# US 7,744,849 B2 · Platinum-alkali/alkaline-earth catalyst formulations for hydrogen generation

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- Number: US 7,744,849 B2
- Document ID: US7744849B2
- Status: Granted
- Kind: B2
- Application number: 10/739,955
- Filed: 2003-12-18
- Published: 2004-09-23
- Granted: 2010-06-29
- Earliest claimed: 2002-12-20
- Assignees: Honda Giken Kogyo Kabushiki Kaisha; Freeslate, Inc.
- Inventors: Alfred Hagemeyer; Raymond E. Carhart; Karin Yaccato; Andreas Lesik; Christopher James Brooks; Cory Bernard Phillips
- Web page: https://patentgrep.com/patent/US7744849B2

## CPC

- B01J 23/652: Chromium, molybdenum or tungsten
- B01J 23/58: with alkali- or alkaline earth metals
- B01J 23/63: with rare earths or actinides
- B01J 23/648: Vanadium, niobium or tantalum {or polonium}
- B01J 23/6562: {Manganese}
- B01J 23/8946: {with alkali or alkaline earth metals}
- C01B 3/16: using catalysts
- C01B 2203/00: Integrated processes for the production of hydrogen or synthesis gas
- C01B 2203/0283: containing a CO-shift step, i.e. a water gas shift step
- C01B 2203/1011: Packed bed of catalytic structures, e.g. particles, packing elements
- C01B 2203/1023: Catalysts in the form of a monolith or honeycomb
- C01B 2203/1041: Composition of the catalyst
- C01B 2203/1047: Group VIII metal catalysts
- C01B 2203/1052: Nickel or cobalt catalysts
- C01B 2203/107: Platinum catalysts
- C01B 2203/1076: Copper or zinc-based catalysts
- C01B 2203/1082: Composition of support materials
- C01B 2203/1088: Non-supported catalysts
- C01B 2203/1094: Promotors or activators
- C01B 2203/1614: Controlling the temperature
- Y02P 20/52: using catalysts, e.g. selective catalysts
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- C01B: NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; {METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C}
- Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS

## Abstract

A method and catalysts and fuel processing apparatus for producing a hydrogen-rich gas, such as a hydrogen-rich syngas are disclosed. According to the method a CO-containing gas, such as a syngas, contacts a water gas shift catalyst in the presence of water, preferably at a temperature of less than about 450° C. to produce a hydrogen-rich gas, such as a hydrogen-rich syngas. Also disclosed is a water gas shift catalyst comprising: a) Pt, its oxides or mixtures thereof; b) at least one of Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, their oxides and mixtures thereof; and c) at least one of Sc, Y, Ti, Zr, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Ir, Ni, Pd, La, Ce, Pr, Nd, Sm, Eu, their oxides and mixtures thereof. The WGS catalyst may be supported on a carrier, such as any one member or a combination of alumina, zirconia, titania, ceria, magnesia, lanthania, niobia, yttria and iron oxide. Fuel processors containing such water gas shift catalysts are also disclosed.

## Claims

### Claim 1

A method for producing a hydrogen-rich gas which comprises:
contacting a CO-containing gas with a water gas shift catalyst in the presence of water at a temperature of not more than about 450° C.,
wherein the water gas shift catalyst consists essentially of:
a) Pt, its oxides or mixtures thereof;
b) at least one of Li, Na, K, Rb, Cs, their oxides and mixtures thereof; and
c) at least one of Sc, Y, Ti, Zr, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Ir, Ni, Pd, La, Ce, Pr, Nd, Sm, Eu, their oxides and mixtures thereof.

### Claim 2 (depends on 1)

The method according to claim 1, wherein the CO-containing gas is a syngas.

### Claim 3 (depends on 1)

The method according to claim 1, wherein element (b) consists essentially of at least one of Li, Na, K, their oxides and mixtures thereof.

### Claim 4 (depends on 3)

The method according to claim 3, wherein element (c) consists essentially of Fe, its oxides or mixtures thereof.

### Claim 5 (depends on 3)

The method according to claim 3, wherein the water gas shift catalyst is selected from the group consisting of:
Pt, its oxides or mixtures thereof, Li, its oxides or mixtures thereof, and Fe, its oxides or mixtures thereof;
Pt, its oxides or mixtures thereof, Li, its oxides or mixtures thereof, and Co, its oxides or mixtures thereof;
Pt, its oxides or mixtures thereof, Li, its oxides or mixtures thereof, and Ce, its oxides or mixtures thereof;
Pt, its oxides or mixtures thereof, Na, its oxides or mixtures thereof, and Zr, its oxides or mixtures thereof;
Pt, its oxides or mixtures thereof, Na, its oxides or mixtures thereof, and La, its oxides or mixtures thereof;
Pt, its oxides or mixtures thereof, Na, its oxides or mixtures thereof, and Y, its oxides or mixtures thereof;
Pt, its oxides or mixtures thereof, Na, its oxides or mixtures thereof, and Ce, its oxides or mixtures thereof;
Pt, its oxides or mixtures thereof, Na, its oxides or mixtures thereof, and Mo, its oxides or mixtures thereof;
Pt, its oxides or mixtures thereof, Na, its oxides or mixtures thereof, and Fe, its oxides or mixtures thereof;
Pt, its oxides or mixtures thereof, Na, its oxides or mixtures thereof, and Co, its oxides or mixtures thereof;
Pt, its oxides or mixtures thereof, Na, its oxides or mixtures thereof, and Mn, its oxides or mixtures thereof;
Pt, its oxides or mixtures thereof, Na, its oxides or mixtures thereof, Zr, its oxides or mixtures thereof, and Co, its oxides or mixtures thereof;
Pt, its oxides or mixtures thereof, K, its oxides or mixtures thereof, and Ce, its oxides or mixtures thereof;
Pt, its oxides or mixtures thereof, K, its oxides or mixtures thereof, and Fe, its oxides or mixtures thereof; and
Pt, its oxides or mixtures thereof, K, its oxides or mixtures thereof, and Co, its oxides or mixtures thereof.

### Claim 6 (depends on 1)

The method according to claim 1, wherein the water gas shift catalyst is supported in a carrier selected from alumina, zirconia, titania, ceria, magnesia, lanthania, niobia, zeolite, perovskite, silica clay, yttria, iron oxide or mixtures thereof.

### Claim 7 (depends on 6)

The method according to claim 6, wherein element (b) consists essentially of at least one of Li, Na, K, their oxides or mixtures thereof.

### Claim 8 (depends on 7)

The method according to claim 7, wherein element (c) consists essentially of Fe, its oxides or mixtures thereof.

### Claim 9 (depends on 7)

The method according to claim 7, wherein the supported water gas shift catalyst is selected from:
Pt, its oxides or mixtures thereof, Li, its oxides or mixtures thereof, and Fe, its oxides or mixtures thereof, on ZrO2;
Pt, its oxides or mixtures thereof, Li, its oxides or mixtures thereof, and Co, its oxides or mixtures thereof, on ZrO2;
Pt, its oxides or mixtures thereof, Li, its oxides or mixtures thereof, and Ce, its oxides or mixtures thereof, on ZrO2;
Pt, its oxides or mixtures thereof, Na, its oxides or mixtures thereof, and Zr, its oxides or mixtures thereof, on Al2O3;
Pt, its oxides or mixtures thereof, Na, its oxides or mixtures thereof, and La, its oxides or mixtures thereof, on Al2O3;
Pt, its oxides or mixtures thereof, Na, its oxides or mixtures thereof, and Y, its oxides or mixtures thereof, on Al2O3;
Pt, its oxides or mixtures thereof, Na, its oxides or mixtures thereof, and Ce, its oxides or mixtures thereof, on Al2O3;
Pt, its oxides or mixtures thereof, Na, its oxides or mixtures thereof, and Mo, its oxides or mixtures thereof, on Al2O3;
Pt, its oxides or mixtures thereof, Na, its oxides or mixtures thereof, and Fe, its oxides or mixtures thereof, on Al2O3;
Pt, its oxides or mixtures thereof, Na, its oxides or mixtures thereof, and Co, its oxides or mixtures thereof, on Al2O3;
Pt, its oxides or mixtures thereof, Na, its oxides or mixtures thereof, and Mn, its oxides or mixtures thereof, on Al2O3;
Pt, its oxides or mixtures thereof, Na, its oxides or mixtures thereof, Zr, its oxides or mixtures thereof, and Co, its oxides or mixtures thereof, on Al2O3;
Pt, its oxides or mixtures thereof, Na, its oxides or mixtures thereof, and Fe, its oxides or mixtures thereof, on ZrO2;
Pt, its oxides or mixtures thereof, Na, its oxides or mixtures thereof, and Co, its oxides or mixtures thereof, on ZrO2;
Pt, its oxides or mixtures thereof, Na, its oxides or mixtures thereof, and Ce, its oxides or mixtures thereof, on ZrO2;
Pt, its oxides or mixtures thereof, K, its oxides or mixtures thereof, and Fe, its oxides or mixtures thereof, on ZrO2;
Pt, its oxides or mixtures thereof, K, its oxides or mixtures thereof, and Co, its oxides or mixtures thereof, on ZrO2; and
Pt, its oxides or mixtures thereof, K, its oxides or mixtures thereof, and Ce, its oxides or mixtures thereof, on ZrO2.

### Claim 10 (depends on 9)

The method according to claim 9, wherein the Al2O3 is γ-Al2O3.

### Claim 11 (depends on 6)

The method according to claim 6, wherein the carrier comprises at least one member selected from the group consisting of iron oxide zirconia, titania and ceria.

### Claim 12 (depends on 11)

The method according to claim 11, wherein the carrier comprises zirconia.

### Claim 13 (depends on 1)

The method according to claim 1, wherein the CO-containing gas is contacted with the water gas shift catalyst at a temperature ranging from about 150° C. to about 450° C.

### Claim 14 (depends on 13)

The method according to claim 13, wherein the CO-containing gas is contacted with a water gas shift catalyst at a temperature ranging from more than about 350° C. to up to about 450° C.

### Claim 15 (depends on 13)

The method according to claim 13, wherein the CO-containing gas is contacted with a water gas shift catalyst at a temperature ranging from about 250° C. to up to about 350° C.

### Claim 16 (depends on 13)

The method according to claim 13, wherein the CO-containing gas is contacted with a water gas shift catalyst at a temperature ranging from about 150° C. to up to about 250° C.

### Claim 17 (depends on 1)

The method according to claim 1, wherein the CO-containing gas is contacted with the water gas shift catalyst at a pressure of no more than about 75 bar.

### Claim 18 (depends on 17)

The method according to claim 17, wherein the CO-containing gas is contacted with the water gas shift catalyst at a pressure of no more than about 50 bar.

### Claim 19 (depends on 17)

The method according to claim 17, wherein the CO-containing gas is contacted with the water gas shift catalyst at a pressure of no more than about 15 bar.

### Claim 20 (depends on 17)

The method according to claim 17, wherein the CO-containing gas is contacted with the water gas shift catalyst at a pressure of no more than about 1 bar.

### Claim 21 (depends on 1)

The method according to claim 1, wherein the water gas shift catalyst comprises about 0.01 wt. % to about 10 wt. %, with respect to the total weight of all catalyst components plus the support material, of each Group 8, 9 or 10 element present in the water gas shift catalyst.

### Claim 22 (depends on 21)

The method according to claim 21, wherein the water gas shift catalyst comprises about 0.01 wt. % to about 2 wt. % of each Group 8, 9 or 10 element present in the water gas shift catalyst.

### Claim 23 (depends on 22)

The method according to claim 22, wherein the water gas shift catalyst comprises about 0.05 wt. % to about 0.5 wt. % of each Group 8, 9 or 10 element present in the water gas shift catalyst.

### Claim 24 (depends on 1)

The method according to claim 1, wherein the water gas shift catalyst comprises about 0.05 wt. % to about 20 wt. %, with respect to the total weight of all catalyst components plus the support material, of each lanthanide element present in the water gas shift catalyst.