METHOD FOR ADJUSTING HYDROGEN TO CARBON MONOXIDE RATIO IN SYNTHESIS GAS

• US 20130005838A1
• Filed: 07/02/2012
• Published: 01/03/2013
• Est. Priority Date: 06/30/2011
• Status: Active Grant

• Current Assignee: Neste Oil Oyj
• Original Assignee: Neste Oil Oyj
• Inventors: EILOS, Isto, KOSKINEN, Jukka, TIITTA, Marja, TOPPINEN, Sami, VUORI, Heli
• Granted Patent: US 8,598,237 B2
• Time in Patent Office: Days
• US Class Current: 518/703
• CPC Class Codes: C01B 2203/0283 containing a CO-shift step, i.e. a water gas shift step
• CPC Class Codes: C01B 2203/062 Hydrocarbon production, e.g. Fischer-Tropsch process
• CPC Class Codes: C01B 3/16 using catalysts
• CPC Class Codes: C10G 2/30 from carbon monoxide with hydrogen
• CPC Class Codes: C10G 2300/1014 of vegetal origin
• CPC Class Codes: C10G 2300/1022 Fischer-Tropsch products
• CPC Class Codes: C10G 2300/202 Heteroatoms content, i.e. S, N, O, P
• CPC Class Codes: C10G 2300/301 Boiling range
• CPC Class Codes: C10G 2400/02 Gasoline
• CPC Class Codes: C10G 2400/04 Diesel oil
• CPC Class Codes: C10G 2400/08 Jet fuel
• CPC Class Codes: C10G 2400/10 Lubricating oil
• CPC Class Codes: C10J 2300/0996 Calcium-containing inorganic materials, e.g. lime
• CPC Class Codes: C10J 3/54 Gasification of granular or pulverulent fuels by the Winkler technique, i.e. by fluidisation
• CPC Class Codes: C10K 3/006 by steam reforming
• CPC Class Codes: C10K 3/04 reducing the carbon monoxide content , e.g. water-gas shift [WGS]
• CPC Class Codes: C10L 1/04 essentially based on blends of hydrocarbons
• CPC Class Codes: Y02E 50/30 Fuel from waste, e.g. synthetic alcohol or diesel
• CPC Class Codes: Y02E 60/32 Hydrogen storage
• CPC Class Codes: Y02P 20/52 using catalysts, e.g. selective catalysts
• CPC Class Codes: Y02P 30/20 : using bio-feedstock

Abstract

A method for adjusting hydrogen to carbon monoxide ratio of syngas contaminated by sulfur impurities involving a water gas shift (WGS) reaction. In light of the presence of the sulfur impurities, the WGS can be implemented as a sour gas shift. WGS can provide good results by using a non-sulfided catalyst. Conditions can be employed which contribute to further enhanced CO-conversion in the reaction. The hydrocarbons or derivatives thereof obtainable from the method can further be refined and used for production of fuels or lubricants for combustion engines.

Claims

1. A method for adjusting hydrogen to carbon monoxide ratio in syngas, the method comprising:

providing a syngas produced from a biomass raw material, said syngas comprising carbon monoxide, hydrogen, 10-40 vol-% of carbon dioxide, and at least one sulfur derivative as an impurity; and

converting at least a part of said carbon monoxide in the presence of steam to carbon dioxide and hydrogen with a water gas shift reaction in the presence of a FeCr catalyst.

2. The method according to claim 1, wherein said syngas further comprises NH₃.

3. The method according to claim 1, wherein a content of said sulfur derivative in said syngas is less than 900 ppm.

4. The method according to claim 1, wherein said water gas shift reaction is conducted at a temperature between 270°

C. and 510°

C.

5. The method according to claim 1, wherein said water gas shift reaction is conducted at a pressure between 1 to 10 bar.

6. The method according to claim 1, wherein said FeCr catalyst is not sulfided prior to use in the water gas shift reaction.

7. The method according to claim 1, further comprising converting the syngas to a product selected from the group consisting of alcohols, alkyl carbonates and hydrocarbons having a carbon number from C4 to C90.

14. The method according to claim 1, wherein the content of said sulfur derivative in said syngas is from 30 ppm to 500 ppm.

15. The method according to claim 1, wherein said water gas shift reaction is conducted at a temperature between 300°

C. and 510°

C.

16. The method according to claim 1, wherein said water gas shift reaction is conducted at a temperature between 380°

C. and 430°

C.

17. The method according to claim 4, wherein said water gas shift reaction is conducted at a pressure between 1 to 10 bar.

18. The method according to claim 1, wherein said water gas shift reaction is conducted at a pressure between 3 to 6 bar.

19. The method according to claim 4, wherein said water gas shift reaction is conducted at a pressure between 3 to 6 bar.

8. A method for producing hydrocarbons from a biomass raw material, the method comprising:

gasifying a biomass raw material in the presence of oxygen to produce a gas comprising carbon monoxide, 10-40 vol-% of carbon dioxide, hydrogen, hydrocarbons, and at least one sulfur derivative as impurity;

converting at least a part of said carbon monoxide to carbon dioxide and hydrogen with a water gas shift reaction in the presence of a FeCr catalyst;

converting in a Fisher-Tropsch reactor at least a part of the carbon monoxide and hydrogen into a hydrocarbon composition comprising C₄-C₉₀ hydrocarbons; and

recovering at least a part of the C₄-C₉₀ hydrocarbons.

9. The method according to claim 8, further comprising reforming the syngas downstream from gasifying the biomass raw material and upstream from said water gas shift reaction.

10. The method according to claim 8, further comprising at least one wash step.

11. The method according to claim 8, wherein the recovered hydrocarbons are treated to produce a fuel or lubricant for combustion engines.

12. The method according to claim 8, comprising producing hydrocarbons suitable for fuel applications having distillation cut points in a range of about 40 to 350°

C.

13. The method according to claim 8, comprising producing hydrocarbons suitable for lubricant applications, said hydrocarbons having carbon numbers in a range of 30 to 40.

20. The method according to claim 9, further comprising at least one wash step.

21. The method according to claim 8, comprising producing hydrocarbons suitable for fuel applications having distillation cut points in a range of 180 to 300°

C.