High purity, high pressure hydrogen production with in-situ CO2 and sulfur capture in a single stage reactor

• US 7,837,975 B2
• Filed: 03/24/2009
• Issued: 11/23/2010
• Est. Priority Date: 09/25/2006
• Status: Active Grant

• Current Assignee: Ohio State University
• Original Assignee: Ohio State University
• Inventors: Iyer, Mahesh V., Fan, Liang-Shih, Ramkumar, Shwetha
• Primary Examiner(s): LANGEL, WAYNE A
• Application Number:
  US12/409,843
• Publication Number:
  US 20090263316A1
• Time in Patent Office: 609 Days
• Field of Search: 423/650, 423/651, 423/652, 423/653, 423/654, 423/648.1, 423/655, 423/656, 252/373
• US Class Current: 423/652
• CPC Class Codes: C01B 2203/0233 the reforming step being a steam reforming step
• CPC Class Codes: C01B 2203/0238 the reforming step being a carbon dioxide reforming step
• CPC Class Codes: C01B 2203/0261 containing a catalytic partial oxidation step [CPO]
• CPC Class Codes: C01B 2203/0283 containing a CO-shift step, i.e. a water gas shift step
• CPC Class Codes: C01B 2203/0425 In-situ adsorption process during hydrogen production
• CPC Class Codes: C01B 2203/043 Regenerative adsorption process in two or more beds, one for adsorption, the other for regeneration
• CPC Class Codes: C01B 2203/0465 Composition of the impurity
• CPC Class Codes: C01B 2203/0475 the impurity being carbon dioxide
• CPC Class Codes: C01B 2203/0485 the impurity being a sulfur compound
• CPC Class Codes: C01B 2203/1041 Composition of the catalyst
• CPC Class Codes: C01B 2203/86 Carbon dioxide sequestration
• CPC Class Codes: C01B 3/38 using catalysts
• CPC Class Codes: C01B 3/386 Catalytic partial combustion
• CPC Class Codes: C01B 3/56 by contacting with solids; Regeneration of used solids C01B3/508 takes precedence
• CPC Class Codes: C10J 2300/093 Coal
• CPC Class Codes: C10J 2300/0996 Calcium-containing inorganic materials, e.g. lime
• CPC Class Codes: C10J 2300/1659 to liquid hydrocarbons Fischer-Tropsch process C10G2/00
• CPC Class Codes: C10K 3/04 reducing the carbon monoxide content , e.g. water-gas shift [WGS]
• CPC Class Codes: Y02P 30/00 Technologies relating to oil refining and petrochemical industry

Abstract

A process for producing hydrogen, comprising the steps of: (a) gasifying a fuel into a raw synthesis gas comprising CO, hydrogen, steam and sulfur and halide contaminants in the form of H₂S, COS and HX, where X is a halide; (b) passing the raw synthesis gas through a water gas shift reactor (WGSR) into which CaO and steam are injected, the CaO reacting with the shifted gas to remove CO₂, sulfur and halides in a solid-phase calcium-containing product comprising CaCO₃, CaS and CaX₂; (c) separating the solid-phase calcium-containing product from an enriched gaseous hydrogen product; and (d) regenerating the CaO by calcining the solid-phase calcium-containing product at a condition selected from the group consisting of: in the presence of steam, in the presence of CO₂, in the presence of synthesis gas, in the presence of H₂ and O₂, under partial vacuum, and combinations thereof. The CaO may have a surface area of at least 12.0 m2/g and a pore volume of at least 0.015 cm3/g, the CaO having a sorption capacity of at least about 70 grams of CO2 per kilogram of CaO.

Claims

1. A process for producing hydrogen, comprising the steps of:

gasifying a fuel into a raw synthesis gas comprising CO, hydrogen, steam and sulfur and halide contaminants in the form of H₂S, COS and HX, where X is a halide;

injecting said raw synthesis gas, CaO and steam simultaneously into a water gas shift reactor (WGSR) wherein said raw synthesis gas transforms into a shifted gas;

allowing said shifted gas to react with said CaO in said water gas shift reactor so as to remove sulfur and halides in a solid-phase calcium-containing product comprising CaCO₃, CaS and CaX₂;

separating the solid-phase calcium-containing product from an enriched gaseous hydrogen product; and

regenerating the CaO by calcining the solid-phase calcium-containing product at a condition selected from the group consisting of;

in the presence of steam, in the presence of CO₂, in the presence of synthesis gas, in the presence of H₂ and O₂, under partial vacuum, and combinations thereof.

2. The process of claim 1 additionally comprising the step of:

recycling at least a portion of a product stream from a Fischer-Tropsch reactor, fed by the WGSR, so as to introduce a chemical species selected from the group consisting of;

methane, C1-C4 hydrocarbons, CO, hydrogen and combinations thereof back into the WGSR.

3. The process of claim 1 wherein said WSGR has disposed therein a catalyst.

4. The process of claim 3 wherein said catalyst includes a material selected from the group consisting of:

Fe, Cu, Co, Mo, W, Cs, Pt, Ph, Pd, other precious metal catalysts, oxides thereof, sulfides thereof, and combinations thereof.

5. The process of claim 2 wherein said WSGR has disposed therein a catalyst.

6. The process of claim 1 wherein said enriched hydrogen product has a purity in the range of from about 70% to about 99.99% H2, a temperature in the range of from about 400 to about 1000 C, and a pressure in the range of from about 1 to about 100 atmosphere.

7. The process of claim 1 wherein said CaO has a surface area of at least 12.0 m2/g and a pore volume of at least 0.015 cm3/g, said CaO having a sorption capacity of at least about 70 grams of CO2 per kilogram of CaO.

8. The process of claim 2 wherein said CaO has a surface area of at least 12.0 m2/g and a pore volume of at least 0.015 cm3/g, said CaO having a sorption capacity of at least about 70 grams of CO2 per kilogram of CaO.

9. A process for producing hydrogen, comprising the steps of:

reforming a gaseous hydrocarbon fuel in the presence of CaO and steam to remove CO2, sulfur and halide contaminants in the form of H₂S, COS and HX, where X is a halide, in a solid-phase calcium-containing product comprising CaCO₃, CaS and CaX₂, thereby producing a mixture of CO and hydrogen;

separating the solid-phase calcium-containing product from an enriched gaseous hydrogen product; and

regenerating the CaO by calcining the solid-phase calcium-containing product at a condition selected from the group consisting of;

in the presence of steam, in the presence of CO₂, in the presence of synthesis gas, in the presence of H₂ and O₂, under partial vacuum, and combinations thereof.

10. The process of claim 9 additionally comprising the step of:

recycling at least a portion of a product stream from a Fischer-Tropsch reactor, fed by the reformer, so as to introduce a chemical species selected from the group consisting of;

methane, C1-C4 hydrocarbons, CO, hydrogen and combinations thereof back into the reformer.

11. The process of claim 9 wherein said reforming step is conducted in the presence of a catalyst.

12. The process of claim 11 wherein said catalyst is selected from the group consisting of:

Ni, Pt, Rh, Pd, Ru, W, Mo, oxide thereof, carbides thereof, and sulfides thereof.

13. The process of claim 10 wherein said reforming step is conducted in the presence of a catalyst.

14. The process of claim 9 wherein said enriched hydrogen product has a purity in the range of from about 70% to about 99.99% H2, a temperature in the range of from about 400 to about 1000 C, and a pressure in the range of from about 1 to about 100 atmosphere.

15. The process of claim 9 wherein said CaO has a surface area of at least 12.0 m2/g and a pore volume of at least 0.015 cm3/g, said CaO having a sorption capacity of at least about 70 grams of CO2 per kilogram of CaO.

16. The process of claim 10 wherein said CaO has a surface area of at least 12.0 m2/g and a pore volume of at least 0.015 cm3/g, said CaO having a sorption capacity of at least about 70 grams of CO2 per kilogram of CaO.

17. A process for producing hydrogen, comprising the steps of:

at least partially oxidizing a fuel into a raw gas comprising CO, hydrogen, steam and sulfur and halide contaminants in the form of H₂S, COS and HX, where X is a halide;

injecting said raw synthesis gas, CaO and steam simultaneously into a water gas shift reactor (WGSR) wherein said raw synthesis gas transforms into a shifted gas;

allowing said shifted gas to react with said CaO in said water gas shift reactor so as to remove sulfur and halides in a solid-phase calcium-containing product comprising CaCO₃, CaS and CaX₂;

separating the solid-phase calcium-containing product from an enriched gaseous hydrogen product; and

regenerating the CaO by calcining the solid-phase calcium-containing product at a condition selected from the group consisting of;

in the presence of steam, in the presence of CO₂, in the presence of synthesis gas, in the presence of H₂ and O₂, under partial vacuum, and combinations thereof.

18. The process of claim 17 wherein said WSGR has disposed therein a catalyst.

19. The process of claim 18 wherein said catalyst includes a material selected from the group consisting of:

Fe, Cu, Co, Mo, W, Cs, Pt, Ph, Pd, other precious metal catalysts, oxides thereof, sulfides thereof, and combinations thereof.

20. The process of claim 17 wherein said enriched hydrogen product has a purity in the range of from about 70% to about 99.99% H2, a temperature in the range of from about 400 to about 1000 C, and a pressure in the range of from about 1 to about 100 atmosphere.

21. The process of claim 17 wherein said CaO has a surface area of at least 12.0 m2/g and a pore volume of at least 0.015 cm3/g, said CaO having a sorption capacity of at least about 70 grams of CO2 per kilogram of CaO.