IP Library Granted Patent US 8,288,594
Granted Patent B2
US 8,288,594 · App. 12/951,296 · Granted Oct 16, 2012

Selective process for conversion of syngas to ethanol

Assignee: Albemarle Corporation
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Quick Facts
Patent No.
US 8,288,594
App. No.
12/951,296
Granted
Oct 16, 2012
Kind
B2
Abstract

The present invention provides processes for selectively producing ethanol from syngas. In some variations, the process comprises converting biomass-derived syngas to dimethyl ether, carbonylating the dimethyl ether to methyl acetate, hydrogenating the methyl acetate to methanol and ethanol, and recovering the ethanol product. The methanol is preferably recycled by converting to hydrogen and carbon monoxide for introduction back into the process at distinct points. In certain variations of this invention, fresh syngas feed is introduced downstream of the first unit operation in the sequence. High yields of ethanol from biomass can be achieved according to the disclosed processes.

Claims (43)

1. A process for producing ethanol from syngas, said process comprising:

(a) providing syngas having an input H 2 /CO ratio;

(b) converting a portion of said syngas to dimethyl ether;

(c) carbonylating at least some of said dimethyl ether to methyl acetate;

(d) hydrogenating at least some of said methyl acetate to methanol and ethanol;

(e) converting at least some of said methanol from step (d) to hydrogen and carbon monoxide;

(f) feeding said carbon monoxide generated in step (e) back to step (c);

(g) feeding said hydrogen generated in step (e) back to step (d); and

(h) recovering said ethanol.

2. The process of claim 1 , wherein said syngas is derived from biomass.

3. The process of claim 1 , wherein said input H 2 /CO ratio is selected from about 0.6 to about 1.4.

4. The process of claim 3 , wherein said input H 2 /CO ratio is selected from about 0.8 to about 1.2.

5. The process of claim 3 , wherein said input H 2 /CO ratio is selected from about 0.9 to about 1.1.

6. The process of claim 1 , wherein step (c) further comprises a CO 2 purge.

7. The process of claim 1 , wherein methanol and ethanol are separated by distillation.

8. The process of claim 1 , further comprising recycling a portion of said methanol directly to step (b).

9. The process of claim 1 , wherein step (e) comprises catalytically converting said methanol to hydrogen and carbon monoxide and then separating said hydrogen from said carbon monoxide.

10. The process of claim 1 , wherein step (e) comprises a two-step methyl formate process to generate separate hydrogen and carbon monoxide streams.

11. A process for producing ethanol from syngas, said process comprising:

(a) providing fresh syngas having an input H 2 /CO ratio;

(b) providing a recycle stream comprising syngas components and methanol;

(c) converting a portion of said recycle stream to dimethyl ether;

(d) carbonylating at least some of said dimethyl ether to methyl acetate;

(e) introducing said fresh syngas and said methyl acetate to a unit for hydrogenating at least some of said methyl acetate to methanol and ethanol;

(f) separating said ethanol from said recycle stream; and

(g) recovering said ethanol.

12. The process of claim 11 , wherein said syngas is derived from biomass.

13. The process of claim 11 , wherein said input H 2 /CO ratio is selected from about 0.6 to about 1.4.

14. The process of claim 13 , wherein said input H 2 /CO ratio is selected from about 0.8 to about 1.2.

15. The process of claim 13 , wherein said input H 2 /CO ratio is selected from about 0.9 to about 1.1.

16. The process of claim 11 , wherein step (d) further comprises a CO 2 purge.

17. The process of claim 11 , further comprising catalytically converting said methanol to hydrogen and carbon monoxide for introducing to step (e).

18. The process of claim 11 , comprising a two-step methyl formate process to generate separate hydrogen and carbon monoxide streams.

19. The process of claim 11 , further comprising recovering a co-product selected from the group consisting of methanol, dimethyl ether, methyl acetate, syngas, hydrogen, carbon monoxide, carbon dioxide, and electricity.

20. A process for producing ethanol from biomass, said process comprising:

(a) converting biomass into syngas having an H 2 /CO ratio from 0.6 to 1.4;

(b) converting said syngas to dimethyl ether;

(c) carbonylating said dimethyl ether to methyl acetate;

(d) hydrogenating said methyl acetate to methanol and ethanol;

(e) converting said methanol to hydrogen and carbon monoxide;

(f) feeding said carbon monoxide generated in step (e) back to step (c);

(g) feeding said hydrogen generated in step (e) back to step (d); and

(h) recovering said ethanol.

Assignments (5)
SECURITY INTEREST Recorded Mar 2, 2026
From: KETJEN LIMITED LIABILITY COMPANY
To: BARCLAYS BANK PLC, AS COLLATERAL AGENT
Reel/Frame 073941/0129 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jan 11, 2024
From: ALBEMARLE CORPORATION
To: KETJEN LIMITED LIABILITY COMPANY
Reel/Frame 066099/0361 →
CORRECTIVE ASSIGNMENT TO CORRECT THE OWNERSHIP OF PROPERTIES LISTED ON THE ATTACHED SHEET, WHICH WERE PREVIOUSLY RECORDED ON REEL 028305 FRAME 0880. ASSIGNOR(S) HEREBY CONFIRMS THE PATENT ASSIGNMENT AGREEMENT. Recorded Nov 22, 2013
From: RANGE FUELS, INC.
To: ALBEMARLE CORPORATION
Reel/Frame 031947/0866 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jun 1, 2012
From: RANGE FUELS, INC.
To: ALBEMARLE CORPORATION
Reel/Frame 028305/0880 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jan 31, 2011
From: STITES, RONALD C.; DEUTCH, STEPHEN; HOHMAN, JERROD; TIRMIZI, SHAKEEL
To: RANGE FUELS, INC.
Reel/Frame 025721/0019 →
Continuity (2)
Provisional Application 61264211 · Nov 24, 2009
Related Publication 20110124927A1 · May 26, 2011