AU767170B2 - Selective catalytic oxidation of CO in presence of H2 - Google Patents
Selective catalytic oxidation of CO in presence of H2 Download PDFInfo
- Publication number
- AU767170B2 AU767170B2 AU34487/00A AU3448700A AU767170B2 AU 767170 B2 AU767170 B2 AU 767170B2 AU 34487/00 A AU34487/00 A AU 34487/00A AU 3448700 A AU3448700 A AU 3448700A AU 767170 B2 AU767170 B2 AU 767170B2
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- AU
- Australia
- Prior art keywords
- oxide
- catalyst
- weight
- mixture
- 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.)
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Classifications
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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
- B01J23/89—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
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- 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)
Description
WO 00/59631 PCT/IB00/00390 -1- SELECTIVE CATALYTIC OXIDATION OF CO IN PRESENCE OF H2 BACKGROUND OF THE INVENTION 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 electronicconductor 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.
CONFIRMATION
COPY
WO 00/59631 PCT/IB00/00390 SUMMARY OF THE INVENTION According to the invention, 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.
According to another aspect of the invention, there is provided 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.
BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a graph showing CO oxidation of a gas containing CO, H 2 and 02; and Figure 2 is a graph showing H 2 oxidation of a gas containing CO, H 2 and 02.
DESCRIPTION OF EMBODIMENTS It has been found that 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 WO 00/59631 PCT/IB00/00390 -3monoxide 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 0
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 to 200 m 2 /g.
The catalyst of the invention may be made by methods described in the art.
Preferably, however, 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 2500C 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 2500C in the presence of oxygen.
WO 00/59631 PCT/IB00/00390 -4- An example of a preferred catalyst of the invention has the following composition (all percentages by weight): 83% CeO 2 TiO 2 0,3% Sn02 1% Au 1% Co, as an oxide.
The catalyst may be made as follows: 42g of CeO 2 and 8g TiO 2 are mixed for 10 minutes in an automatic mixer. The mixed oxides are dried at 120°C for 30 minutes and impregnated with 22,5ml of 0,4 molar Co(N0 3 2 and 10,5ml of 0,1 molar SnC/ 2 solutions at 500C. The so formed sludge is dried at 1200C for 12 hours and impregnated with 21ml of 0,13 molar HAuC.
4 The material is washed with water and dried at 120°C for 3 hours and calcined at 400°C for 30 minutes.
The catalyst is preferably made as follows: Stage One 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.
Solutions of cobalt nitrate and tin nitrate are introduced into a vessel and heated to 80°C. The heated mixture of cerium and titanium oxides, the support for the catalyst, is then added under constant stirring.
WO 00/59631 PCT/IBOO/00390 The pressure in the mixing vessel is reduced and water is distilled off at a constant temperature of 65°C over a 4 hour period.
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.
Stage Two 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 HN0 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 600C over a 60 minute period.
The slurry is filtered producing a filtered catalyst. The filtered catalyst is reslurried 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 -35i.m and calcined at 450°C under 5% 02 for 3 hours.
The catalyst is stored prior to use.
P:\OPERRdU2110Scplt\344H7400 msFdo-I I SCptonbr, 2003 -6- The selective oxidation of carbon monoxide in a mixture containing 0.5 percent CO, 2 percent H 2 0,8 percent 02, the balance being nitrogen, was evaluated using a catalyst of the type described above, designated FC6, and a similar catalyst, except that the tin oxide was omitted, designated FC2. The oxidation of CO is shown in Figure 1 and the oxidation of H 2 is shown in Figure 2.
It will be noted from the graphs that the carbon monoxide oxidation of the catalyst without the tin oxide achieved excellent carbon monoxide oxidation, but also significant hydrogen oxidation, particularly at higher temperatures. In contrast, at higher temperatures, the oxidation of the carbon monoxide in the presence of the catalyst of the invention approached that of the other catalyst but with significantly lower hydrogen oxidation.
Throughout this specification and the claims which follow, unless the context requires otherwise, the word "comprise", and variations such as "comprises" and "comprising", will be understood to imply the inclusion of a stated integer or step or group of integers or steps but not the exclusion of any other integer or step or group of integers or steps.
0..0
Claims (14)
1. A method of selectively oxidising carbon monoxide in a carbon monoxide/hydrogen mixture comprises contacting the mixture with a suitable oxidant in the presence of a catalyst which comprises gold, a transition metal 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.
2. A method according to claim 1 wherein the transition metal oxide is cobalt oxide.
3. A method according to claim 1 or claim 2, wherein the ratio of cerium oxide to titanium dioxide is in the range 4:1 to 5:1 on a weight basis.
4. A method according to any one of claims 1 to 3, wherein the tin oxide is present in an amount of 0,03 to 0,3 percent by weight of the catalyst.
A method according to claim 1, wherein the catalyst has the composition (all percentages being by weight): 83 CeO 2 TiO 2 0,3% SnO 2 1% Au 1% Co, as an oxide.
6. A method according to any one of the preceding claims wherein the oxidant is oxygen. WO 00/59631 PCT/IB00/00390 -8-
7. A method according to any one of the preceding claims wherein the oxidation takes place at a temperature in the range 80 to 130°C.
8. A catalyst comprising gold, a transition metal oxide to which the gold is complexed. and tin oxide captured on an oxide support comprising a mixture of cerium oxide and titanium oxide, the tin oxide being present in an amount of less than 0,4% by weight of the catalyst.
9. A catalyst according to claim 8, wherein the transition metal oxide is cobalt oxide.
A catalyst according to claim 8 or claim 9, wherein the ratio of cerium oxide to titanium dioxide is in the range 4:1 to 5:1 on a weight basis.
11. A catalyst according to any one of claims 8 to 10, wherein the tin oxide is present in an amount of 0,03 to 0,3 percent by weight of the catalyst.
12. A catalyst according to claim 8, which has the composition (all percentages by weight): 83 CeO 2 TiO 2 0,3% SnO 2 1% Au 1% Co, as an oxide.
13. A method according to claim 1, substantially as herein described.
14. A catalyst according to claim 8. substantially as herein described.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| ZA99/2510 | 1999-04-01 | ||
| ZA992510 | 1999-04-01 | ||
| PCT/IB2000/000390 WO2000059631A1 (en) | 1999-04-01 | 2000-03-31 | Selective catalytic oxidation of co in presence of h2 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| AU3448700A AU3448700A (en) | 2000-10-23 |
| AU767170B2 true AU767170B2 (en) | 2003-11-06 |
Family
ID=25587657
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| AU34487/00A Ceased AU767170B2 (en) | 1999-04-01 | 2000-03-31 | Selective catalytic oxidation of CO in presence of H2 |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP1165229A1 (en) |
| JP (1) | JP2002541043A (en) |
| AU (1) | AU767170B2 (en) |
| CA (1) | CA2368378A1 (en) |
| IL (1) | IL145713A0 (en) |
| RU (1) | RU2001129358A (en) |
| WO (1) | WO2000059631A1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080014494A1 (en) * | 2006-07-11 | 2008-01-17 | Coca Iordache | Catalysts Including Metal Oxide For Organic Fuel Cells |
| CN100500293C (en) * | 2007-04-13 | 2009-06-17 | 中国科学院山西煤炭化学研究所 | Composite CeO2-CoOx oxide carrier and its preparation process |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08295502A (en) * | 1995-04-25 | 1996-11-12 | Agency Of Ind Science & Technol | Method for removing carbon monoxide in hydrogen-containing gas with gold catalyst |
| WO1998051401A1 (en) * | 1997-05-15 | 1998-11-19 | Laman Consultancy Limited | Gold based catalyst for exhaust gas purification |
-
2000
- 2000-03-31 EP EP00912846A patent/EP1165229A1/en not_active Withdrawn
- 2000-03-31 AU AU34487/00A patent/AU767170B2/en not_active Ceased
- 2000-03-31 CA CA002368378A patent/CA2368378A1/en not_active Abandoned
- 2000-03-31 WO PCT/IB2000/000390 patent/WO2000059631A1/en active Search and Examination
- 2000-03-31 IL IL14571300A patent/IL145713A0/en unknown
- 2000-03-31 JP JP2000609184A patent/JP2002541043A/en active Pending
- 2000-03-31 RU RU2001129358/15A patent/RU2001129358A/en unknown
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08295502A (en) * | 1995-04-25 | 1996-11-12 | Agency Of Ind Science & Technol | Method for removing carbon monoxide in hydrogen-containing gas with gold catalyst |
| WO1998051401A1 (en) * | 1997-05-15 | 1998-11-19 | Laman Consultancy Limited | Gold based catalyst for exhaust gas purification |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2000059631A1 (en) | 2000-10-12 |
| IL145713A0 (en) | 2002-07-25 |
| JP2002541043A (en) | 2002-12-03 |
| AU3448700A (en) | 2000-10-23 |
| CA2368378A1 (en) | 2000-10-12 |
| EP1165229A1 (en) | 2002-01-02 |
| RU2001129358A (en) | 2004-01-27 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MK6 | Application lapsed section 142(2)(f)/reg. 8.3(3) - pct applic. not entering national phase | ||
| TH | Corrigenda |
Free format text: IN VOL 15, NO 4, PAGE(S) 702-705 UNDER THE HEADING APPLICATIONS LAPSED, REFUSED OR WITHDRAWN PLEASE DELETE ALL REFERENCE TO APPLICATION NO. 34487/00 |
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| FGA | Letters patent sealed or granted (standard patent) |