01

This article examines the case of Catch Me Excel (CeMeE), an electronic feedback system developed to facilitate video, image and written feedback in the workplace to educators about pedagogical-related outcomes. It comprises a sophisticated, technological feedback system of which the resultant data can be used to enhance classroom, schools and…

Dialing in single-site reactivity of a supported calixarene-protected tetrairidium cluster catalyst

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

Palermo, Andrew; Solovyov, Andrew; Ertler, Daniel

2017-05-04

A closed Ir 4carbonyl cluster,1, comprising a tetrahedral metal frame and threetert-butyl-calix[4]arene(OPr) 3(OCH 2PPh 2) (Ph = phenyl; Pr = propyl) ligands at the basal plane, was silica supported and consists of “*” and “S” sites, which could be dialed in selectively for controlling ethylene hydrogenation catalysis.

Pd@Pt Core–Shell Nanoparticles with Branched Dandelion-like Morphology as Highly Efficient Catalysts for Olefin Reduction

EPA Science Inventory

A facile synthesis based on the addition of ascorbic acid to a mixture of Na2PdCl4, K2PtCl6, and Pluronic P123 results in highly branched core–shell nanoparticles (NPs) with a micro–mesoporous dandelion-like morphology comprising Pd core and Pt shell. The slow reduction kinetics ...

Purification of crude glycerol from transesterification reaction of palm oil using direct method and multistep method

NASA Astrophysics Data System (ADS)

Nasir, N. F.; Mirus, M. F.; Ismail, M.

2017-09-01

Crude glycerol which produced from transesterification reaction has limited usage if it does not undergo purification process. It also contains excess methanol, catalyst and soap. Conventionally, purification method of the crude glycerol involves high cost and complex processes. This study aimed to determine the effects of using different purification methods which are direct method (comprises of ion exchange and methanol removal steps) and multistep method (comprises of neutralization, filtration, ion exchange and methanol removal steps). Two crude glycerol samples were investigated; the self-produced sample through the transesterification process of palm oil and the sample obtained from biodiesel plant. Samples were analysed using Fourier Transform Infrared Spectroscopy, Gas Chromatography and High Performance Liquid Chromatography. The results of this study for both samples after purification have showed that the pure glycerol was successfully produced and fatty acid salts were eliminated. Also, the results indicated the absence of methanol in both samples after purification process. In short, the combination of 4 purification steps has contributed to a higher quality of glycerol. Multistep purification method gave a better result compared to the direct method as neutralization and filtration steps helped in removing most excess salt, fatty acid and catalyst.

The Investigation and Development of Low Cost Hardware Components for Proton-Exchange Membrane Fuel Cells - Final Report

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

George A. Marchetti

1999-12-15

Proton exchange membrane (PEM) fuel cell components, which would have a low-cost structure in mass production, were fabricated and tested. A fuel cell electrode structure, comprising a thin layer of graphite (50 microns) and a front-loaded platinum catalyst layer (600 angstroms), was shown to produce significant power densities. In addition, a PEM bipolar plate, comprising flexible graphite, carbon cloth flow-fields and an integrated polymer gasket, was fabricated. Power densities of a two-cell unit using this inexpensive bipolar plate architecture were shown to be comparable to state-of-the-art bipolar plates.

Process for the conversion of lower alcohols to higher branched oxygenates

DOEpatents

Barger, Paul T.

1996-01-01

A process is provided for the production of branched C.sub.4+ oxygenates from lower alcohols such as methanol, ethanol, propanol and mixtures thereof. The process comprises contacting the lower alcohols with a solid catalyst comprising a mixed metal oxide support having components selected from the group consisting of oxides of zinc, magnesium, zirconia, titanium, manganese, chromium, and lanthanides, and an activation metal selected from the group consisting of Group VIII metal, Group IB metals, and mixtures thereof. The advantage of the process is improved yields and selectivity to isobutanol which can subsequently be employed in the production of high octane motor gasoline.

Process for the conversion of lower alcohols to higher branched oxygenates

DOEpatents

Barger, P.T.

1996-09-24

A process is provided for the production of branched C{sub x} oxygenates from lower alcohols such as methanol, ethanol, propanol and mixtures thereof. The process comprises contacting the lower alcohols with a solid catalyst comprising a mixed metal oxide support having components selected from the group consisting of oxides of zinc, magnesium, zirconia, titanium, manganese, chromium, and lanthanides, and an activation metal selected from the group consisting of Group VIII metal, Group IB metals, and mixtures thereof. The advantage of the process is improved yields and selectivity to isobutanol which can subsequently be employed in the production of high octane motor gasoline.

Valorization of Lignin to Simple Phenolic Compounds over Tungsten Carbide: Impact of Lignin Structure.

PubMed

Guo, Haiwei; Zhang, Bo; Qi, Zaojuan; Li, Changzhi; Ji, Jianwei; Dai, Tao; Wang, Aiqin; Zhang, Tao

2017-02-08

Lignins isolated from representative hardwood, softwood, and grass materials were effectively hydrocracked to aromatics catalyzed by tungsten carbide over activated carbon (W 2 C/AC). The effects of botanical species and fractionation methods on lignin structure and the activity of W 2 C/AC were studied in detail. Gas permeation chromatography (GPC), FTIR, elemental analysis, and 2 D HSQC NMR showed that all the extracted samples shared the basic skeleton of lignin, whereas the fractionation method significantly affected the structure. The organosolv process provided lignin with a structure more similar to the native lignin, which was labile to be depolymerized by W 2 C/AC. Softwood lignins (i.e., spruce and pine) possessed higher molecular weights than hardwood lignins (i.e., poplar and basswood); whereas corn stalk lignin that has noncanonical subunits and exhibited the lowest molecular weight owing to its shorter growth period. β-O-4 bonds were the major linkages in all lignin samples, whereas softwood lignins contained more resistant linkages of β-5 and less β-β than corn stalk and hardwood lignins; as a result, lowest hydrocracking efficiency was obtained in softwood lignins, followed by corn stalk and hardwood lignins. 2 D HSQC NMR spectra of lignin and the liquid oil as well as the solid residue showed that W 2 C/AC exhibited high activity not only in β-O-4 cleavage, but also in deconstruction of other ether linkages between aromatic units, so that high yield of liquid oil was obtained from lignin. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis of Ultra-Small Palladium Nanoparticles Deposited on CdS Nanorods by Pulsed Laser Ablation in Liquid: Role of Metal Nanocrystal Size in the Photocatalytic Hydrogen Production.

PubMed

Park, Hanbit; Reddy, D Amaranatha; Kim, Yujin; Lee, Seunghee; Ma, Rory; Kim, Tae Kyu

2017-09-21

It is imperative to suppress the rate of recombination of photogenerated carriers to improve the semiconductor-catalyzed solar-driven production of hydrogen. To this end, photocatalysts comprising active sunlight-harvesting photo-absorbers and stable metal co-catalysts have attracted significant attention. However, the size, clean surface, and highly dispersed nature of the metal co-catalysts are crucial factors affecting catalyst performance and reaction rate. Nevertheless, most of the available metal nanocrystals have been synthesized by complex procedures using harmful organic templates and stabilizers, affording high-purity compounds with difficulty and high cost. To overcome these problems, in this study, the pulsed laser ablation in liquid approach was utilized to generate palladium and bimetallic palladium-platinum nanoparticles with an average size and distribution by adjusting the laser wavelength and fluence. A high rate of evolution of hydrogen of 130.33 mmol g -1  h -1 was obtained by using the optimized CdS-PdPt catalyst under simulated sunlight irradiation. This value is 51.31 times greater than that observed for bare CdS nanostructures. Furthermore, the amount of hydrogen evolved was significantly better than that obtained by using several other noble-metal co-catalysts deposited on CdS. This proposed strategy is thought to open new avenues for the design of advanced photocatalytic materials for efficient solar-driven production of hydrogen. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Photocatalytic Conversion of CO2 to CO by a Copper(II) Quaterpyridine Complex.

PubMed

Guo, Zhenguo; Yu, Fei; Yang, Ying; Leung, Chi-Fai; Ng, Siu-Mui; Ko, Chi-Chiu; Cometto, Claudio; Lau, Tai-Chu; Robert, Marc

2017-10-23

The invention of efficient systems for the photocatalytic reduction of CO 2 comprising earth-abundant metal catalysts is a promising approach for the production of solar fuels. One bottleneck is to design highly selective and robust molecular complexes that are able to transform the CO 2 gas. The Cu II quaterpyridine complex [Cu(qpy)] 2+ (1) is found to be a highly efficient and selective catalyst for visible-light driven CO 2 reduction in CH 3 CN using [Ru(bpy) 3 ] 2+ (bpy: bipyridine) as photosensitizer and BIH/TEOA (1,3-dimethyl-2-phenyl-2,3-dihydro-1H-benzo[d]imidazole/triethanolamine) as sacrificial reductant. The photocatalytic reaction is greatly enhanced by the presence of H 2 O (1-4 % v/v), and a turnover number of >12 400 for CO production can be achieved with 97 % selectivity, which is among the highest of molecular 3d CO 2 reduction catalysts. Results from Hg poisoning and dynamic light scattering experiments suggest that this photocatalyst is homogenous. To the best of our knowledge, 1 is the first example of molecular Cu-based catalyst for the photoreduction of CO 2 . © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Co3O4 nanowires as efficient catalyst precursor for hydrogen generation from sodium borohydride hydrolysis

NASA Astrophysics Data System (ADS)

Wei, Lei; Cao, Xurong; Ma, Maixia; Lu, Yanhong; Wang, Dongsheng; Zhang, Suling; Wang, Qian

Hydrogen generation from the catalytic hydrolysis of sodium borohydride has many advantages, and therefore, significant research has been undertaken on the development of highly efficient catalysts for this purpose. In our present work, Co3O4 nanowires were successfully synthesized as catalyst precursor by employing SBA-15 as a hard template. For material characterization, high-resolution transmission electron microscopy (HRTEM), powder X-ray diffraction (XRD), fourier-transform infrared spectroscopy (FT-IR), thermogravimetric analysis (TGA), inductively coupled plasma-atomic emission spectroscopy (ICP-AES) and N2 adsorption isotherms were employed, respectively. To measure the catalyst activity, typical water-displacement method was carried out. Using a reaction solution comprising 10wt.% NaBH4 and 2wt.% NaOH, the hydrogen generation rate (HGR) was observed to be as high as 7.74L min-1 g-1 at 25∘C in the presence of Co3O4 nanowires, which is significantly higher than that of CoB nanoparticles and commercial Co3O4 powder. Apparent activation energy was calculated to be 50.9kJ mol-1. After recycling the Co3O4 nanowires six times, HGR was decreased to be 72.6% of the initial level.

High performance robust F-doped tin oxide based oxygen evolution electro-catalysts for PEM based water electrolysis

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

Datta, Moni Kanchan; Kadakia, Karan; Velikokhatnyi, Oleg I

2013-01-01

Identification and development of non-noble metal based electro-catalysts or electro-catalysts comprising compositions with significantly reduced amounts of expensive noble metal contents (e.g. IrO{sub 2}, Pt) with comparable electrochemical performance to the standard noble metal/metal oxide for proton exchange membrane (PEM) based water electrolysis would signify a major breakthrough in hydrogen generation via water electrolysis. Development of such systems would lead to two primary outcomes: first, a reduction in the overall capital costs of PEM based water electrolyzers, and second, attainment of the targeted hydrogen production costs (<$3.00/gge delivered by 2015) comparable to conventional liquid fuels. In line with these goals,more » by exploiting a two-pronged theoretical first principles and experimental approach herein, we demonstrate for the very first time a solid solution of SnO{sub 2}:10 wt% F containing only 20 at.% IrO{sub 2} [e.g. (Sn{sub 0.80}Ir{sub 0.20})O{sub 2}:10F] displaying remarkably similar electrochemical activity and comparable or even much improved electrochemical durability compared to pure IrO{sub 2}, the accepted gold standard in oxygen evolution electro-catalysts for PEM based water electrolysis. We present the results of these studies.« less

Processing real-world waste plastics by pyrolysis-reforming for hydrogen and high-value carbon nanotubes.

PubMed

Wu, Chunfei; Nahil, Mohamad A; Miskolczi, Norbert; Huang, Jun; Williams, Paul T

2014-01-01

Producing both hydrogen and high-value carbon nanotubes (CNTs) derived from waste plastics is reported here using a pyrolysis-reforming technology comprising a two-stage reaction system, in the presence of steam and a Ni-Mn-Al catalyst. The waste plastics consisted of plastics from a motor oil container (MOC), commercial waste high density polyethylene (HDPE) and regranulated HDPE waste containing polyvinyl chloride (PVC). The results show that hydrogen can be produced from the pyrolysis-reforming process, but also carbon nanotubes are formed on the catalyst. However, the content of 0.3 wt.% polyvinyl chloride in the waste HDPE (HDPE/PVC) has been shown to poison the catalyst and significantly reduce the quantity and purity of CNTs. The presence of sulfur has shown less influence on the production of CNTs in terms of quantity and CNT morphologies. Around 94.4 mmol H2 g(-1) plastic was obtained for the pyrolysis-reforming of HDPE waste in the presence of the Ni-Mn-Al catalyst and steam at a reforming temperature of 800 °C. The addition of steam in the process results in an increase of hydrogen production and reduction of carbon yield; in addition, the defects of CNTs, for example, edge dislocations were found to be increased with the introduction of steam (from Raman analysis).

Solar photocatalysis for treatment of Acid Yellow-17 (AY-17) dye contaminated water using Ag@TiO2 core-shell structured nanoparticles.

PubMed

Khanna, Ankita; Shetty K, Vidya

2013-08-01

Wastewater released from textile industries causes water pollution, and it needs to be treated before discharge to the environment by cost effective technologies. Solar photocatalysis is a promising technology for the treatment of dye wastewater. The Ag@TiO2 nanoparticles comprising of Ag core and TiO2 shell (Ag@TiO2) have unique photocatalytic property of inhibition of electron-hole recombination and visible light absorption, which makes it a promising photocatalyst for use in solar photocatalysis and with higher photocatalytic rate. Therefore, in the present work, the Ag@TiO2 nanoparticles synthesized by one pot method with postcalcination step has been used for the degradation of Acid Yellow-17 (AY-17) dye under solar light irradiation. The Ag@TiO2 nanoparticles were characterized using thermogravimetric-differential thermal analysis, X-ray diffraction, transmission electron microscopy, selected area electron diffraction, and energy dispersive X-ray analysis. The catalyst has been found to be very effective in solar photocatalysis of AY-17, as compared to other catalysts. The effects of pH, catalyst loading, initial dye concentration, and oxidants on photocatalysis were also studied. The optimized parameters for degradation of AY-17 using Ag@TiO2 were found to be pH 3, dye/catalyst ratio of 1:10 (g/g), and 2 g/L of (NH4)2S2O8 as oxidant. Efficient decolorization and mineralization of AY-17 was achieved. The kinetics of color, total organic carbon, and chemical oxygen demand removal followed the Langmuir-Hinshelwood model. Ag@TiO2 catalyst can be reused thrice without much decline in efficiency. The catalyst exhibited its potential as economic photocatalyst for treatment of dye wastewater.

Process for detoxifying coal tars

DOEpatents

Longwell, John P.; Peters, William A.

1983-01-01

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

Methods for deoxygenating biomass-derived pyrolysis oil

DOEpatents

Brandvold, Timothy A.

2015-07-14

Methods for deoxygenating a biomass-derived pyrolysis oil are provided. A method comprising the steps of diluting the biomass-derived pyrolysis oil with a phenolic-containing diluent to form a diluted pyoil-phenolic feed is provided. The diluted pyoil-phenolic feed is contacted with a deoxygenating catalyst in the presence of hydrogen at hydroprocessing conditions effective to form a low-oxygen biomass-derived pyrolysis oil effluent.

Upper Stage Flight Experiment 10K Engine Design and Test Results

NASA Technical Reports Server (NTRS)

Ross, R.; Morgan, D.; Crockett, D.; Martinez, L.; Anderson, W.; McNeal, C.

2000-01-01

A 10,000 lbf thrust chamber was developed for the Upper Stage Flight Experiment (USFE). This thrust chamber uses hydrogen peroxide/JP-8 oxidizer/fuel combination. The thrust chamber comprises an oxidizer dome and manifold, catalyst bed assembly, fuel injector, and chamber/nozzle assembly. Testing of the engine was done at NASA's Stennis Space Center (SSC) to verify its performance and life for future upper stage or Reusable Launch Vehicle applications. Various combinations of silver screen catalyst beds, fuel injectors, and combustion chambers were tested. Results of the tests showed high C* efficiencies (97% - 100%) and vacuum specific impulses of 275 - 298 seconds. With fuel film cooling, heating rates were low enough that the silica/quartz phenolic throat experienced minimal erosion. Mission derived requirements were met, along with a perfect safety record.

Method for absorbing hydrogen using an oxidation resisant organic hydrogen getter

DOEpatents

Shepodd, Timothy J [Livermore, CA; Buffleben, George M [Tracy, CA

2009-02-03

A composition for removing hydrogen from an atmosphere, comprising a mixture of a polyphenyl ether and a hydrogenation catalyst, preferably a precious metal catalyst, and most preferably platinum, is disclosed. This composition is stable in the presence of oxygen, will not polymerize or degrade upon exposure to temperatures in excess of 200.degree. C., or prolonged exposure to temperatures in the range of 100-300.degree. C. Moreover, these novel hydrogen getter materials can be used to efficiently remove hydrogen from mixtures of hydrogen/inert gas (e.g., He, Ar, N.sub.2), hydrogen/ammonia atmospheres, such as may be encountered in heat exchangers, and hydrogen/carbon dioxide atmospheres. Water vapor and common atmospheric gases have no adverse effect on the ability of these getter materials to absorb hydrogen.

Cermet anode with continuously dispersed alloy phase and process for making

DOEpatents

Marschman, Steven C.; Davis, Norman C.

1989-01-01

Cermet electrode compositions and methods for making are disclosed which comprise NiO--NiFe.sub.2 O.sub.4 --Cu--Ni. Addition of an effective amount of a metallic catalyst/reactant to a composition of a nickel/iron/oxide, NiO, copper, and nickel produces a stable electrode having significantly increased electrical conductivity. The metallic catalyst functions to disperse the copper and nickel as an alloy continuously throughout the oxide phase of the cermet to render the electrode compositon more highly electrically conductive than were the third metal not present in the base composition. The third metal is preferably added to the base composition as elemental metal and includes aluminum, magnesium, sodium and gallium. The elemental metal is converted to a metal oxide during the sintering process.

Two-stage coal liquefaction process

DOEpatents

Skinner, Ronald W.; Tao, John C.; Znaimer, Samuel

1985-01-01

An improved SRC-I two-stage coal liquefaction process which improves the product slate is provided. Substantially all of the net yield of 650.degree.-850.degree. F. heavy distillate from the LC-Finer is combined with the SRC process solvent, substantially all of the net 400.degree.-650.degree. F. middle distillate from the SRC section is combined with the hydrocracker solvent in the LC-Finer, and the initial boiling point of the SRC process solvent is increased sufficiently high to produce a net yield of 650.degree.-850.degree. F. heavy distillate of zero for the two-stage liquefaction process.

Identifying Different Types of Catalysts for CO2 Reduction by Ethane through Dry Reforming and Oxidative Dehydrogenation.

PubMed

Porosoff, Marc D; Myint, Myat Noe Zin; Kattel, Shyam; Xie, Zhenhua; Gomez, Elaine; Liu, Ping; Chen, Jingguang G

2015-12-14

The recent shale gas boom combined with the requirement to reduce atmospheric CO2 have created an opportunity for using both raw materials (shale gas and CO2 ) in a single process. Shale gas is primarily made up of methane, but ethane comprises about 10 % and reserves are underutilized. Two routes have been investigated by combining ethane decomposition with CO2 reduction to produce products of higher value. The first reaction is ethane dry reforming which produces synthesis gas (CO+H2 ). The second route is oxidative dehydrogenation which produces ethylene using CO2 as a soft oxidant. The results of this study indicate that the Pt/CeO2 catalyst shows promise for the production of synthesis gas, while Mo2 C-based materials preserve the CC bond of ethane to produce ethylene. These findings are supported by density functional theory (DFT) calculations and X-ray absorption near-edge spectroscopy (XANES) characterization of the catalysts under in situ reaction conditions. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Identifying different types of catalysts for CO 2 reduction by ethane through dry reforming and oxidative dehydrogenation

DOE PAGES

Marc D. Porosoff; Chen, Jingguang G.; Myint, Myat Noe Zin; ...

2015-11-10

In this study, the recent shale gas boom combined with the requirement to reduce atmospheric CO 2 have created an opportunity for using both raw materials (shale gas and CO 2) in a single process. Shale gas is primarily made up of methane, but ethane comprises about 10 % and reserves are underutilized. Two routes have been investigated by combining ethane decomposition with CO 2 reduction to produce products of higher value. The first reaction is ethane dry reforming which produces synthesis gas (CO+H 2). The second route is oxidative dehydrogenation which produces ethylene using CO 2 as a softmore » oxidant. The results of this study indicate that the Pt/CeO 2 catalyst shows promise for the production of synthesis gas, while Mo 2C-based materials preserve the C—C bond of ethane to produce ethylene. These findings are supported by density functional theory (DFT) calculations and X-ray absorption near-edge spectroscopy (XANES) characterization of the catalysts under in situ reaction conditions.« less

Hydrogen storage materials and method of making by dry homogenation

DOEpatents

Jensen, Craig M.; Zidan, Ragaiy A.

2002-01-01

Dry homogenized metal hydrides, in particular aluminum hydride compounds, as a material for reversible hydrogen storage is provided. The reversible hydrogen storage material comprises a dry homogenized material having transition metal catalytic sites on a metal aluminum hydride compound, or mixtures of metal aluminum hydride compounds. A method of making such reversible hydrogen storage materials by dry doping is also provided and comprises the steps of dry homogenizing metal hydrides by mechanical mixing, such as be crushing or ball milling a powder, of a metal aluminum hydride with a transition metal catalyst. In another aspect of the invention, a method of powering a vehicle apparatus with the reversible hydrogen storage material is provided.

Single-reactor process for producing liquid-phase organic compounds from biomass

DOEpatents

Dumesic, James A.; Simonetti, Dante A.; Kunkes, Edward L.

2015-12-08

Disclosed is a method for preparing liquid fuel and chemical intermediates from biomass-derived oxygenated hydrocarbons. The method includes the steps of reacting in a single reactor an aqueous solution of a biomass-derived, water-soluble oxygenated hydrocarbon reactant, in the presence of a catalyst comprising a metal selected from the group consisting of Cr, Mn, Fe, Co, Ni, Cu, Mo, Tc, Ru, Rh, Pd, Ag, W, Re, Os, Ir, Pt, and Au, at a temperature, and a pressure, and for a time sufficient to yield a self-separating, three-phase product stream comprising a vapor phase, an organic phase containing linear and/or cyclic mono-oxygenated hydrocarbons, and an aqueous phase.

Single-reactor process for producing liquid-phase organic compounds from biomass

DOEpatents

Dumesic, James A [Verona, WI; Simonetti, Dante A [Middleton, WI; Kunkes, Edward L [Madison, WI

2011-12-13

Disclosed is a method for preparing liquid fuel and chemical intermediates from biomass-derived oxygenated hydrocarbons. The method includes the steps of reacting in a single reactor an aqueous solution of a biomass-derived, water-soluble oxygenated hydrocarbon reactant, in the presence of a catalyst comprising a metal selected from the group consisting of Cr, Mn, Fe, Co, Ni, Cu, Mo, Tc, Ru, Rh, Pd, Ag, W, Re, Os, Ir, Pt, and Au, at a temperature, and a pressure, and for a time sufficient to yield a self-separating, three-phase product stream comprising a vapor phase, an organic phase containing linear and/or cyclic mono-oxygenated hydrocarbons, and an aqueous phase.

Mild and selective vanadium-catalyzed oxidation of benzylic, allylic, and propargylic alcohols using air

DOEpatents

Hanson, Susan Kloek; Silks, Louis A; Wu, Ruilian

2013-08-27

The invention concerns processes for oxidizing an alcohol to produce a carbonyl compound. The processes comprise contacting the alcohol with (i) a gaseous mixture comprising oxygen; and (ii) an amine compound in the presence of a catalyst, having the formula: ##STR00001## where each of R.sup.1-R.sup.12 are independently H, alkyl, aryl, CF.sub.3, halogen, OR.sup.13, SO.sub.3R.sup.14, C(O)R.sup.15, CONR.sup.16R.sup.17 or CO.sub.2R.sup.18; each of R.sup.13-R.sup.18 is independently alkyl or aryl; and Z is alkl or aryl.