[go: up one dir, main page]

WO2005072871A1 - Catalyseur - Google Patents

Catalyseur Download PDF

Info

Publication number
WO2005072871A1
WO2005072871A1 PCT/GB2004/004812 GB2004004812W WO2005072871A1 WO 2005072871 A1 WO2005072871 A1 WO 2005072871A1 GB 2004004812 W GB2004004812 W GB 2004004812W WO 2005072871 A1 WO2005072871 A1 WO 2005072871A1
Authority
WO
WIPO (PCT)
Prior art keywords
metal
catalyst
metal oxide
metal particles
water
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/GB2004/004812
Other languages
English (en)
Inventor
Mei Yu Yeung
Shik Chi Tsang
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Johnson Matthey PLC
Original Assignee
Johnson Matthey PLC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Johnson Matthey PLC filed Critical Johnson Matthey PLC
Publication of WO2005072871A1 publication Critical patent/WO2005072871A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • 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
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/63—Platinum group metals with rare earths or actinides
    • 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
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/66—Silver or gold
    • 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
    • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
    • B01J35/45—Nanoparticles
    • 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
    • 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
    • B01J37/033—Using Hydrolysis
    • 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
    • C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
    • C01B3/12—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide
    • C01B3/16—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide using catalysts
    • 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
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
    • 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
    • C01B2203/0283—Processes for making hydrogen or synthesis gas containing a CO-shift step, i.e. a water gas shift 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
    • 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
    • C01B2203/1064—Platinum group metal catalysts
    • C01B2203/107—Platinum 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
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1082—Composition of support materials
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • the present invention relates to catalysts comprising precious metal particles and reducible meta ⁇ oxide materials.
  • the catalysts are active for the water gas shift reaction.
  • the invention further relates to processes for preparing the catalysts and the use of the catalysts in the water gas shift reaction.
  • the water gas shift (WGS) reaction converts water and carbon monoxide into hydrogen and carbon dioxide: H 2 O + CO ⁇ H 2 + C0 2
  • the reaction is commonly used to remove carbon monoxide from gas streams, e.g. hydrogen-rich gas streams produced by the reforming of hydrocarbon fuels.
  • the reaction is catalysed by heterogeneous catalysts, which are usually classified as high, temperature WGS catalysts (capable of catalysing the reaction at 400-450°C) and low temperature WGS catalysts (capable of catalysing the reaction at 200-400°C).
  • state-of-the-art WGS catalysts include iron/chromium/copper oxide (for high temperature WGS) and copper oxide/zinc oxide (for low temperature WGS).
  • WGS catalysts comprising precious metals dispersed on ceria have recently been developed, see e.g. Fu et al (Science, 2003 (301), 935-938).
  • One problem with known precious metal WGS catalysts is that the methanation reaction competes with the WGS reaction:
  • the methanation reaction consumes hydrogen, so is especially undesirable when the WGS process is being used to remove carbon monoxide in a fuel processing system for hydrogen generation.
  • the present inventors have sought to provide catalysts that are highly active for the WGS reaction but have reduced activity (or totally eliminated activity) for methanation.
  • the present invention provides a water gas shift catalyst comprising metal particles comprising at least one precious metal, and a metal oxide material comprising at least one reducible metal oxide. wherein substantially all of the metal particles are encapsulated by the metal oxide material such that the catalyst has substantially no activity for methanation, and wherein the loading of the metal particles is between 0.5-25 wl% based on the weight of the metal oxide material.
  • the metal particles are not at the surface of the catalyst and are therefore not accessible to gas molecules during the catalytic process.
  • substantially all of the metal particles we mean at least 95% of the metal particles, preferably at least 99% of the metal particles. Most preferably all of the metal particles are encapsulated by the metal oxide material.
  • the catalyst has no activity for methanation.
  • the present inventors have prepared catalysts by practical methods and have found that substantially complete encapsulation of metal particles provides advantageous WGS catalysts, Catalysts wherein at least some of the precious metals particles are encapsulated in reducible metal oxides are known from EP 602 865. However, the present inventors have found that WGS catalysts produced by co-precipitation methods similar to those disclosed in EP 602 865 are active for methanation. Microemulsion processes used by the present inventors ensure that substantially all of the metal particles are encapsulated and that the catalyst is substantially not active for methanation.
  • a microemulsion is a dispersion of two immiscible liquids, generally termed "water 5* and "oil " ', which is stabilised by surfactants.
  • Figure 1 shows a "water in oil' * microemulsion. Surfactants (1) hold water within the oil. Adjacent to the surfactants (1 ) is a region of rigidly held water (2). In the centre there is a region of mobile water (3).
  • the metal particles in the WGS catalyst suitably comprise one or more of Au or Pt and preferably contain only Au and or Pt.
  • the loading of the metal particles is between 0.5-25 t% based on the weight of the metal oxide material, preferably between 2 ⁇ 15 t%. WGS activity is reduced at low loadings, possibly because small metal particles are embedded deep down within the metal oxide overlayers. Conversely high metal loading not only reduces the contact interface between the metal particles and the metal oxide but may also disturb the embedment (encapsulation) process.
  • the average diameter of the metal particles is suitably in the range 2-50nm, preferably 2-3 Onm. Smaller particles are advantageous because they provide better interaction between the metal and the metal oxide material for the same amount of metal. However, very small metal particles (diameter less than 2nm) can exhibit strange non- metallic properties so are not preferred.
  • the at least one reducible metal oxide is suitably chosen from ceria, titania, iron oxide, manganese oxide or tin oxide and is preferably ceria.
  • the metal oxide material may further comprise metal oxides that are not reducible, such as zirconia, alumina or lanthana.
  • the catalysts of the invention can be prepared by a microemulsion method using a
  • the present invention further provides a process for preparing a water gas shift catalyst comprising steps of: a) preparing a microemulsion comprising an organic solvent, a surfactant and water, wherein a precious metal precursor and a reducible metal oxide precursor are dissolved in the water; and b) adding a hydrolysis agent to the microemulsion and aging the microemulsion, thereby encapsulating precious metal particles in a layer of metal oxide material.
  • precious metal particles and reducible metal oxide are co-precipitated in an aqueous solution.
  • reducible metal oxide is precipitated in the presence of a precious metal colloid, again in aqueous solution.
  • precipitation of the precious metal and the reducible metal oxide will take place within aqueous regions within the microemulsion.
  • Precipitation within the microemulsion provides a different catalyst compared to precipitation within an aqueous solution as disclosed in EP 602 865, The present inventors have found that the microemulsion method can be used to provide a catalyst wherein substantially all of the precious metal is encapsulated by the metal oxide. These catalysts are active for the WGS reaction and exhibit substantially no methanation activity.
  • the organic solvent is suitably a non-polar s ⁇ h ent such as toluene, cyclohexane or a C 5 -C 15 alkane, and is preferably toluene.
  • the surfactant may be an ionic surfactant or a non-Ionic surfactant, and may be fluorinated. Suitable surfactants include CTAB
  • AOT sodium bis (2-ethyIhexyl) suifb-succinate
  • CPC cetylpyridinram chloride
  • Triton ® X- ⁇ 00 Triton ® X- ⁇ 00.
  • a preferred surfactant is CTAB.
  • the organic solvent, surfactant and water must be in a suitable ratio for forming a microemulsion wherein the water is held within the organic solvent. Suitable ratios for forming a microemulsion will be known to the skilled person.
  • the molar ratio of water: surfactant is suitably between 2-100:1 and is preferably about 30: 1. This ratio dictates the size of the regions of water within the microemulsion, so will affect the formation of the catalyst particles.
  • Suitable precious metal precursors will be well known to the skilled person and include NHAP Cl ⁇ and HAuCl 4 .3H 2 0, The concentration of the precious metal precursor in the aqueous regions of the microemulsion can be varied and this will affect the size of the precious metal particles.
  • Suitable reducible metal oxide precursors will also be well known to the skilled person and include Ce(N0 3 ) 3 ,6H 2 ⁇ . The concentration of the reducible metal oxide precursor in the aqueous regions of the microemulsion can be varied, and this will affect the ratio of reducible metal oxide: precious metal (usually expressed as the loading of the precious metal).
  • the microemulsion may be prepared by mixing the surfactant with the organic solvent, and then adding aqueous solutions of the precious metal precursor and reducible metal oxide precursor.
  • the precious metal precursor and reducible metal oxide precursor can be present in a single aqueous solution that is added to the organic solvent and surfactant.
  • the present inventors have found that it is preferable to add the reducible metal oxide precursor after the addition of the precious metal precursor. Precious metal encapsulation is improved and methanation activity of the catalysts is reduced.
  • the hydrolysis agent is suitably sodium hydroxide or ammonia.
  • the microemulsion is suitably stirred during the aging process.
  • the aging process may take several days, e.g. up to six days may be required to achieve encapsulation of the precious metal particles by the reducible metal oxide.
  • the skilled person can sample the reaction mixture throughout the aging process and measure the WGS activity of the sample or take microscopy images to see if substantial encapsulation has occurred.
  • the microemulsion can be filtered and dried to provide the catalyst.
  • the catalyst may be calcined at a temperature of about 400°C before use.
  • the invention further provides the use of a catalyst according to the invention in a water gas shift reaction. Hydrogen and carbon monoxide are suitably supplied to the catalyst and thereby converted to water and carbon dioxide.
  • the catalyst may be used to remove carbon monoxide from a hydrogen stream that v,ill be supplied to a fuel cell.
  • the invention further provides a catalyst according to the invention deposited on a catalyst substrate such as a monolith, which may be metallic or ceramic, or a heat exchanger substrate.
  • Example 1 Encapsulated 5wt% Pt/ Ceria 8.0915 g of cetyltrimethylammonium bromide (CTAB) w r as added into 300.0 ml of dry toluene with vigorous stirring overnight. A suspension of CTAB in toluene was formed.
  • the Pt precursor salt solution was prepared by dissolving 0.1930 g of ammonium letraehloroplatinate (II). ( AhPtCU, into 4.0 ml of deionised water. The aqueous solution of Pt precursor salt was added dropwise to the suspension of CTAB in toluene and was stirred overnight.
  • a solution of 1 ,9869 g of sodium hydroxide dissolved in 4.0 ml of deionised water was added dropwise into the reaction mixture and stirred for another 2 hours.
  • a ceria precursor solution was then prepared by dissolving 4.8420 g of cerium (III) nitrate hexahydrate, Ce(NG 3 ) 3 6H 2 O, salt into 4.0 ml deionised water.
  • the ceria precursor solution was added dropwise into the reaction mixture.
  • the reaction mixture was aged for 6 days with stirring. After the ageing step, the reaction mixture was centrifuged for 20 minutes (1000 revs/min) to collect the solid product.
  • the solid product was then washed four times with hot ethanol to remove the excess surfactants in the solution, The solution was centrifuged after each washing. The final product obtained was then dried in air overnight.
  • the catalyst was prepared as for example 1 except that 12.9844 g of CTAB was added into 300.0 ml of dry toluene and instead of the Pt precursor solution, a Pt-Au precursor salt solution was prepared by dissolving 0.2117 g of ammonium tetrachloroplatinate (II), (NH ) 2 PtCl 4 . and 0.2266 g of hydrogen tetrachloroaurate (HI), HAuCl 4 3H 2 O, into 5.4 ml of deionised water.
  • II ammonium tetrachloroplatinate
  • HI hydrogen tetrachloroaurate
  • HAuCl 4 3H 2 O HAuCl 4 3H 2 O
  • the sodium hydroxide solution contained 1.S570 g of sodium hydroxide in 4.6 ml of deionised water and the ceria precursor solution contained 4.5230 g of cerium (III) nitrate hexahydrate salt, Ce(N0 3 ) 3 6H 2 0, into 2.8 ml deionised water.
  • Example 3 Encapsulated lwt% Pt Ceria
  • the catalyst was prepared as for example 1 except that the amounts of Pt precursor salt solution and ceria precursor solution were varied to give a loading of 1 wt% Pt.
  • Example 4 Encapsulated 10wt% Pt Ceria
  • the catalyst was prepared as for example 1 except that the amounts of Pt precursor salt solution and ceria precursor solution were varied to give a loading of 10wt% Pt
  • ammonium tetracliloroplatinate (II) 0.1541 g ammonium tetracliloroplatinate (II), was dissolved in a 100.0 ml aqueous solution of 0.2 M cerium (III) nitrate hexahydrate. Ce(NOj) 3 6H 2 0, and sprayed into a 250.0 ml ammonia solution under constant stirring. The precipitate in ammonia solution was allowed to age at room temperature with stirring for another two hours. The precipitate was collected by centrifugation (1000 revs/min) and washed twice with water and once with hot ethanol to remove any remaining ammonia and reaction byproduct. The solid was dried in a vacuum oven at 333 for 2 hours.
  • the reaction mixture was allowed to age for 6 days with stirring. After the ageing step, the reaction mixture was centrifuged for 20 minutes (1000 revs/min) to collect the solid product. The product collected was then washed four times with hot ethanol to remove the excess surfactants in the solution. The solution was centrifuged after each washing. The product obtained was dried in air for overnight. The sample was calcined under air with temperature increasing (2 K/min) up to 523 where it remained for 2 hours.
  • a Pt precursor salt solution was prepared by dissolving 0.0483 g of ammonium tetrachloroplatinate (II), (NH s tCLt, in 0,85 ml deionised water. The Pt precursor solution was added onto 0.4769 g calcined ceria. The reaction mixture was dried in air with temperature increasing (5 K/min) up to 373 K where It remained for 1 hours. Then, the product was calcined in air with temperature increasing (20 K/min) up to 773 K for 2 hours.
  • II ammonium tetrachloroplatinate
  • Comparative Example 3 Encapsulated 27.11wt% Pt Ceria
  • the catalyst was prepared as for example 1 except that the amounts of Pt precursor salt solution and ceria precursor solution were varied to give a loading of 27.11wt% Pt.
  • the reactor was in the form of a quartz tube inside a temperature programmable furnace with an internal diameter of 4 mm.
  • the catalyst powder (normally 50 mg used) was then packed and sandwiched between two glass wool plugs in this quartz reactor tube and was located in the middle of the furnace zone.
  • the feed gases were passed directly into the quartz reactor.
  • the gas composition used was 0.77 % CH 4 , 6.15 % CO, 7.68 % COa, 24.99 % IHk 23.08 % H 2 O balance N 2 .
  • the reactor temperatures were raised between 120 °C and 500 °C and catalytic performances were evaluated at 150, 200, 250, 300, 350, 400, 450, 500°C intervals. All the incoming and outgoing lines were pre-heated at 120 °C.
  • the catalyst was first placed in a stream of 70 ml/min pure H 2 with temperature programming from room temperature to 400 °C (10 °C/min) and was held at this temperature for 30 minutes. Then, it was cooled to room temperature under the H 2 , The catalyst was then pre-conditioned at 300 °C with tlie reactant gas mixture overnight before the proceeding to the catalytic activity evaluation.
  • the catalyst was then allowed to cool to 150°C with the same feed gases and studied the catalytic results at each temperature (from 150 to 500°C) for 30 minutes before tlie next measurement.
  • the product gases from the reactor were analysed by a GC equipped with a methanator and a flame ionizatlon detector (FID). Three samples of product gases were taken at each temperature point to ensure the results were reproducible.
  • Tl e catalysts of the invention show high WGS activity, but are not active for methanation. By contrast, catalysts wherein precious metal particles are present on tlie surface of metal oxide material are active for both WGS and methanation.
  • Figure 2 shows the WGS activity of the catalysts of examples 1, 3 and 4 and comparative example 3. The result shows that the best WGS activity is observed for the catalysts with 5 t% or 10wt% of platinum metal loading. For the catalysts of example 1 , 3 and 4 (5wt%, lwt% and 10 t% platinum metal loaded ceria catalysts), no methane production was detected during the whole temperature range ( 120 °C to 500 °C). For the catalyst of comparative example 3 (27.11 wt% platinum metal loaded ceria catalyst), about 5% methane production compared with the marker methane was detected.

Landscapes

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

Abstract

L'invention concerne un catalyseur de conversion du CO qui comprend des particules métalliques et un matériau en oxyde métallique. Les particules comprennent au moins un métal précieux et le matériau en oxyde métallique comprend au moins un oxyde de métal réductible. On encapsule sensiblement la totalité des particules dans le matériau en oxyde métallique de sorte que le catalyseur n'ait sensiblement aucune activité de méthanisation. La charge en particules est comprise entre 0,5 et 25 %, par rapport au poids du matériau en oxyde métallique. L'invention concerne également un procédé relatif à l'élaboration du catalyseur.
PCT/GB2004/004812 2004-02-02 2004-11-16 Catalyseur Ceased WO2005072871A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GBGB0402104.4A GB0402104D0 (en) 2004-02-02 2004-02-02 Water gas shift catalyst
GB0402104.4 2004-02-02

Publications (1)

Publication Number Publication Date
WO2005072871A1 true WO2005072871A1 (fr) 2005-08-11

Family

ID=31971773

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB2004/004812 Ceased WO2005072871A1 (fr) 2004-02-02 2004-11-16 Catalyseur

Country Status (2)

Country Link
GB (1) GB0402104D0 (fr)
WO (1) WO2005072871A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012025897A1 (fr) 2010-08-26 2012-03-01 Basf Se Catalyseurs de conversion hautement actifs
CN103084174A (zh) * 2011-10-28 2013-05-08 中国石油化工股份有限公司 一种脱除碳氧化物的甲烷化催化剂及其制备方法和应用
US8597407B2 (en) 2008-12-17 2013-12-03 Basf Se Method for removing contaminants from gas flows containing water
CN104084213A (zh) * 2014-07-01 2014-10-08 南京大学 用于固定源烟气低温脱硝的铁锰钛催化剂的制法及其制备的催化剂
US9248436B2 (en) 2010-08-26 2016-02-02 Basf Se Highly active shift catalysts

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0602865A1 (fr) * 1992-12-18 1994-06-22 Johnson Matthey Public Limited Company Catalyseur

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0602865A1 (fr) * 1992-12-18 1994-06-22 Johnson Matthey Public Limited Company Catalyseur

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
FU Q., SALTSBURG H., FLYTZANI-STEPHANOPOULOS M.: "Active Nonmetallic Au and Pt Species on Ceria-Based Water-Gas Shift Catalysts", SCIENCE, vol. 301, 2003, pages 935 - 938, XP002313685 *
HARDACRE C., ORMEROD R.M. AND LAMBERT R.M.: "Platinum-Promoted Catalysis by Ceria: A Study of Carbon Monoxide Oxidation over Pr(111)/CeO2", J. PHYS. CHEM., vol. 98, 1994, pages 10901 - 10905, XP002313684 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8597407B2 (en) 2008-12-17 2013-12-03 Basf Se Method for removing contaminants from gas flows containing water
WO2012025897A1 (fr) 2010-08-26 2012-03-01 Basf Se Catalyseurs de conversion hautement actifs
US9248436B2 (en) 2010-08-26 2016-02-02 Basf Se Highly active shift catalysts
CN103084174A (zh) * 2011-10-28 2013-05-08 中国石油化工股份有限公司 一种脱除碳氧化物的甲烷化催化剂及其制备方法和应用
CN104084213A (zh) * 2014-07-01 2014-10-08 南京大学 用于固定源烟气低温脱硝的铁锰钛催化剂的制法及其制备的催化剂

Also Published As

Publication number Publication date
GB0402104D0 (en) 2004-03-03

Similar Documents

Publication Publication Date Title
US12102989B2 (en) Functional nanoscale metal oxides for stable metal single atom and cluster catalysts
Zou et al. Core–shell NiO@ PdO nanoparticles supported on alumina as an advanced catalyst for methane oxidation
Zou et al. Sequential growth reveals multi-spinel interface promotion for methane combustion over alumina supported palladium catalyst
RU2730496C2 (ru) Содержащие родий катализаторы для обработки автомобильных выхлопов
CN109718807B (zh) 甲烷干重整催化剂及其制备方法和应用以及甲烷干重整制合成气的方法
US10537881B2 (en) Methods of making supported Ni/Pt bimetallic nanoparticles and Ni/Pt multilayer core-shell structures and their uses for CO2 reforming
Kibis et al. Redox and Catalytic Properties of Rh x Ce1–x O2− δ Solid Solution
CN107456965B (zh) 一种以氧化铈为载体的负载型钯催化剂及其制备方法
KR102611089B1 (ko) 철-세리아 쉘에 캡슐화된 금속 클러스터 코어를 포함하는 촉매 복합체 및 이를 이용한 이산화탄소 환원반응을 통한 선택적 일산화탄소 생산방법
EP2870997B1 (fr) Catalyseur pour la purification de gaz d'émission, et son procédé de production
Camposeco et al. Synthesis and characterization of highly dispersed bimetallic Au-Rh nanoparticles supported on titanate nanotubes for CO oxidation reaction at low temperature
JP6131370B1 (ja) 合成ガス製造触媒用担体及びその製造方法、合成ガス製造触媒及びその製造方法、並びに合成ガスの製造方法
WO2005072871A1 (fr) Catalyseur
Yeung et al. Some optimization in preparing core-shell Pt–ceria catalysts for water gas shift reaction
JPWO2005094988A1 (ja) 一酸化炭素除去触媒及びその製造方法並びに一酸化炭素除去装置
CN113209999A (zh) 一种用于甲烷干气重整反应的催化剂及其制备方法
CN103635256A (zh) 制备含钴的费-托合成催化剂的方法
JP2000342968A (ja) 触媒およびその製造方法
JP2007516825A (ja) 改質触媒
CN105944733B (zh) 一种稀土改性的多级孔负载型镍基催化剂、制备方法及应用
JP6909405B2 (ja) メタン化触媒、その製造方法、及びそれを用いたメタンの製造方法
JP2017217630A (ja) マグネシア系触媒担体及びその製造方法
KR102027379B1 (ko) 귀금속 도핑 처리를 통한 일산화탄소 산화용 금속산화물 촉매, 그 제조 방법 및 이를 포함하는 배기가스 정화 장치
JPH0848502A (ja) 炭化水素の水蒸気改質方法
JP4875295B2 (ja) 部分酸化用改質触媒および改質方法

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BW BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE EG ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NA NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GM KE LS MW MZ NA SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LU MC NL PL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
NENP Non-entry into the national phase

Ref country code: DE

WWW Wipo information: withdrawn in national office

Country of ref document: DE

122 Ep: pct application non-entry in european phase