Sulfur-tolerant and carbon-resistant catalysts

• US 20080265212A1
• Filed: 01/17/2008
• Published: 10/30/2008
• Est. Priority Date: 01/19/2007
• Status: Active Grant

• Current Assignee: Penn State Research Foundation
• Original Assignee: Penn State Research Foundation
• Inventors: Zheng, Jian, Song, Chunshan, Wang, Xiaoxing, Strohm, James J., Gu, Weidong, Xie, Chao
• Granted Patent: US 9,387,470 B2
• Time in Patent Office: Days
• US Class Current: 252/373
• CPC Class Codes: B01J 21/04 Alumina
• CPC Class Codes: B01J 23/60 with zinc, cadmium or mercury
• CPC Class Codes: B01J 23/62 with gallium, indium, thallium, germanium, tin or lead
• CPC Class Codes: B01J 23/6525 Molybdenum
• CPC Class Codes: B01J 23/89 combined with noble metals
• CPC Class Codes: B01J 23/8913 Cobalt and noble metals
• CPC Class Codes: B01J 23/892 Nickel and noble metals
• CPC Class Codes: B01J 23/894 with rare earths or actinides
• CPC Class Codes: B01J 23/8946 with alkali or alkaline earth metals
• CPC Class Codes: B01J 23/896 with gallium, indium or thallium
• CPC Class Codes: B01J 37/0009 Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
• CPC Class Codes: B01J 37/0207 Pretreatment of the support
• CPC Class Codes: B01J 37/0236 Drying, e.g. preparing a suspension, adding a soluble salt and drying
• CPC Class Codes: C01B 2203/0233 the reforming step being a steam reforming step
• CPC Class Codes: C01B 2203/0244 the reforming step being an autothermal reforming step, e.g. secondary reforming processes
• CPC Class Codes: C01B 2203/066 with fuel cells
• CPC Class Codes: C01B 2203/1047 Group VIII metal catalysts
• CPC Class Codes: C01B 2203/1058 Nickel catalysts
• CPC Class Codes: C01B 2203/1082 Composition of support materials
• CPC Class Codes: C01B 2203/1211 Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
• CPC Class Codes: C01B 3/38 : using catalysts
• CPC Class Codes: C01B 3/382 : Multi-step processes
• CPC Class Codes: C01B 3/40 : characterised by the catalyst
• CPC Class Codes: Y02P 20/52 : using catalysts, e.g. selective catalysts

Abstract

The invention relates to novel bimetallic and trimetallic catalysts, their manufacture and use in both steam reforming and oxidative steam reforming of liquid fuels such as jet fuels, diesel fuels and gasoline to produce synthesis gas and/or hydrogen for fuel cell applications. The invention further relates to manufacture of synthesis gas and/or hydrogen gas for chemicals synthesis and fuel processing. The catalysts have high sulfur tolerance and carbon resistance when used in steam reforming and/or oxidative steam reforming of heavy hydrocarbon fuels.

Claims

1. A sulfur-tolerant and carbon-resistant noble-metal based bimetallic catalyst of the formula M1(x)M2(Y) on a R stabilized alumina support where 0.5% ≦

x≦

5% and 2% ≦

y≦

20% where all amounts are based on the total weight of the catalyst including support, and where M1 is selected from the group consisting of Rh, Ru, Pt or mixtures thereof and M2 is selected from the group consisting of Ni, Co, Fe, Mo, Cu, Zn or mixtures thereof and where R is selected from the group consisting of Ce, Zr, Ga, La, Y or mixtures thereof.

2. The catalyst of claim 1 where R is Ce, M1 is Rh and M2 is Ni.

3. The catalyst of claim 1 where R is Zr, M1 is Rh and M2 is Ni.

4. The catalyst of claim 1 where R is Ga, M1 is Rh and M2 is Ni.

5. The catalyst of claim 1 where R is La, M1 is Rh and M2 is Ni.

6. The catalyst of claim 1 further comprising Ca.

7. The catalyst of claim 1 further comprising K.

8. A sulfur-tolerant and carbon-resistant noble-metal based trimetallic catalyst of the formula M1(x)M2(y)M3(z) on a R stabilized alumina support where 0.5%≦

x≦

5%, 2%≦

y≦

20% and 2%≦

z≦

20% where all amounts are based on the total weight of the catalyst including support, and where M1 is selected from the group consisting of Rh, Ru, Pt or mixtures thereof, M2 and M3 are different and each is selected from the group consisting of Ni, Co, Fe, Mo, Cu, Zn or mixtures and R is selected from the group consisting of Ce, Zr, Ga, La, Y or mixtures thereof.

9. The catalyst of claim 8 where M1 is Rh, M2 is Ni, M3 is Co and R is Ce.

10. The catalyst of claim 8 where M1 is Rh, M2 is Ni, M3 is Co and R is Zr.

11. A method of steam reforming of a hydrocarbon fuel containing sulfur comprising,

heating any of bimetallic catalysts of the formula M1(x)M2(y) where 0.5% ≦

x≦

5% and 2% ≦

y≦

20% where all amounts are based on the weight of the catalyst including support and where M1 is selected from the group consisting of Rh, Ru, Pt or mixtures thereof and M2 is selected from the group consisting of Ni, Co, Fe, Mo, Cu, Zn or mixtures thereof or trimetallic catalyst of the formula M1(x)M2(y)M3(z) on a R stabilized alumina where 0.5%≦

x≦

5%, 2%≦

y≦

20% and 2%≦

z≦

20% where all amounts are based on the total weight of the catalyst including support, and where M1 is selected from the group consisting of Rh, Ru, Pt or mixtures thereof, M2 and M3 are different and each is selected from the group consisting of Ni, Co, Fe, Mo, Cu, Zn or mixtures and R is selected from the group consisting of Ce, Zr, Ga, La, Y or mixtures thereof in a reducing atmosphere to yield an activated catalyst, and then passing a hydrocarbon fuel containing sulfur over the activated catalyst at an elevated temperature to produce hydrogen and/or synthesis gas for applications.

12. The method of claim 11 wherein the catalysts is supported on a R stabilized alumina where R is selected from the group consisting of Ce, Zr, Ga, La, Y or mixtures thereof.

13. The method of claim 12 wherein the catalyst is the bimetallic catalyst of the formula M1(x)M2(y) where M1 is Rh and M2 is Ni.

14. The method of claim 12 wherein M1 is Rh, M2 is Ni and R is Zr.

15. The method of claim 12 wherein M1 is Rh, M2 is Ni and R is Ga

16. The method of claim 12 wherein M1 is Rh, M2 is Ni and R is La.

17. The method of claim 12 wherein M1 is Rh, M2 is Ni and R is Ce.

18. The method of claim 12 wherein the catalyst is the trimetallic catalyst of the formula M1(x)M2(y)M3(z) where M1 is Rh, M2 is Ni, M3 is Co and R is Ce.

19. The method of claim 12 wherein the catalyst is the trimetallic catalyst of the formula M1(x)M2(y)M3(z) where M1 is Rh, M2 is Ni, M3 is Co