Synthetic fuels and chemicals production with in-situ CO;capture

• US 9,518,236 B2
• Filed: 09/08/2010
• Issued: 12/13/2016
• Est. Priority Date: 09/08/2009
• Status: Active Grant

• Current Assignee: The Ohio State University Research Foundation
• Original Assignee: The Ohio State University Research Foundation
• Inventors: Fan, Liang-Shih, Li, Fanxing, Zeng, Liang
• Primary Examiner(s): HINES, LATOSHA D
• Application Number:
  US13/394,396
• Publication Number:
  US 20120159841A1
• Time in Patent Office: 2,288 Days
• Field of Search: 444/57, 518/700
• US Class Current: 1/1
• CPC Class Codes: C01B 2203/062 Hydrocarbon production, e.g. Fischer-Tropsch process
• 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 2203/86 Carbon dioxide sequestration
• CPC Class Codes: C01B 3/344 using non-catalytic solid particles
• CPC Class Codes: C10G 1/02 by distillation
• CPC Class Codes: C10G 2/50 from carbon dioxide with hydrogen
• CPC Class Codes: C10G 2300/1011 Biomass
• CPC Class Codes: C10G 2300/807 Steam
• 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 2300/1612 CO2-separation and sequestration, i.e. long time storage
• CPC Class Codes: C10J 2300/1659 to liquid hydrocarbons
• 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 3/466 Entrained flow processes
• CPC Class Codes: C10J 3/725 Redox processes
• CPC Class Codes: C10J 3/86 combined with waste-heat boilers
• 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: Y02P 20/145 : the feedstock being materials of biological origin
• CPC Class Codes: Y02P 30/00 : Technologies relating to oil refining and petrochemical industry
• CPC Class Codes: Y02P 30/20 : using bio-feedstock

Abstract

Novel redox based systems for fuel and chemical production with in-situ CO₂ capture are provided. A redox system using one or more chemical intermediates is utilized in conjunction with liquid fuel generation via indirect Fischer-Tropsch synthesis, direct hydrogenation, or pyrolysis. The redox system is used to generate a hydrogen rich stream and/or CO₂ and/or heat for liquid fuel and chemical production. A portion of the byproduct fuels and/or steam from liquid fuel and chemical synthesis is used as part of the feedstock for the redox system.

Claims

1. A method for producing synthetic liquid fuel from a carbonaceous fuel comprising:

indirectly gasifying the carbonaceous fuel using steam and optionally, an oxygen containing gas, and forming separate streams of carbon dioxide and hydrogen rich gases, wherein metal oxide particles containing Fe₂O₃ are used in an indirect gasification reaction, and the carbonaceous fuel is indirectly gasified by;

reducing the Fe₂O₃ containing particles with the carbonaceous fuel in a first reaction zone comprising a packed moving bed with a countercurrent gas-solids contacting pattern such that an average valence of iron is less than 1, wherein the first reaction zone is operated at a temperature of greater than or equal to 400°

C. and less than or equal to 1200°

C. and at a pressure of greater than or equal to 1.01×

10⁵ Pa and less than or equal to 8.10×

10⁶ Pa;

at least partially oxidizing a portion of the reduced iron oxide containing particles from the first reaction zone with steam to generate a hydrogen rich gas in a second reaction zone comprising countercurrent gas-solids contacting pattern such that the iron oxide containing particle is at least partially oxidized to contain Fe₃O₄;

directly sending a portion of the reduced iron oxide particles from the first reaction zone to a third reaction zone;

oxidizing the reduced iron oxide particles from the first reaction zone and the iron oxide containing particles from the second reaction zone with an oxygen containing gas in the third reaction zone, and returning the oxidized iron oxide containing particles to the first reaction zone; and

reacting the hydrogen rich gas and a portion of the carbon dioxide in a CO₂ hydrogenation reaction to form a synthetic fuel, wherein remaining CO₂ is sequestered.

2. A method as claimed in claim 1 in which at least a portion of the steam is produced using heat generated from the CO₂ hydrogenation reaction.

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 a mixture thereof.

4. A method as claimed in claim 1 in which at least a portion of the synthetic liquid fuel is used as a feed for the carbonaceous fuel.

5. A method as claimed in claim 1 in which the metal oxide particles contain supporting material comprising a ceramic material selected from 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.

6. A method as claimed in claim 1 in which gaseous species selected from CO₂, H₂O, or gaseous fuels from CO₂ hydrogenation, are introduced to the bottom of the first reaction zone to enhance conversions of both the iron oxide particles and the carbonaceous fuel.

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

8. A method as claimed in claim 1 in which a calcium oxide containing CO₂ sorbent is used to assist in the indirect gasification of the carbonaceous fuels.