WO2007100333A1 - Nanoparticules d'oxyde de nickel utiles en tant que précurseur de catalyseur pour la production d'hydrogène - Google Patents

Nanoparticules d'oxyde de nickel utiles en tant que précurseur de catalyseur pour la production d'hydrogène Download PDF

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Publication number
WO2007100333A1
WO2007100333A1 PCT/US2006/007688 US2006007688W WO2007100333A1 WO 2007100333 A1 WO2007100333 A1 WO 2007100333A1 US 2006007688 W US2006007688 W US 2006007688W WO 2007100333 A1 WO2007100333 A1 WO 2007100333A1
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Prior art keywords
solution
nickel
catalyst
ions
methane
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PCT/US2006/007688
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English (en)
Inventor
Mei Cai
Yong Li
Wenjie Shen
Jerry Dale Rogers
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General Motors Global Technology Operations, Inc.
Chinese Academy Of Sciences
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Priority to PCT/US2006/007688 priority Critical patent/WO2007100333A1/fr
Publication of WO2007100333A1 publication Critical patent/WO2007100333A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/755—Nickel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
    • B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/031—Precipitation
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/22—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds
    • C01B3/24—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons
    • C01B3/26—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons using catalysts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
    • C01B2203/0277—Processes for making hydrogen or synthesis gas containing a decomposition step containing a catalytic decomposition step
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1047—Group VIII metal catalysts
    • C01B2203/1052—Nickel or cobalt catalysts
    • C01B2203/1058—Nickel catalysts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1205—Composition of the feed
    • C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
    • C01B2203/1235—Hydrocarbons
    • C01B2203/1241—Natural gas or methane

Definitions

  • This invention pertains to the production of hydrogen from the decomposition of methane or other lower molecular weight hydrocarbon gasses. More specifically, this invention pertains to the preparation of nickel oxide nanoparticles as catalyst precursors for stepwise steam reforming of methane.
  • Methane has been decomposed over supported metal catalyst particles at temperatures of about 300 0 C to 500 0 C to produce hydrogen and carbon.
  • a goal of the process is to obtain hydrogen gas uncontaminated with carbon monoxide.
  • Metals such as iron, nickel or palladium deposited as fine particles on high surface area oxides of aluminum, cerium, molybdenum, silicon, thorium or zirconium have been evaluated as catalysts.
  • Certain zeolites have also been used as catalyst supports. Catalysts formed of nickel particles deposited on alumina, ceria, silica, or zirconia supports have attracted attention.
  • the supported catalyst is confined in a heated flow-through reactor and methane, usually diluted with nitrogen, helium or the like, is passed over the catalyst at a suitable space velocity. Some methane decomposes to hydrogen and carbon. Hydrogen exits in the exhaust stream, also containing un-decomposed methane and diluent; and fine carbon particles deposit on the catalyst. Sometimes the metal oxide carrier also promotes the formation of carbon monoxide.
  • the overall process comprises two-steps; hydrogen is produced in step one, and hydrogen and CO 2 are produced in step two.
  • the process has been conducted using two parallel catalytic reactors with one bed catalyzing the decomposition of methane and the other bed being treated with steam for carbon removal and catalyst reactivation.
  • a single bed is alternately and cyclically contacted, first with methane and then with steam, to produce the hydrogen and CO 2 product streams.
  • the methane content of the feed stream is not wholly decomposed and often the product stream contains some CO due to the use of oxygen-containing catalyst supports.
  • This invention provides un-supported, nanometer size, nickel oxide particles as catalyst precursors for carbon monoxide-free methane decomposition at relatively low temperatures of the order of 300 0 C to 500 0 C.
  • the nickel oxide particles are reduced with hydrogen before hydrocarbon decomposition begins.
  • the catalyst particles promote uniformly high conversion levels of methane over prolonged periods before requiring interruption of methane flow for steam oxidation of deposited carbon particles and regeneration of the catalytic activity of the particles.
  • the nanometer size nickel oxide catalyst precursor particles are made using a precipitation process. A compound of nickel is dissolved in a convenient solvent to produce Ni +2 ions.
  • Nickel is precipitated from a stirred solution as a hydroxide or hydrated oxide under conditions that the precipitate can be easily filtered, dried and calcined to form NiO particles of nanometer scale, hi general, it is preferred that the NiO particles have a diameter or major dimension no greater than about ten to fifteen nanometers for methane or lower alkane decomposition to hydrogen and carbon particles.
  • Common nickel (+2) compounds such as nickel chloride, nickel nitrate and nickel acetate are suitable precursors for the formation of NiO particles for methane decomposition and steam regeneration.
  • Inexpensive and convenient bases such as sodium hydroxide or sodium carbonate may be used as the precipitating agent.
  • the base is also used in solution for controlled addition to the precursor solution and the formation of a suitably small particle precipitate for conversion to nickel oxide particles of suitably uniform and small size.
  • the selection of the solvent, the temperature of the solutions, the rate of their mixing and the aging of the precipitate-solution are processing factors that are evaluated in specifying a process for producing specific NiO catalyst particles.
  • the dried precipitate is calcined at a temperature of, e.g., 400 0 C.
  • a mass of calcined individual nanometer sized NiO particles may be consolidated into clusters or grains of suitable mesh size for retention in a gas flow-through reactor for hydrogen production.
  • the nickel oxide particles Prior to methane decomposition the nickel oxide particles are exposed to a reducing atmosphere, such as a stream of hydrogen at 45O 0 C, for a couple of hours.
  • the catalyst bed of reduced nickel oxide particles presumably nickel particles, is then maintained at a suitable methane decomposition temperature such as 500 0 C.
  • a feed gas comprising methane (which may be diluted with nitrogen or helium) is flowed through the particulate catalyst bed at a space velocity of, e.g., 15,000 ml g "1 h "1 .
  • Methane molecules decompose to form hydrogen and very small carbon filaments or fibers which deposit on or between the catalyst particles.
  • Methane flow to the reactor is then diverted or interrupted and superheated steam at, e.g., 500 0 C, is flowed into contact with the carbon filament containing nickel catalyst bed. The water reacts with the carbon to form an effluent stream of hydrogen and carbon dioxide.
  • the mixed hydrogen containing stream may be used in a different application than the effluent stream from methane decomposition, or the carbon dioxide separated from the hydrogen. Following carbon removal, methane flow is restored to the regenerated catalytic reactor.
  • An advantage of using the un-supported reduced NiO catalyst of this invention is that the hydrogen product is free of carbon monoxide. Further, the decomposition of methane is accomplished at a lower catalytic reactor temperature than other alkane reformation processes.
  • uniform methane to hydrogen conversion rates of nearly 50% have been obtained over periods of two to three hours before carbon removal has been required. It appears this methane decomposition catalyst, made from NiO precursor particles, better accommodates carbon deposits which form as small filaments or fibers. And the methane decomposition step and carbon removal step can be repeated over prolonged periods in useful hydrogen production.
  • Figure 1 is a graph of methane conversion (in percentage of methane charged) versus time (minutes) in a stream of diluted methane (10% methane in helium) flowing at a gas hourly space velocity (GHSV) of 15,000 ml g "1 h "1 over unsupported reduced NiO catalysts at 500 0 C.
  • the nickel oxide catalyst precursors were produced, respectively, from nickel acetate, nickel chloride and nickel nitrate. Each NiO precursor was reduced with hydrogen before methane conversion was started.
  • Figure 2 is a graph of hydrogen formation in millimoles per minute per 0.2 gram of catalyst versus time in minutes for the same experimental methane decomposition conditions used to produce the data of
  • Figure 3 is a graph of methane conversions (in percentage of methane charged) versus time (minutes) in streams of diluted methane (10% methane in helium) flowing at a gas hourly space velocity (GHSV) of 15,000 ml g "1 h "1 over unsupported, hydrogen reduced NiO catalysts at 500 0 C.
  • the nickel oxide catalyst precursors were produced from nickel nitrate using sodium carbonate as the precipitating agent and added at specified rates to identical aqueous solutions of nickel nitrate at room temperature. Each NiO precursor was reduced with hydrogen before methane conversion was started.
  • Figure 4 is a graph of hydrogen formation in millimoles per minute per 0.2 gram of catalyst versus time in minutes for the same experimental methane decomposition conditions used to produce the data of Figure 3.
  • Figure 5 is a graph of methane conversion (in percentage of methane charged) and hydrogen formation (millimoles per min. per 0.2 g catalyst) versus time (minutes) in a stream of diluted methane (10% methane in helium) flowing at a gas hourly space velocity (GHSV) of 15,000 ml g ⁇ h "1 over unsupported, hydrogen reduced NiO catalyst at 500 0 C.
  • the nickel oxide catalyst precursor was produced from nickel chloride in an aqueous solution to which sodium chloride had been added before precipitation of the nickel hydroxide.
  • Nickel oxide catalyst precursors with different particle sizes were prepared by a precipitation technique through controlling processing parameters, such as the composition of nickel precursor compounds, solvent composition, solvent temperature and temperature at which the precipitating agent is added, composition of the base precipitating agent, and the rate of precipitating agent addition.
  • the physico-chemical features of the NiO catalyst precursor materials were characterized with XRD, temperature-programmed techniques, and Transmission Electronic Microscopy (TEM). In general, the activities of these catalysts for methane decomposition were tested at 500 0 C, a desirably low temperature for hydrogen production by methane decomposition.
  • a precipitation process was employed to prepare nickel oxide particles by using different nickel precursors and precipitating agents.
  • the nickel precursors were dissolved into water or water miscible solvents at ambient and warmer temperatures, followed by the addition of the precipitating solution through a liquid injection pump under vigorous stirring until the pH value of the mixed solution reached 10.
  • the precipitate/mother liquor suspension was further aged for a few hours under stirring.
  • the solid precipitate obtained was then filtered and washed with deionized water.
  • the precipitate was dried overnight and calcined at 400 0 C for 4 hours in air.
  • X-ray diffraction (XRD) analysis was used to confirm the formation of NiO particles and to determine their average particle size.
  • the average particle sizes of nickel oxide particles were calculated form the Scherrer equation using the half-widths of their (111) diffraction lines.
  • Each sample of calcined NiO powder was aggregated into a 40-60 mesh powder to facilitate loading into a flow-through catalytic reactor for evaluation of its methane decomposition and hydrogen production activity.
  • Methane decomposition reactions over the nickel catalysts were carried out in a fixed-bed quartz tube reactor.
  • the selected catalyst precursor powder sample (0.2 g, 40-60 mesh) was reduced with a stream of diluted hydrogen (5%H 2 /N 2 ) at 45O 0 C for 2.5 hours. Then, the catalyst was heated to 500 0 C under the flow of helium. The feed gas of methane mixed with helium (10% CH 4 /He) was then introduced. The effluent gas was analyzed by on-line Gas Chromatography (HP 6890N) with a thermal conductivity detector (TCD) and a flame ionization detector (FID).
  • HP 6890N on-line Gas Chromatography
  • TCD thermal conductivity detector
  • FID flame ionization detector
  • Nickel nitrate, nickel acetate and nickel chloride were used as nickel precursors to produce nickel oxide.
  • An equivalent amount of each Ni +2 compound was dissolved in water at ambient conditions (about 2O 0 C).
  • Aqueous sodium carbonate solution was added at the same relatively low rate to the respective precursor solutions with vigorous stirring.
  • Table 1 lists the average particle sizes in nanometers of nickel oxides obtained from these precursors after calcining of the respective precipitates.
  • NiO particle catalyst precursors were tested as described above for their respective catalytic activities over time for the decomposition of methane and the production of hydrogen.
  • Figure 1 compares the catalytic activities of the three hydrogen reduced nickel oxides at 500 0 C by presenting graphical data of the percentage conversion of methane in the feed stream over a period of 180 to 300 minutes as determined by analysis of the effluent stream from each experiment.
  • Figure 2 provides graphical data of the formation of hydrogen in millimoles per minute per 0.2 gram of catalyst.
  • NiO catalyst provided the most promising catalytic performance.
  • the NiO generated from the nickel chloride precursor showed the smallest particle size of 7.5 nm and the highest methane conversion (>45%) combined with the longest catalytic stability up to three hours before the pressure drop of gas flow through the reactor increased.
  • This high stability implied that the carbon deposition capacity (often expressed by C/Ni ratio) is very high.
  • the 9 nm size NiO particles prepared from nickel nitrate provided an intermediate activity and stability performance among the three experimental catalysts, and the 10 run size NiO particles prepared from the nickel acetate exhibited the lowest catalytic activity as well as the lowest stability over time.
  • the addition rate of the base precipitating solution affects the precipitation rate of nickel hydroxide, and consequently the particle size of NiO after calcination.
  • an aqueous sodium carbonate solution was used at room temperature to precipitate nickel hydroxide from a room temperature aqueous nickel salt precursor solution.
  • the effect of the addition rate of sodium carbonate solution on the catalytic activity of reduced NiO was studied by using nickel nitrate as nickel precursor.
  • Sodium carbonate solution (0.25 M) was added to aqueous solutions of nickel nitrate, initially of about 200 ml or so in volume.
  • the nickel nitrate solutions were of 0.2 molar concentration, suitably 0.1-0.5 M.
  • the pH of the nickel nitrate solution was monitored as precipitation proceeded, and the sodium carbonate addition was continued until a pH of 10 was reached at which level of alkalinity the Ni +2 content of the solution was deemed fully precipitated.
  • the precipitates were filtered, dried and calcined as described.
  • the particle sizes of the NiO catalyst precursors as well as catalytic properties of the hydrogen reduced particles are summarized in Table 2 and Figures 3-4.
  • Figure 3 compares the catalytic activities of the five reduced nickel oxides at 500 0 C by presenting graphical data of the percentage conversion of methane in the feed stream over a period of 60 to 300 minutes as determined by analysis of the effluent stream from each experiment.
  • Figure 4 provides graphical data over the same time period of the formation of hydrogen in millimoles per minute per 0.2 gram of catalyst.
  • the 6.5 nm size NiO catalyst precursor particles produced with the slowest precipitant addition rate maintained high methane conversion rates (>45 %) over two hours.
  • the progressively larger NiO particles, made with progressively higher base addition rates had progressively lower conversion rates and lower hydrogen formation rates.
  • the precipitation agent has a marginal effect on the particle sizes and the catalytic activities.
  • the NiO catalysts made using Na 2 CO 3 , NaOH, and KOH precipitation agent solutions had similar nanometer scale particle sizes and showed similar catalytic activity and stability.
  • NiO particle sizes become smaller with increasing the aging time of nickel hydroxide in the mother liquids.
  • Ni(AC) 2 and Ni(NO 3 ) 2 were employed as nickel precursors. With longer aging time, there is an increase in the catalytic activity and a greatly improved stability.
  • Particle size data resulting from increased ageing times is summarized in Table 3. This data was obtained from room temperature aging tests.
  • the precipitation temperature plays a significant role in governing the formation of nickel hydroxide and controlling the particle size of NiO.
  • the NiO particle size ranged from 13.1nm at 2O 0 C to 9.0 nm at 8O 0 C.
  • the NiO particle of 13. lnm had almost no activity towards methane decomposition, while the methane conversion approached 40% over the NiO particles of 9.0 nm.
  • Precipitation at 12O 0 C resulted in the smallest NiO particles of 4.1 nm.
  • this rather small particle did not show better catalytic activity than the NiO prepared at 8O 0 C with a relative larger particle size of 7.1 nm.
  • the solvent also appears to have an effect on NiO particle size.
  • NiO changed from 10 nm to 6.4 nm by employing different solvents to dissolve the nickel precursors (Table 4).
  • the NiO particles of 6.4-6.8 nm prepared in ethanol (ETOH) and ethylene glycol (EG) showed the best catalytic activities. This result may be attributed to the nature of the fine dispersion of the nickel hydroxides in these organic solvents.
  • the NiO prepared in propylene glycol (PG) solvent has additional two peaks in XRD spectra, which suggests that the solvent has additional effects in determining the morphology of NiO.
  • Ni nickel ions
  • the temperature of the Ni ion solution is suitably between ambient temperature and an elevated temperature below the boiling point of the solvent.
  • a suitable base such as sodium hydroxide or sodium carbonate is dissolved in a like solvent, miscible with the Ni ion solution and added to the Ni ion solution at a rate to form a uniformly fine precipitate.
  • aqueous solutions are used the base is added until the pH of the mixture is at least about 10.
  • the solvent-precipitate mixture is preferably stirred and aged.
  • NiO catalyst precursor particles have a particle size below about ten to fifteen nanometers for methane decomposition.
  • the particles may be aggregated into larger granules for containment and use in a catalytic reactor for hydrogen production.
  • the NiO particles are suitably reduced by hydrogen before use in methane decomposition.
  • Nickel chloride was dissolved in water at 8O 0 C (suitably 0.1-0.5 M, preferably 0.2-0.3 M). NaCl was added to the Ni +2 ion solution to form a supersaturated, or more saturated, aqueous solution. An aqueous NaOH solution was slowly added using a liquid injection pump with vigorous stirring of the saturated Ni and Cl ion solution until the pH value of the precipitate water mixture reached 10. The precipitate-water mixture was aged at 8O 0 C for 120 minutes (suitably about one to three hours) and the Ni containing precipitate was removed by filtration and dried. The dried precipitate was calcined and prepared for catalyst usage as described. The NiO had a particle size of about ten nanometers.
  • NiO catalyst precursors with different particle sizes ranging from 4.0 nm to 15 nm were prepared by the described precipitation method practices.
  • NiO particle sizes in the range of 6-10 nm displayed particularly good activity and durability in hydrogen production from methane.
  • the particle size decreased to 4.0 nm, the catalytic activity decreased or vanished, while a NiO catalyst with a particle size of 10.0 nm showed the extremely long stability.
  • NiO catalysts of this invention appear to cause carbon to deposit in catalyst bed in the form of small fine filaments or fibers that lie between and around the catalyst particles. This form of carbon deposit seems to permit somewhat longer methane decomposition cycles. The deposited carbon does not appear to coat and inhibit the catalyst particles as readily as in other CH 4 decomposition practices. [0037] The practices of this invention are also believed to be applicable to the decomposition of other lower saturated hydrocarbons such as ethane and propane to produce hydrogen, but more rapid build-up of carbon on the catalyst is to be expected.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
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Abstract

On effectue la décomposition du méthane pour produire de l'hydrogène dépourvu de monoxyde de carbone au moyen de particules d'oxyde de nickel, de taille nanométrique et sans support qui sont soumises à une réduction par l'hydrogène et produites par un processus de précipitation. Un composé de nickel, tel que NiCl2 ou Ni(NO3) est dissous dans de l'eau et précipité de manière appropriée en tant qu'hydroxyde de nickel. Le précipité est ensuite séparé, déshydraté et calciné pour former les particules de précurseur de catalyseur NiO.
PCT/US2006/007688 2006-03-03 2006-03-03 Nanoparticules d'oxyde de nickel utiles en tant que précurseur de catalyseur pour la production d'hydrogène WO2007100333A1 (fr)

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PCT/US2006/007688 WO2007100333A1 (fr) 2006-03-03 2006-03-03 Nanoparticules d'oxyde de nickel utiles en tant que précurseur de catalyseur pour la production d'hydrogène

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PCT/US2006/007688 WO2007100333A1 (fr) 2006-03-03 2006-03-03 Nanoparticules d'oxyde de nickel utiles en tant que précurseur de catalyseur pour la production d'hydrogène

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111167495A (zh) * 2020-01-07 2020-05-19 郑州大学 一种氨硼烷制氢用催化剂Ni2-xFex@CN-G及其制备方法
CN113527031A (zh) * 2020-04-14 2021-10-22 中国石油化工股份有限公司 四氢双环戊二烯的制备方法
US11332367B2 (en) * 2018-04-01 2022-05-17 Ihara Co., Ltd. Hydrogen producing apparatus, method for separating solid product and system for discharging and recycling solid product
IL253738B (en) * 2015-02-03 2022-11-01 Gencell Ltd A nickel-based catalyst for the decomposition of ammonia

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US2602070A (en) * 1950-09-15 1952-07-01 Int Nickel Co Process for the preparation of pure nickel hydroxide
US2696475A (en) * 1948-11-12 1954-12-07 Phillips Petroleum Co Method of preparation of supported nickel, cobalt, or copper catalysts
US2776244A (en) * 1953-05-11 1957-01-01 Wigton Abbott Corp Preparation of nickel oxide desulfurizing catalyst and utilization thereof for desulfurizing
US3133029A (en) * 1960-12-27 1964-05-12 Universal Oil Prod Co Method of preparing a copper, cobalt or nickel catalyst
US3186957A (en) * 1960-04-14 1965-06-01 Du Pont Method of preparing a nickel oxidealumina catalyst composition and the product thereof
US3320182A (en) * 1963-10-21 1967-05-16 Exxon Research Engineering Co High activity nickel-alumina catalyst
US3988262A (en) * 1974-07-03 1976-10-26 Haldor Topsoe A/S Methanation catalyst and process for preparing the catalyst
US4490480A (en) * 1982-04-23 1984-12-25 Internationale Octrooi Maatschappij "Octropa"B.V. Nickel catalyst on alumina support
US6953488B2 (en) * 1999-10-01 2005-10-11 Bp Corporation North America Inc. Preparing synthesis gas using hydrotalcite-derived nickel catalysts
US7005405B2 (en) * 2001-09-21 2006-02-28 Kabushiki Kaisha Toshiba Metal oxide sintered structure and production method therefor

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Publication number Priority date Publication date Assignee Title
US2696475A (en) * 1948-11-12 1954-12-07 Phillips Petroleum Co Method of preparation of supported nickel, cobalt, or copper catalysts
US2602070A (en) * 1950-09-15 1952-07-01 Int Nickel Co Process for the preparation of pure nickel hydroxide
US2776244A (en) * 1953-05-11 1957-01-01 Wigton Abbott Corp Preparation of nickel oxide desulfurizing catalyst and utilization thereof for desulfurizing
US3186957A (en) * 1960-04-14 1965-06-01 Du Pont Method of preparing a nickel oxidealumina catalyst composition and the product thereof
US3133029A (en) * 1960-12-27 1964-05-12 Universal Oil Prod Co Method of preparing a copper, cobalt or nickel catalyst
US3320182A (en) * 1963-10-21 1967-05-16 Exxon Research Engineering Co High activity nickel-alumina catalyst
US3988262A (en) * 1974-07-03 1976-10-26 Haldor Topsoe A/S Methanation catalyst and process for preparing the catalyst
US4490480A (en) * 1982-04-23 1984-12-25 Internationale Octrooi Maatschappij "Octropa"B.V. Nickel catalyst on alumina support
US6953488B2 (en) * 1999-10-01 2005-10-11 Bp Corporation North America Inc. Preparing synthesis gas using hydrotalcite-derived nickel catalysts
US7005405B2 (en) * 2001-09-21 2006-02-28 Kabushiki Kaisha Toshiba Metal oxide sintered structure and production method therefor

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IL253738B (en) * 2015-02-03 2022-11-01 Gencell Ltd A nickel-based catalyst for the decomposition of ammonia
IL253738B2 (en) * 2015-02-03 2023-03-01 Gencell Ltd A nickel-based catalyst for the decomposition of ammonia
US11332367B2 (en) * 2018-04-01 2022-05-17 Ihara Co., Ltd. Hydrogen producing apparatus, method for separating solid product and system for discharging and recycling solid product
CN111167495A (zh) * 2020-01-07 2020-05-19 郑州大学 一种氨硼烷制氢用催化剂Ni2-xFex@CN-G及其制备方法
CN113527031A (zh) * 2020-04-14 2021-10-22 中国石油化工股份有限公司 四氢双环戊二烯的制备方法
CN113527031B (zh) * 2020-04-14 2024-02-20 中国石油化工股份有限公司 四氢双环戊二烯的制备方法

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