Process for preparing furfural from biomass

• US 10,093,639 B2
• Filed: 08/13/2015
• Issued: 10/09/2018
• Est. Priority Date: 08/14/2014
• Status: Active Grant

• Current Assignee: Shell USA Incorporated (Shell Plc)
• Original Assignee: Shell Oil Company (Shell Plc)
• Inventors: Chheda, Juben Nemchand, Lange, Jean Paul Andre Marie Joseph Ghislain, Weider, Paul Richard, Blackbourn, Robert Lawrence
• Primary Examiner(s): Rozof, Timothy R
• Application Number:
  US15/502,845
• Publication Number:
  US 20170240518A1
• Time in Patent Office: 1,153 Days
• CPC Class Codes: C07D 307/50 Preparation from natural products
• CPC Class Codes: C13K 1/02 obtained by saccharification of cellulosic materials manufacture of fodder A23K10/32
• CPC Class Codes: C13K 13/002 Xylose

Abstract

Furfural is produced from biomass material containing pentosan, in high yields, in a production process comprising treating the biomass with a solution containing at least one α-hydroxysulfonic acid thereby hydrolyzing the biomass to produce a product stream containing at least one C₅-carbohydrate compound in monomeric and/or oligomeric form, and dehydrating the C5-carbohydrate compound in the presence of an acid, in a biphasic reaction medium comprising an aqueous phase and a water-immiscible organic phase, at a temperature in the range of from about 100° C. to about 250° C. to produce a dehydration product stream containing furfural. An aqueous stream is separated from the dehydration product that can be optionally recycled to the hydrolysis step.

Claims

1. A method for producing furfural from biomass material containing pentosan:

(a) providing a biomass containing pentosan;

(b) contacting the biomass with a solution containing at least one α

-hydroxysulfonic acid thereby hydrolyzing the biomass to produce a product stream containing at least one C₅-carbohydrate compound in monomeric and/or oligomeric form, and α

-hydroxysulfonic acid;

(c) separating at least a portion of the α

-hydroxysulfonic acid from the product stream containing at least one C₅-carbohydrate compound to provide an acid-removed product stream containing the at least one C₅-carbohydrate compound and recovering the a-hydroxysulfonic acid in its component form;

(d) separating a liquid stream containing said at least one C₅-carbohydrate compound and a wet solid stream containing remaining biomass from the acid-removed product;

(e) dehydrating the C₅-carbohydrate compound in at least a first portion of the liquid stream in the presence of a dehydration acid, in a biphasic reaction medium comprising an aqueous phase and a water-immiscible organic phase, at a temperature in the range of from about 100°

C. to about 250°

C.;

(f) separating an organic phase stream containing furfural and an aqueous stream containing the acid from the dehydration product stream;

(g) recycling at least a portion of the aqueous stream or a second portion of the liquid stream to step (b);

(h) recovering furfural from the organic phase stream.

2. The method of claim 1 wherein the amount of the dehydration acid is in the range of 0.2 wt % to 5 wt %, based on the liquid stream.

3. The method of claim 1 wherein the dehydration step is carried out at a temperature in the range of from about 140°

C. to about 250°

C.

4. The method of claim 1 wherein at least a second portion of the liquid stream from step (d) is recycled to step (b).

5. The method of claim 1 wherein at least a portion of the aqueous stream from step (f) is recycled to step (b).

6. The method of claim 1 wherein at least a portion of the aqueous stream from step (f) and a second portion of the liquid stream from step (d) are recycled to step (b).

7. The method of claim 1 wherein at least a portion of the organic phase stream after recovery of furfural is recycled to step (e) to provide the biphasic reaction medium.

8. The method of claim 7 wherein the organic phase stream after recovery of furfural is purified prior to recycling to step (e).

9. The method of claim 2 wherein the amount of the dehydration acid is in the range of from 0.5 wt %, to 2.0 wt %, based on the liquid stream.

10. The method of claim 1 wherein step (b) is carried out at a temperature within the range of about 50°

C. to about 150°

C. and a pressure within the range of 0.1 bara to about 11 bara.

11. The method of claim 1 wherein the dehydration acid is a mineral acid or an organic acid.

12. The method of claim 11 wherein the mineral acid is selected from the group consisting of sulfuric acid, phosphoric acid, hydrochloric acid, and mixtures thereof.

13. The method of claim 11 wherein the organic acid is selected from the group consisting of acetic acid, formic acid, oxalic acid, levulinic acid, citric acid, and mixtures thereof.

14. The method of claim 12 wherein the dehydration acid is a mineral acid.

15. The process of claim 1, wherein the liquid stream separated from the wet solid stream comprises C5 carbohydrates in a concentration ranging from about 0.1 wt % to about 15wt %.

16. The method of claim 14 wherein recovering a-hydroxysulfonic acid from a salt of α

-hydroxysulfonic acid formed in step (b) in its component form.

17. The method of claim 7 wherein the separation in step (c) is carried out at a temperature within the range from about 50°

C. to about 150°

C. and a pressure within the range from about 0.1 bara to about 5 bara.

18. The method of claim 1 wherein at least a portion of the aqueous stream from step (f) is contacted with the wet solid stream prior to recycling to step (b).

19. The method of claim 9 wherein the amount of the dehydration acid is in the range of from 0.7wt to 1.5 wt %, based on the liquid stream.

20. The method of claim 1 wherein the α

-hydroxysulfonic acid is present in an amount of from about 1% wt. to about 55% wt., based on the solution.

21. The method of claim 1 wherein the α

-hydroxysulfonic acid is produced from (a) a carbonyl compound or a precursor to a carbonyl compound with (b) sulfur dioxide or a precursor to sulfur dioxide and (c) water.

22. The method of claim 1 wherein the α

-hydroxysulfonic acid is in-situ generated.

23. The method of claim 1 wherein recycling at least a portion of the aqueous stream and a second portion of the liquid stream to step (b).