BIOMASS GASIFICATION AND INTEGRATED PROCESSES FOR MAKING INDUSTRIAL CHEMICALS THROUGH AN ACETIC ACID INTERMEDIATE

• US 20130143972A1
• Filed: 11/30/2012
• Published: 06/06/2013
• Est. Priority Date: 12/02/2011
• Status: Abandoned Application

• Current Assignee: Celanese International Corporation (Celanese Corporation)
• Original Assignee: Celanese International Corporation (Celanese Corporation)
• Inventors: Townsend, David W., Arora, Dinesh, Shuff, Andrew M.
• Application Number:
  US13/691,193
• Publication Number:
  US 20130143972A1
• Time in Patent Office: Days
• US Class Current: 518/703
• CPC Class Codes: B01J 23/462 Ruthenium
• CPC Class Codes: B01J 23/50 Silver
• CPC Class Codes: B01J 23/52 Gold
• CPC Class Codes: B01J 23/626 with tin
• CPC Class Codes: B01J 23/6567 Rhenium
• CPC Class Codes: B01J 23/80 with zinc, cadmium or mercury
• CPC Class Codes: B01J 23/864 Cobalt and chromium
• CPC Class Codes: B01J 23/8906 Iron and noble metals
• CPC Class Codes: B01J 23/8913 Cobalt and noble metals
• CPC Class Codes: B01J 23/892 Nickel and noble metals
• CPC Class Codes: B01J 23/8926 Copper and noble metals
• CPC Class Codes: B01J 29/40 of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
• CPC Class Codes: B01J 37/0201 Impregnation
• CPC Class Codes: C01B 2203/0283 containing a CO-shift step, i.e. a water gas shift step
• CPC Class Codes: C01B 2203/061 Methanol production
• CPC Class Codes: C01B 3/02 Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
• CPC Class Codes: C07C 29/147 of carboxylic acids or derivatives thereof
• CPC Class Codes: C07C 29/149 with hydrogen or hydrogen-containing gases
• CPC Class Codes: C07C 29/1518 one step being the formation of initial mixture of carbon oxides and hydrogen for synthesis
• CPC Class Codes: C07C 29/44 increasing the number of carbon atoms by addition reactions, i.e. reactions involving at least one carbon-to-carbon double or triple bond C07C29/16 takes precedence
• CPC Class Codes: C07C 31/04 : Methanol
• CPC Class Codes: C07C 31/08 : Ethanol
• CPC Class Codes: C07C 51/12 : on an oxygen-containing group in organic compounds, e.g. alcohols
• CPC Class Codes: C07C 53/08 : Acetic acid pyroligneous acid C10C; preparation of vinegar C12J
• CPC Class Codes: C10G 2300/1014 : of vegetal origin
• CPC Class Codes: C10J 2300/0916 : Biomass
• CPC Class Codes: C10J 2300/0959 : Oxygen
• CPC Class Codes: C10J 2300/0976 : as steam
• CPC Class Codes: C10J 2300/1665 : to alcohols, e.g. methanol or ethanol preparation of alcohols in general C07C29/00
• CPC Class Codes: C10J 2300/1678 : with air separation separating gases using rectification of air F25J3/04521
• CPC Class Codes: C10J 3/00 : Production of combustible gases containing carbon monoxide from solid carbonaceous fuels destructive distillation processes C10B
• CPC Class Codes: C10J 3/46 : Gasification of granular or pulverulent flues in suspension
• CPC Class Codes: C10J 3/54 : Gasification of granular or pulverulent fuels by the Winkler technique, i.e. by fluidisation
• CPC Class Codes: C10K 1/005 : Carbon dioxide
• CPC Class Codes: C10K 3/04 : reducing the carbon monoxide content , e.g. water-gas shift [WGS]
• CPC Class Codes: Y02E 20/18 : Integrated gasification combined cycle [IGCC], e.g. combined with carbon capture and storage [CCS]
• CPC Class Codes: Y02E 50/10 : Biofuels, e.g. bio-diesel
• CPC Class Codes: Y02E 50/30 : Fuel from waste, e.g. synthetic alcohol or diesel
• CPC Class Codes: Y02P 20/10 : Process efficiency
• CPC Class Codes: Y02P 20/133 : Renewable energy sources, e.g. sunlight
• CPC Class Codes: Y02P 20/145 : the feedstock being materials of biological origin
• CPC Class Codes: Y02P 20/50 : Improvements relating to the production of bulk chemicals
• CPC Class Codes: Y02P 20/52 : using catalysts, e.g. selective catalysts
• CPC Class Codes: Y02P 30/20 : using bio-feedstock

Abstract

The invention relates to integrated processes for producing industrial chemicals, such as alcohols, carboxylic acids, esters, aldehydes, olefins and polymers from biomass. In one embodiment, the invention is to a process comprising the steps of (a) introducing biomass and an oxygen stream to a gasifier and converting the biomass into a product gas, wherein the gasifier is operated at a pressure of at least 10 bar; (b) compressing the product gas at a compression ratio that is less than 5:1 to form compressed product gas; (c) directing a first portion of the compressed product gas to an alcohol synthesis reactor to produce methanol; (d) directing a second portion of the compressed product gas to a gas separator to produce a hydrogen stream and a carbon monoxide stream; (e) reacting the carbon monoxide stream with the methanol to produce acetic acid; and (f) reacting the hydrogen stream with acetic acid to produce ethanol.

Claims

1. An integrated process for producing ethanol from biomass, comprising:

introducing biomass and an oxygen stream to a gasifier and converting the biomass into a product gas, wherein the gasifier is operated at a pressure of at least 10 bar;

compressing the product gas at a compression ratio that is less than 5;

1 to form compressed product gas;

directing a first portion of the compressed product gas to an alcohol synthesis reactor to produce methanol;

directing a second portion of the compressed product gas to a gas separator to produce a hydrogen stream and a carbon monoxide stream;

reacting the carbon monoxide stream with the methanol to produce acetic acid; and

reacting the hydrogen stream with acetic acid to produce ethanol.

2. The process of claim 1, further comprising drying the biomass to form dried biomass having less than 20 wt. % water.

3. The process of claim 1, further comprising subjecting the product gas to a water gas shift reaction to increase hydrogen content of the product gas.

4. The process of claim 3, wherein the ratio of hydrogen to carbon monoxide after subjecting the product gas to the water-gas shift reaction is greater than 1.8:

1.

5. The process of claim 4, wherein the reacting of the hydrogen stream with the acetic acid to produce the ethanol further produces product water, the process further comprising using at least some of the product water in the water gas shift reaction to increase hydrogen content.

6. The process of claim 1, wherein the pressurized gasifier comprises a fluidized bed.

7. The process of claim 6, wherein the fluidized bed is heated to a temperature from 700°

C. to 1100°

C.

8. The process of claim 1, wherein the biomass comprises a material selected from the group consisting of timber harvesting residues, forest residues, softwood chips, hardwood chips, tree branches, tree stumps, leaves, bark, sawdust, off-spec paper pulp, paper mill wastes, paper mill sludge, highway clippings, wood pellets, pelletized refuse-derived fuel, and combinations thereof.

9. The process of claim 1, wherein the biomass comprises a material selected from the group consisting of wheat straw, rice straw, willow, alfalfa, bagasse, and combinations thereof.

10. The process of claim 1, wherein the biomass is derived from a second generation biomass source.

11. The process of claim 1, wherein the biomass is substantially free of sugar.

12. The process of claim 1, wherein the oxygen stream is substantially free of nitrogen.

13. The process of claim 1, wherein the ethanol is produced in a non-fermentation process.

14. The process of claim 1, wherein the gasifier is a non-slurry gasifier.

15. The process of claim 1, further comprising reducing carbon dioxide concentration of the compressed product gas to less than 1 mol. %.

16. The process of claim 15, further comprising separating a carbon dioxide stream from the product gas and drying the biomass with the carbon dioxide stream.

17. The process of claim 1, wherein at least 75 wt. % of the biomass is obtained from a biomass source located within a 97 km radius of the gasifier.

18. The process of claim 1, wherein the process produces at least 120 gallons of ethanol per dry ton of the biomass.

19. The process of claim 1, further comprising burning a portion of the biomass to produce steam for the gasification process.

20. The process of claim 1, wherein the product gas is compressed at a compression ratio that is less than 3:

1 to form the compressed product gas.

21. The process of claim 1, further comprising producing the oxygen stream from air in an air separation unit, wherein the oxygen stream comprises less than 1 mol. % nitrogen.

22. The process of claim 1, further comprising passing the biomass through one or more lock hoppers prior to being introduced into the gasifier.

23. The process of claim 1, wherein the hydrogen stream is reacted with acetic acid in the presence of a catalyst comprising:

a first metal selected from the group consisting of cobalt, nickel, rhodium, palladium, osmium, iridium, platinum, titanium, zinc, chromium, rhenium, molybdenum, and tungsten;

a second metal selected from the group consisting of molybdenum, tin, chromium, cobalt, vanadium, tungsten, palladium, platinum, lanthanum, cerium, manganese, rhenium, gold, and nickel, provided that the second metal is different than the first metal, wherein the total content of the first and second metals is from 0.1 to 25 wt. %, based on the total weight of the catalyst;

a silicaceous support, and

optionally at least one support modifier selected from the group consisting of (i) alkaline earth metal oxides, (ii) alkali metal oxides, (iii) alkaline earth metal metasilicates, (iv) alkali metal metasilicates, (v) Group IIB metal oxides, (vi) Group IIB metal metasilicates, (vii) Group IIIB metal oxides, (viii) Group IIIB metal metasilicates, and mixtures thereof.

24. The process of claim 1, wherein the hydrogen stream is reacted with acetic acid in the presence of a catalyst comprising a combination of metals selected from the group consisting of platinum/tin, platinum/ruthenium, platinum/rhenium, palladium/ruthenium, palladium/rhenium, cobalt/palladium, cobalt/platinum, cobalt/chromium, cobalt/ruthenium, silver/palladium, copper/palladium, nickel/palladium, gold/palladium, ruthenium/rhenium, and ruthenium/iron.

25. The process of claim 1, wherein the ethanol has a ¹⁴C:

¹²C ratio from 0.5 to 1 times the ¹⁴C;

¹²C ratio for living organisms.

26. An integrated process for co-producing acetic acid and ethanol from biomass, comprising:

introducing biomass and an oxygen stream to a pressurized gasifier and converting the biomass into a product gas having a hydrogen to carbon monoxide ratio of less than 1.8;

1, wherein the product gas is not subjected to a water gas shift reaction;

separating a first portion of the product gas into a hydrogen stream and a carbon monoxide stream;

directing a second portion of the product gas and a first portion of the hydrogen stream to an alcohol synthesis reactor to produce methanol;

reacting the carbon monoxide stream with the methanol to produce acetic acid; and

reacting a second portion of the hydrogen stream with less than 90% of the acetic acid to produce ethanol.

27. The process of claim 26, further comprising drying the biomass, wherein the water content of the biomass is less than 20 wt %.

28. The process of claim 26, wherein the pressurized gasifier comprises a fluidized bed.

29. The process of claim 28, wherein the fluidized bed is heated to a temperature from 700°

C. to 1100°

C.

30. The process of claim 26, wherein the biomass comprises a material selected from the group consisting of timber harvesting residues, forest residues, softwood chips, hardwood chips, tree branches, tree stumps, leaves, bark, sawdust, off-spec paper pulp, paper mill wastes, paper mill sludge, highway clippings, wood pellets, pelletized refuse-derived fuel, and combinations thereof.

31. The process of claim 26, wherein the biomass feedstock comprises a material selected from the group consisting of wheat straw, rice straw, willow, alfalfa, bagasse, and combinations thereof.

32. The process of claim 26, wherein the biomass is derived from a second generation biomass source.

33. The process of claim 26, wherein the biomass is substantially free of sugar.

34. The process of claim 26, wherein the oxygen stream is substantially free of nitrogen.

35. The process of claim 26, wherein the ethanol is produced in a non-fermentation process.

36. The process of claim 26, wherein the gasifier is a non-slurry gasifier.

37. The process of claim 26, further comprising reducing carbon dioxide concentration of the compressed product gas to less than 1 mol. %.

38. The process of claim 37, further comprising separating a carbon dioxide stream from the product gas and drying the biomass with the carbon dioxide stream.

39. The process of claim 26, wherein at least 75 wt. % of the biomass is obtained from a biomass source located within a 97 km radius of the gasifier.

40. The process of claim 26, wherein the process produces at least 120 gallons of ethanol per dry ton of the biomass.

41. The process of claim 26, further comprising burning a portion of the biomass to produce steam for the gasification process.

42. The process of claim 26, wherein the product gas is compressed at a compression ratio that is less than 3:

1 to form the compressed product gas.

43. The process of claim 26, further comprising producing the oxygen stream from air in an air separation unit, wherein the oxygen stream comprises less than 1 mol. % nitrogen.

44. The process of claim 26, further comprising passing the biomass through one or more lock hoppers prior to being introduced into the gasifier.

45. The process of claim 26, wherein the carbon monoxide stream is reacted with methanol to produce acetic acid using a finite amount of water and a rhodium-based catalyst.

46. The process of claim 26, wherein the second portion of the hydrogen stream is reacted with the acetic acid in the presence of a catalyst comprising:

a first metal selected from the group consisting of cobalt, nickel, rhodium, palladium, osmium, iridium, platinum, titanium, zinc, chromium, rhenium, molybdenum, and tungsten;

a second metal selected from the group consisting of molybdenum, tin, chromium, cobalt, vanadium, tungsten, palladium, platinum, lanthanum, cerium, manganese, rhenium, gold, and nickel, provided that the second metal is different than the first metal, wherein the total content of the first and second metals is from 0.1 to 25 wt. %, based on the total weight of the catalyst;

a silicaceous support, and

optionally at least one support modifier selected from the group consisting of (i) alkaline earth metal oxides, (ii) alkali metal oxides, (iii) alkaline earth metal metasilicates, (iv) alkali metal metasilicates, (v) Group IIB metal oxides, (vi) Group IIB metal metasilicates, (vii) Group IIIB metal oxides, (viii) Group IIIB metal metasilicates, and mixtures thereof.

47. The process of claim 26, wherein the hydrogen stream is reacted with the acetic acid in the presence of a catalyst comprising a combination of metals selected from the group consisting of platinum/tin, platinum/ruthenium, platinum/rhenium, palladium/ruthenium, palladium/rhenium, cobalt/palladium, cobalt/platinum, cobalt/chromium, cobalt/ruthenium, silver/palladium, copper/palladium, nickel/palladium, gold/palladium, ruthenium/rhenium, and ruthenium/iron.

48. The process of claim 26, wherein the molar ratio of acetic acid produced to ethanol produced is from 1:

1 to 1;

5.