Using fossil fuels to increase biomass-based fuel benefits

• US 8,592,492 B2
• Filed: 03/04/2011
• Issued: 11/26/2013
• Est. Priority Date: 03/08/2010
• Status: Active Grant

• Current Assignee: Praxair Technology Incorporated (Linde Plc)
• Original Assignee: Praxair Technology Incorporated (Linde Plc)
• Inventors: Chakravarti, Shrikar, Drnevich, Raymond Francis, Bonaquist, Dante Patrick, Panuccio, Gregory
• Primary Examiner(s): PARSA, JAFAR F
• Application Number:
  US13/040,459
• Publication Number:
  US 20110218254A1
• Time in Patent Office: 998 Days
• Field of Search: 518700-705
• US Class Current: 518/703
• 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 2203/0255 containing a non-catalytic partial oxidation step
• CPC Class Codes: C01B 2203/0283 containing a CO-shift step, i.e. a water gas shift step
• CPC Class Codes: C01B 2203/0405 Purification by membrane separation
• CPC Class Codes: C01B 2203/0415 Purification by absorption in liquids
• 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 2203/062 Hydrocarbon production, e.g. Fischer-Tropsch process
• CPC Class Codes: C01B 3/36 using oxygen or mixtures containing oxygen as gasifying agents
• CPC Class Codes: C01B 3/382 Multi-step processes
• CPC Class Codes: C01B 3/384 the catalyst being continuously externally heated
• CPC Class Codes: C01B 3/48 followed by reaction of water vapour with carbon monoxide
• CPC Class Codes: C10G 2/30 from carbon monoxide with hydrogen
• CPC Class Codes: C10G 2/32 with the use of catalysts
• CPC Class Codes: C10G 2300/1011 Biomass
• CPC Class Codes: C10G 2300/807 Steam
• CPC Class Codes: C10J 2300/0909 Drying
• CPC Class Codes: C10J 2300/0916 Biomass
• CPC Class Codes: C10J 2300/0956 Air or oxygen enriched air
• CPC Class Codes: C10J 2300/0959 Oxygen
• CPC Class Codes: C10J 2300/0976 : as steam
• CPC Class Codes: C10J 2300/1618 : Modification of synthesis gas composition, e.g. to meet some criteria
• CPC Class Codes: C10J 2300/1659 : to liquid hydrocarbons Fischer-Tropsch process C10G2/00
• CPC Class Codes: C10J 2300/1846 : Partial oxidation, i.e. injection of air or oxygen only
• CPC Class Codes: C10J 2300/1853 : Steam reforming, i.e. injection of steam only
• CPC Class Codes: C10J 3/18 : using electricity
• CPC Class Codes: C10J 3/463 : in stationary fluidised beds
• CPC Class Codes: C10J 3/726 : Start-up
• CPC Class Codes: C10K 3/005 : by partial oxidation
• CPC Class Codes: C10K 3/06 : by mixing with gases
• CPC Class Codes: Y02P 20/129 : Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
• CPC Class Codes: Y02P 20/145 : the feedstock being materials of biological origin
• CPC Class Codes: Y02P 30/20 : using bio-feedstock

Abstract

In the production of fuel such as ethanol from carbonaceous feed material such as biomass, a stream comprising hydrogen and carbon monoxide is added to the raw gas stream derived from the feed material, and the resulting combined stream is converted into fuel and a gaseous byproduct such as by a Fischer-Tropsch reaction. The gaseous byproduct may be utilized in the formation of the aforementioned stream comprising hydrogen and carbon monoxide.

Claims

1. A method, comprising

(A) providing fossil-fuel hydrocarbon feed;

(B) forming from said fossil-fuel hydrocarbon feed a gaseous product stream comprising hydrogen and carbon monoxide at a mole ratio of H₂;

CO of at least 2.0;

1;

(C) forming a syngas stream that is derived from carbonaceous feed material and subjecting this syngas stream to partial oxidation;

(D) adding the gaseous product stream formed in step (B) to a the partially oxidized syngas stream derived from carbonaceous feed material, in a sufficient amount to form a mixed syngas stream having a H₂;

CO mole ratio greater than that of said partially oxidized syngas stream derived from carbonaceous feed material;

(E) converting said mixed syngas stream to form product fuel and recovering from said converting a byproduct stream comprising one or more of hydrogen, CO, water vapor, methane, and hydrocarbons containing 2 to 8 carbon atoms and 0 to 2 oxygen atoms; and

(F) reacting up to 100% of said byproduct stream in said formation of said gaseous product stream in step (B).

2. A method according to claim 1 wherein said syngas stream that is derived from carbonaceous feed material is derived by gasification.

3. A method according to claim 1 wherein the fossil-fuel-based hydrocarbon feed provided in step (A) comprises methane.

4. A method according to claim 1 wherein the fossil-fuel-based hydrocarbon feed provided in step (A) comprises hydrocarbons containing up to 8 carbon atoms.

5. A method according to claim 1 wherein the fossil-fuel-based hydrocarbon feed provided in step (A) comprises LPG.

6. A method according to claim 1 wherein said gaseous product stream is formed by steam-methane reforming.

7. A method according to claim 1 wherein said gaseous product stream is formed by secondary reforming of a stream that is formed by steam-methane reforming.

8. A method according to claim 7 wherein the secondary reforming is autothermal reforming.

9. A method according to claim 1 wherein said gaseous product stream is formed by autothermal reforming.

10. A method according to claim 1 wherein said gaseous product stream is formed by non-catalytic partial oxidation.

11. A method according to claim 1 wherein the mole ratio of hydrogen:

carbon monoxide in the mixed syngas stream formed in step (C) is at least 1.5;

1.

12. A method according to claim 1 wherein said combined stream is converted in step (D) to product fuel by a Fischer-Tropsch reaction.

13. A method according to claim 1 wherein said fuel formed in step (D) comprises alkanol containing up to 5 carbon atoms.

14. A method according to claim 1 wherein up to 100% of a byproduct stream produced in step (D) is fed to step (B) and is combusted to produce heat which is consumed in the formation of said gaseous product stream in step (B).

15. A method according to claim 1 wherein up to 100% of a byproduct stream produced in step (D) is fed to step (B) and is reacted in the formation of said gaseous product stream in step (B).

16. A method according to claim 2 further comprising evaporating a feed stream of water with heat produced by the conversion of said mixed syngas stream in step (D) to produce steam and using up to all of said steam in said gasification of carbonaceous feed material.

17. A method according to claim 1 further comprising evaporating a feed stream of water with heat produced by the conversion of said mixed syngas stream in step (D) to produce steam and reacting up to all of said steam with fossil-fuel-based hydrocarbon feed in step (B).

18. A method according to claim 1 further comprising (I) treating a portion up to 100% of the gaseous product stream formed in step (B) to produce a hydrogen-enriched stream which contains hydrogen at a hydrogen content greater than that of said gaseous product stream and which also contains carbon dioxide, (II) adding the hydrogen-enriched stream to one or more of (i) said gaseous product stream, (ii) said syngas stream derived from carbonaceous feed material, or (iii) said mixed syngas stream, and (III) removing carbon dioxide from said mixed syngas stream, from said hydrogen-enriched stream, or from any of streams (i) or (ii) to which said hydrogen-enriched stream is added.

19. A method according to claim 1 further comprising (I) treating a portion up to 100% of the gaseous product stream formed in step (B) to produce a hydrogen-enriched stream having a hydrogen content greater than that of said gaseous product stream as well as carbon dioxide, and (II) recovering hydrogen from said hydrogen-enriched stream.

20. A method for improving the carbon conversion efficiency of fuel production from carbonaceous feed material, comprising

(A) deriving a raw gaseous stream comprising hydrogen and carbon monoxide in a mole ratio of hydrogen:

carbon monoxide of less than 2;

1 from carbonaceous feed material;

(B) forming a second gaseous stream comprising hydrogen and carbon monoxide in a mole ratio of hydrogen;

carbon monoxide greater than 2;

1 and also comprising carbon dioxide, and combining said second gaseous stream and the stream derived in step (A);

(C) converting said combined stream into liquid product fuel, and a gaseous byproduct mixture comprising hydrogen, carbon monoxide, water vapor and methane;

(D) reacting hydrocarbon fuel and steam to form said second gaseous stream, wherein at least a portion of said gaseous byproduct mixture is combusted to produce heat which is consumed in said reaction.

21. A method, comprising:

(A) providing fossil-fuel hydrocarbon feed to a reactor;

(B) forming from said fossil-fuel hydrocarbon feed a gaseous product stream comprising hydrogen and carbon monoxide at a mole ratio of H₂;

CO of at least 2.0;

1;

(C) converting up to all of said gaseous product stream to form product fuel and recovering from said converting a byproduct stream comprising one or more of hydrogen, CO, water vapor, methane, and hydrocarbons containing 2 to 8 carbon atoms and 0 to 2 oxygen atoms; and

(D) reacting up to 100% of said byproduct stream in said formation of said gaseous product stream in step (B);

wherein steps (A)-(D) are performed sequentially without adding to said gaseous product stream any other gaseous product derived from carbonaceous feed material; and

thereafter

(E) forming a syngas stream containing hydrogen and CO that is derived from carbonaceous feed material, in a sufficient amount to form a mixed syngas stream having a H₂;

CO mole ratio greater than that of said syngas stream derived from carbonaceous feed material and adding the gaseous product stream formed in step (B) to the syngas derived from carbonaceous feed material in this step (E);

(F) converting said mixed syngas stream to form product fuel and recovering from said converting a byproduct stream comprising one or more of hydrogen, CO, water vapor, methane, and hydrocarbons containing 2 to 8 carbon atoms and 0 to 2 oxygen atoms; and

(G) reacting up to 100% of said byproduct stream in said formation of said gaseous product stream in step (B).

22. A method according to claim 21, wherein steps (A) through (G) are preceded by the steps of

(a) providing fossil-fuel hydrocarbon feed;

(b) forming from said fossil-fuel hydrocarbon feed a gaseous product stream comprising hydrogen and carbon monoxide at a mole ratio of H₂;

CO of at least 2.0;

1;

(c) adding the gaseous product stream formed in step (b) to a syngas stream containing hydrogen and CO that is derived from carbonaceous feed material, in a sufficient amount to form a mixed syngas stream having a H₂;

CO mole ratio greater than that of said syngas stream derived from carbonaceous feed material;

(d) converting said mixed syngas stream to form product fuel and recovering from said converting a byproduct stream comprising one or more of hydrogen, CO, water vapor, methane, and hydrocarbons containing 2 to 8 carbon atoms and 0 to 2 oxygen atoms; and

(e) reacting up to 100% of said byproduct stream in said formation of said gaseous product stream in step (b).

23. The method of claim 21, wherein the gaseous product stream formed from said fossil-fuel hydrocarbon comprises hydrogen to carbon monoxide at a mole ratio of H₂:

CO in a range of about 2.0;

1 to 10;

1.