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

• US 20130143973A1
• 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:
  US13/691,217
• Publication Number:
  US 20130143973A1
• 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: 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 3:1 to form a compressed product gas; directing a first portion of the compressed product gas to an alcohol synthesis reactor to produce methanol; reacting carbon monoxide with the methanol to produce acetic acid; esterifying the acetic acid with ethanol to form ethyl acetate; and reducing the ethyl acetate with hydrogen in the presence of a catalyst to form 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 3;

1 to form a compressed product gas;

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

reacting carbon monoxide with the methanol to produce acetic acid;

reducing a first portion of the acetic acid with hydrogen to produce ethanol in the presence of a catalyst having a selectivity to ethanol that is greater than 50%;

esterifying a second portion of the acetic acid and the ethanol to produce ethyl acetate; and

reducing the ethyl acetate with hydrogen to produce ethanol, provided that at least times more ethanol is produced by reducing the ethyl acetate than is formed by reducing the acetic acid, and wherein none of the ethanol produced by reducing the ethyl acetate is esterified with acetic acid.

2. The process of claim 1, wherein the gasifier is operated at a pressure of at least 15 bar.

3. The process of claim 1, wherein the product gas is compressed at a compression ratio less than 2:

1.

4. 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.

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

(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 3;

1 to form a compressed product gas;

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

(d) reacting carbon monoxide with the methanol to produce acetic acid;

(e) reducing a first portion of the acetic acid with hydrogen to produce ethanol in the presence of a catalyst having a selectivity to ethanol that is greater than 50%;

(f) esterifying a second portion of the acetic acid and the methanol to produce methyl acetate; and

(g) reducing the methyl acetate with hydrogen to produce methanol and ethanol, wherein methanol produced by reducing the methyl acetate is recycled to at least one of step (d) or step (f).

6. The process of claim 5, provided that at least 1.5 times more ethanol is produced by reducing the methyl acetate than is formed by reducing the acetic acid.

7. The process of claim 5, wherein the methanol produced by reducing the methyl acetate is recycled to step (d).

8. The process of claim 5, wherein methanol produced by reducing the methyl acetate is recycled to step (f).

9. The process of claim 5, wherein the gasifier is operated at a pressure of at least 15 bar.

10. The process of claim 5, wherein the product gas is compressed at a compression ratio less than 2:

1.

11. The process of claim 5, wherein the ethanol has a ¹⁴C:

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

¹²C ratio for living organisms.

12. 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 3;

1 to form a compressed product gas;

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

reacting carbon monoxide with the methanol to produce acetic acid;

reducing the acetic acid with hydrogen to produce ethyl acetate in the presence of a catalyst having a selectivity to ethyl acetate that is greater than 50%; and

reducing the ethyl acetate to ethanol.

13. The process of claim 12, wherein the catalyst has a selectivity to ethanol that is greater than 5% and less than 50%.

14. The process of claim 13, further comprising the step of:

separating a majority of the ethanol from a majority of the ethyl acetate before reducing the ethyl acetate to ethanol.

15. The process of claim 12, wherein the gasifier is operated at a pressure of at least 15 bar.

16. The process of claim 12, wherein the product gas is compressed at a compression ratio less than 2:

1

17. 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 3;

1 to form a compressed product gas;

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

reacting carbon monoxide with the methanol to produce acetic acid;

esterifying the acetic acid with ethanol to form ethyl acetate; and

reducing the ethyl acetate with hydrogen in the presence of a catalyst to form ethanol.

18. The process of claim 17, wherein a portion of the ethanol formed in the process is separated and recycled to the esterifying step.

19. The process of claim 17, wherein the gasifier is operated at a pressure of at least 15 bar.

20. The process of claim 17, wherein the product gas is compressed at a compression ratio less than 2:

1