Integration of reforming/water splitting and electrochemical systems for power generation with integrated carbon capture

• US 9,371,227 B2
• Filed: 09/08/2010
• Issued: 06/21/2016
• Est. Priority Date: 09/08/2009
• Status: Active Grant

• Current Assignee: Ohio State Innovation Foundation (Ohio State University)
• Original Assignee: Ohio State Innovation Foundation (Ohio State University)
• Inventors: Fan, Liang-Shih, Li, Fanxing, Zeng, Liang, Sridhar, Deepak
• Primary Examiner(s): Barcena, Carlos
• Assistant Examiner(s): Nedialkova, Lilia V
• Application Number:
  US13/394,572
• Publication Number:
  US 20120171588A1
• Time in Patent Office: 2,113 Days
• US Class Current: 1/1
• CPC Class Codes: B01J 7/00 Apparatus for generating gases production of inert gas mixtures B01J19/14; for generating specific gases, see the relevant subclasses, e.g. C01B, C10J ; in "air bags" on vehicles B60R21/26; for starter gas F02C7/26; blasting cartridges for producing gas under pressure F42B3/04
• CPC Class Codes: C01B 2203/0216 containing a non-catalytic steam reforming step
• CPC Class Codes: C01B 2203/0222 containing a non-catalytic carbon dioxide reforming step
• 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 2203/066 with fuel cells
• CPC Class Codes: C01B 2203/0827 at least part of the fuel being a recycle stream
• CPC Class Codes: C01B 2203/148 involving a recycle stream to the feed of the process for making hydrogen or synthesis gas
• CPC Class Codes: C01B 3/063 Cyclic methods
• CPC Class Codes: C01B 3/34 by reaction of hydrocarbons with gasifying agents
• CPC Class Codes: C01B 3/344 using non-catalytic solid particles
• CPC Class Codes: C10J 2300/0916 Biomass
• CPC Class Codes: C10J 2300/093 Coal
• CPC Class Codes: C10J 2300/0959 Oxygen
• CPC Class Codes: C10J 2300/0993 Inert particles, e.g. as heat exchange medium in a fluidized or moving bed, heat carriers, sand
• CPC Class Codes: C10J 2300/1612 CO2-separation and sequestration, i.e. long time storage
• CPC Class Codes: C10J 2300/1646 integrated with a fuel cell
• CPC Class Codes: C10J 2300/1678 with air separation
• CPC Class Codes: C10J 2300/1807 Recycle loops, e.g. gas, solids, heating medium, water
• CPC Class Codes: C10J 3/46 Gasification of granular or pulverulent flues in suspension
• CPC Class Codes: C10J 3/725 : Redox processes
• CPC Class Codes: C10K 1/003 : of acid contaminants, e.g. acid gas removal
• CPC Class Codes: C10K 1/024 : by filtration
• CPC Class Codes: C10K 3/026 : Increasing the carbon monoxide content, e.g. reverse water-gas shift [RWGS]
• CPC Class Codes: C25B 1/04 : by electrolysis of water
• CPC Class Codes: C25B 3/00 : Electrolytic production of organic compounds
• CPC Class Codes: H01M 2008/1293 : Fuel cells with solid oxide electrolytes
• CPC Class Codes: H01M 2008/147 : Fuel cells with molten carbonates
• CPC Class Codes: H01M 2300/0051 : Carbonates
• CPC Class Codes: H01M 2300/0071 : Oxides
• CPC Class Codes: H01M 8/0618 : Reforming processes, e.g. autothermal, partial oxidation or steam reforming
• CPC Class Codes: H01M 8/0643 : Gasification of solid fuel
• CPC Class Codes: H01M 8/1007 : with both reactants being gaseous or vaporised H01M8/12 takes precedence
• CPC Class Codes: H01M 8/1016 : characterised by the electrolyte material H01M8/12 takes precedence
• CPC Class Codes: H01M 8/145 : comprising carbonates
• CPC Class Codes: Y02E 20/18 : Integrated gasification combined cycle [IGCC], e.g. combined with carbon capture and storage [CCS]
• CPC Class Codes: Y02E 60/36 : Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
• CPC Class Codes: Y02E 60/50 : Fuel cells
• CPC Class Codes: Y02P 20/00 : Technologies relating to chemical industry
• CPC Class Codes: Y02P 20/133 : Renewable energy sources, e.g. sunlight
• CPC Class Codes: Y02P 70/50 : Manufacturing or production processes characterised by the final manufactured product

Abstract

High efficiency electricity generation processes and systems with substantially zero CO₂ emissions are provided. A closed looping between the unit that generates gaseous fuel (H₂, CO, etc) and the fuel cell anode side is formed. In certain embodiments, the heat and exhaust oxygen containing gas from the fuel cell cathode side are also utilized for the gaseous fuel generation. The resulting power generation efficiencies are improved due to the minimized steam consumption for the gaseous fuel production in the fuel cell anode loop as well as the strategic mass and energy integration schemes.

Claims

1. A method for producing electricity and a separate CO₂ rich stream from a carbonaceous fuel and steam comprising:

reducing Fe₂O₃ containing particles to lower oxidation state metallic iron containing particles by reacting the Fe₂O₃ containing particles with a carbonaceous fuel in a first reaction zone, the first reaction zone having a top and a bottom;

oxidizing a first portion of the metallic iron containing particles with a steam or CO₂ rich gas from a fuel cell anode in a second reaction zone to provide iron oxide containing particles while generating a fuel rich gas stream comprising H₂ or CO;

returning the fuel rich gas stream from the second reaction zone to the anode of the fuel cell via a closed loop between the second reactor zone and the fuel cell, wherein the closed loop comprises a working fluid stream of (1 ) fuel and (2 ) steam or CO₂;

directly sending a second portion of the metallic iron containing particles from the first reaction zone to a third reaction zone, and oxidizing the second portion of the metallic iron containing particles and iron oxide containing particles obtained from the oxidation reaction in the second reaction zone with an oxygen containing gas to produce Fe₂O₃ containing particles in a third reaction zone; and

returning the Fe₂O₃ containing particles to the first reaction zone;

wherein at least a portion of the oxygen containing gas used in the third reaction zone is the oxygen containing gas produced from the outlet of a fuel cell cathode.

2. A method as claimed in claim 1 in which the fuel cell comprises a stack of solid oxide fuel cells.

3. A method as claimed in claim 1 in which the carbonaceous fuel comprises syngas, carbon monoxide, methane rich gas, light hydrocarbons, liquid carbonaceous fuels, coal, biomass, tar sand, oil shale, petroleum coke, heavy liquid hydrocarbons, wax, or mixtures thereof.

4. A method as claimed in claim 1 in which CO₂ remaining is sequestered after condensing out moisture.

5. A method as claimed in claim 1 in which at least a portion of the oxygen containing gas exits the third reaction zone and is introduced to an inlet of the fuel cell cathode.

6. A method as claimed in claim 1 in which less than 10% of the fuel rich gas stream or the steam or CO₂ rich gas is purged.

7. A method as claimed in claim 1 in which the Fe₂O₃ containing particles contain supporting material comprising a ceramic material selected from at least one of the group consisting of oxides of Al, Ti, Zr, Y, Si, La, Cr, Mg, Mn, Cu, Ca, carbides of Si and Ti, sepiolite, bentonite, and kaolin.

8. A method as claimed in claim 1 in which the steam or CO₂ rich gas or a portion of the fuel rich gas stream is introduced to the bottom of the first reaction zone to enhance the conversions of both Fe₂O₃ containing particles and the carbonaceous fuel.

9. A method as claimed in claim 1 in which the carbonaceous fuel is in the form of solid particles which are suspended by gases in the first reaction zone until they are at least 50% converted before being elutriated towards the top of the first reaction zone.

10. A method as claimed in claim 1 in which a portion of the fuel rich gas stream is purged from the closed loop and is repressurized and introduced back to the closed loop.

11. A method as claimed in claim 1 in which heat released from the third reaction zone is used to preheat feed gas streams to the fuel cell cathode or the third reaction zone.

12. A method as claimed in claim 1 in which the fuel cell comprises a molten carbonate fuel cell and at least a portion of CO₂ required by the fuel cell cathode is provided by a CO₂ rich gas stream produced by the first reaction zone.

13. A method as claimed in claim 1, wherein the fuel of the working fuel stream comprises H₂ and CO.

14. A method as claimed in claim 1, wherein the working fluid stream comprises H₂, CO, steam, and CO₂.

15. A method as claimed in claim 1, in which a portion of the steam or CO₂ rich gas is purged from the closed loop and is repressurized and introduced back to the closed loop.

16. A method for producing electricity and a separate CO₂ rich stream from a carbonaceous fuel and steam comprising:

reducing Fe₂O₃ containing particles to oxidation state metallic iron containing particles by reacting the Fe₂O₃ containing particles with a carbonaceous fuel in a first reaction zone, the first reaction zone having a top and a bottom;

oxidizing a first portion of the metallic iron containing particles with a steam or CO₂ rich gas from a fuel cell anode in a second reaction zone to provide iron oxide containing particles while generating a fuel rich gas stream comprising H₂ or CO;

returning the fuel rich gas stream from the second reaction zone to the anode of the fuel cell via a closed loop between the second reactor zone and the fuel cell, the closed loop comprising a working fluid stream comprising (1) fuel and (2 ) steam or CO₂;

directly sending a second portion of the metallic iron containing particles from the first reaction zone to the third reaction zone, and oxidizing the second portion of the metallic iron containing particles and iron oxide containing particles obtained from the oxidation reaction in the second reaction zone with an oxygen containing gas to produce Fe₂O₃ containing particles in a third reaction zone; and

returning the Fe₂O₃ containing particles to the first reaction zone.

17. The method of claim 16, wherein the fuel of the working fluid stream comprises H₂ and CO.

18. The method of claim 16, wherein the working fluid stream comprises H₂, CO, steam, and CO₂.