EP1165229A1 - Oxydation catalytique selective de co en presence de h2 - Google Patents

Oxydation catalytique selective de co en presence de h2

Info

Publication number
EP1165229A1
EP1165229A1 EP00912846A EP00912846A EP1165229A1 EP 1165229 A1 EP1165229 A1 EP 1165229A1 EP 00912846 A EP00912846 A EP 00912846A EP 00912846 A EP00912846 A EP 00912846A EP 1165229 A1 EP1165229 A1 EP 1165229A1
Authority
EP
European Patent Office
Prior art keywords
oxide
catalyst
mixture
weight
gold
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.)
Withdrawn
Application number
EP00912846A
Other languages
German (de)
English (en)
Inventor
Bojidara Grigorova
John Mellor
Atanas Palazov
Fourie Greyling
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.)
Anglo American Research Laboratories Pty Ltd
Original Assignee
Anglo American Research Laboratories Pty Ltd
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 Anglo American Research Laboratories Pty Ltd filed Critical Anglo American Research Laboratories Pty Ltd
Publication of EP1165229A1 publication Critical patent/EP1165229A1/fr
Withdrawn legal-status Critical Current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
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8966—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with germanium, tin or lead
    • 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
    • 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
    • C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
    • C01B3/56—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids
    • C01B3/58—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids including a catalytic reaction
    • C01B3/583—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids including a catalytic reaction the reaction being the selective oxidation of carbon monoxide
    • 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
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0435—Catalytic purification
    • C01B2203/044—Selective oxidation of carbon monoxide
    • 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
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0465—Composition of the impurity
    • C01B2203/047—Composition of the impurity the impurity being carbon monoxide

Definitions

  • This invention relates to catalytic oxidation.
  • Fuel cells are electrochemical devices for continuously converting chemical energy into direct-current electricity.
  • the cell consists of two electronic- conductor electrodes separated by an ionic conducting electrolyte with provision for the continuous flow of fuel, oxidant and reaction product into and out of the cell.
  • the fuel may be gaseous or a liquid; the electrolyte liquid or solid; and the oxidant is gaseous.
  • the electrodes are solid, but may be porous and contain a catalyst.
  • Fuel cells differ from batteries in that electricity is produced from chemical fuels fed to them as needed.
  • One of the fuels which is used in a fuel cell is hydrogen.
  • a contaminant in many sources of hydrogen is carbon monoxide which tends to poison the electrodes.
  • Carbon dioxide on the other hand, does not poison the electrodes of a fuel cell and it is therefore desirable to oxidise as much of the carbon monoxide to carbon dioxide before such hydrogen is fed to the fuel cell.
  • One of the problems encountered in oxidising carbon monoxide to carbon dioxide is that there is simultaneous oxidation of the hydrogen. Selective oxidation of the carbon monoxide is difficult to achieve.
  • a method of selectively oxidising carbon monoxide in a carbon monoxide/hydrogen mixture comprises contacting the mixture with a suitable oxidant, generally oxygen, in the presence of a catalyst which comprises gold, a transition metal oxide, preferably cobalt oxide, to which the gold is complexed, and tin oxide captured on an oxide support comprising a mixture of cerium oxide and titanium dioxide, the tin oxide being present in an amount of less than 0,4% by weight of the catalyst
  • a catalyst which comprises gold, a transition metal oxide, preferably cobalt oxide, to which the gold is complexed, and tin oxide captured on an oxide support comprising a mixture of cerium oxide and titanium dioxide, the tin oxide being present in an amount of less than 0,4% by weight of the catalyst
  • the complexing of the gold and the transition metal oxide includes both chemical and physical bonding Some such complexing of the tin oxide and the gold may also be present
  • Figure 1 is a graph showing CO oxidation of a gas containing CO, H 2 and O 2 .
  • Figure 2 is a graph showing H 2 oxidation of a gas containing CO, H 2 and O 2
  • the gold-based catalyst described above is particularly effective in the selective oxidation of carbon monoxide in a mixture of carbon monoxide and hydrogen "Selective" means that the oxidation of the carbon monoxide takes place in preference to that of the hydrogen. Some oxidation of the hydrogen will occur.
  • the oxidation of the mixture will take place in the presence of an oxidant such as oxygen and will typically take place at a temperature in the range 80 to 130°C.
  • the ratio of cerium oxide to titanium dioxide in the oxide support will generally be in the range of 4:1 to 5:1 on a weight basis.
  • the catalyst of the invention is further characterised by containing tin oxide. It is important that this oxide is present in a relatively low amount, i.e. 0,4 percent by weight of the catalyst or less. Preferably, such oxide is present in an amount of 0,03 to 0,3 percent by weight of the catalyst.
  • the oxide support may be made by providing a particulate mixture of the cerium oxide and titanium dioxide and, drying the mixture.
  • the mixture will be in finely particulate form and will typically have a surface area of approximately 80 to 200 m 2 tg.
  • the catalyst of the invention may be made by methods described in the art.
  • the catalyst is made by a method which includes the steps of providing a mixture of cerium oxide and titanium oxide, impregnating the mixture with a transition metal solution and optionally a tin solution, drying the impregnated oxide mixture, heating the impregnated oxide mixture at a temperature of at least 250°C in the presence of oxygen, contacting the thus treated oxide mixture with a gold solution at a pH above 12, decreasing the pH of the gold solution to a pH in the range 7 to 8,5, causing gold to precipitate on to the oxide mixture, optionally drying the thus treated oxide mixture and heating the treated oxide mixture at a temperature of at least 250°C in the presence of oxygen.
  • An example of a preferred catalyst of the invention has the following composition (all percentages by weight)
  • the catalyst may be made as follows
  • the catalyst is preferably made as follows
  • Powdered cerium oxide and titanium oxide are accurately measured into a 100ml sample bottle and mixed in a mixer mill for 10 minutes This mixture is heated at 120°C for 30 minutes
  • the oxide support impregnated with cobalt and tin nitrates is dried at 120°C for 2 hours
  • the dried oxide support is sieved through a 35 micron mesh sieve and then heated under air at 300°C for 6 hours This has the effect of converting the cobalt and tin nitrates to their oxides
  • Hydrogen tetrachloroaurate solution is added to 500ml potassium hydroxide solution at pH 13
  • the combined solution has a pH of just below 13
  • the temperature of the solution is increased to 60°C and the preheated oxide support impregnated with the cobalt and tin oxides is added to form a slurry
  • the pH of the slurry is reduced to 8 by addition of 0,1 M HNO 3
  • Magnesium citrate solution (six times the mole equivalent of the hydrogen tetrachloroaurate) is added to the slurry at a constant rate over a 30 minute period
  • the slurry is maintained at pH 8 and 60°C over a 60 minute period
  • the slurry is filtered producing a filtered catalyst
  • the filtered catalyst is re- slurned in de-ionised water and stirred for a further 30 minutes before being filtered and washed with de-ionised water
  • the catalyst is then dried at 120°C under air for 2 hours
  • the dried catalyst is sieved to -35 ⁇ m and calcined at 450°C under 5% 0 2 for 3 hours
  • the catalyst is stored prior to use
  • FC6 a catalyst of the type described above
  • FC2 a similar catalyst, except that the tin oxide was omitted

Landscapes

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

Abstract

Catalyseur composé d'or, d'un oxyde de métal de transition avec lequel l'or forme un complexe et d'un oxyde d'étain capturé sur un support d'oxyde composé d'un mélange d'oxyde de cérium et de dioxyde de titane. L'oxyde d'étain est présent en quantité inférieure à 0,4 % en poids du catalyseur. On peut utiliser ce catalyseur, de façon spécifique, pour l'oxydation sélective d'oxyde de carbone dans un mélange d'hydrogène et d'oxyde de carbone.
EP00912846A 1999-04-01 2000-03-31 Oxydation catalytique selective de co en presence de h2 Withdrawn EP1165229A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
ZA992510 1999-04-01
ZA9902510 1999-04-01
PCT/IB2000/000390 WO2000059631A1 (fr) 1999-04-01 2000-03-31 Oxydation catalytique selective de co en presence de h2

Publications (1)

Publication Number Publication Date
EP1165229A1 true EP1165229A1 (fr) 2002-01-02

Family

ID=25587657

Family Applications (1)

Application Number Title Priority Date Filing Date
EP00912846A Withdrawn EP1165229A1 (fr) 1999-04-01 2000-03-31 Oxydation catalytique selective de co en presence de h2

Country Status (7)

Country Link
EP (1) EP1165229A1 (fr)
JP (1) JP2002541043A (fr)
AU (1) AU767170B2 (fr)
CA (1) CA2368378A1 (fr)
IL (1) IL145713A0 (fr)
RU (1) RU2001129358A (fr)
WO (1) WO2000059631A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008006210A1 (fr) * 2006-07-11 2008-01-17 Tekion, Inc. Catalyseurs incluant de l'oxyde métallique pour piles à combustible organiques
CN100500293C (zh) * 2007-04-13 2009-06-17 中国科学院山西煤炭化学研究所 一种CeO2-CoOx复合氧化物载体及其制备方法

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08295502A (ja) * 1995-04-25 1996-11-12 Agency Of Ind Science & Technol 金触媒による水素含有ガス中の一酸化炭素除去方法
BG62687B1 (bg) * 1997-05-15 2000-05-31 "Ламан-Консулт"Оод Златен катализатор за окисление на въглероден оксид и въглеводороди, редуциране на азотни оксиди иразлагане на озон

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO0059631A1 *

Also Published As

Publication number Publication date
IL145713A0 (en) 2002-07-25
JP2002541043A (ja) 2002-12-03
AU3448700A (en) 2000-10-23
AU767170B2 (en) 2003-11-06
CA2368378A1 (fr) 2000-10-12
WO2000059631A1 (fr) 2000-10-12
RU2001129358A (ru) 2004-01-27

Similar Documents

Publication Publication Date Title
US7384986B2 (en) Process for the selective methanation of carbonmonoxide (CO) contained in a hydrogen-rich reformate gas
JP2004525047A (ja) 非発火性の水−気体転化反応用触媒
JP5182850B2 (ja) ペロブスカイト型複合酸化物
US20020045538A1 (en) CdZnMS photocatalyst including cations for water decomposition and preparation thereof and method for producing hydrogen by use of the same
US20080241038A1 (en) Preparation of manganese oxide-ferric oxide-supported nano-gold catalyst and using the same
JP2008155111A (ja) 耐酸性電極触媒
JP2001522122A (ja) 燃料電池用金触媒
EP2905260A1 (fr) Procédé de production d'oxyde composite et de catalyseur d'oxyde composite
US20080193354A1 (en) Preparation of manganese oxide-cerium oxide-supported nano-gold catalyst and the application thereof
JP2005050760A (ja) 固体高分子電解質型燃料電池アノード電極触媒
KR101410856B1 (ko) Ｃｕ, Ｍｎ 및 선택적으로 적어도 하나의 희토류 원소를 포함하는 혼합 산화물 촉매로 연료 전지의 양극 폐가스로부터 ＣＯ, Ｈ2 및/또는 ＣＨ4를 제거하는 방법
JP2009101257A (ja) バーミキュライト（Ｅｘｐａｎｄｅｄｖｅｒｍｉｃｕｌｉｔｅ）を担体に用いた一酸化炭素選択酸化触媒
AU767170B2 (en) Selective catalytic oxidation of CO in presence of H2
KR20010079869A (ko) 수소 함유 가스중의 일산화탄소의 선택적 산화용 촉매
WO2022186232A1 (fr) Procédé de réduction électrochimique, catalyseur et procédé de production d'un catalyseur
KR100286425B1 (ko) 용융 탄산염 연료 전지용 개질 촉매 및 그의 제조 방법
US6548034B2 (en) Process for reducing concentration of carbon monoxide in hydrogen-containing gas
JP2006346535A (ja) Ｃｏ除去触媒及び燃料電池システム
KR100460433B1 (ko) 개질가스 정제용 촉매 및 이를 이용하여 수소가 풍부한개질가스 내의 일산화탄소를 선택적으로 제거하는 방법
JP3914984B2 (ja) 燃料改質ガスの水性ガスシフト反応用触媒
TWI398298B (zh) 奈米金承載於氧化銅及二氧化鈦觸媒之製法及其在選擇性一氧化碳氧化之應用
JP2008161742A (ja) 水素ガス中の一酸化炭素除去用触媒
JP4264514B2 (ja) ジメチルエーテル改質用触媒およびこれを用いる水素含有ガスの製造方法
JP2003251181A (ja) 水素ガス中の一酸化炭素除去用触媒
TWI469830B (zh) 奈米金承載於氧化鐵及二氧化鈦觸媒之製法及其在選擇性一氧化碳氧化之應用

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20011016

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE

AX Request for extension of the european patent

Free format text: AL;LT;LV;MK;RO;SI

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20031022