Process for preparing furfural from biomass

Patent metadata

Field	Value
Publication number	US-10138218-B2
Application number	US-201515502897-A
Country	US
Kind code	B2
Filing date	Aug 13, 2015
Priority date	Aug 14, 2014
Publication date	Nov 27, 2018
Grant date	Nov 27, 2018

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 C 5 -carbohydrate compound in monomeric and/or oligomeric form, and dehydrating the C 5 -carbohydrate compound in the presence of a heterogeneous solid acid catalyst, 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, which can be optionally recycled to the hydrolysis step.

First claim

We claim:

1. A method for producing furfural from biomass material containing pentosane comprising:
(a) providing a biomass comprising a polysaccharide containing C5 carbohydrate monomeric units;
(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 C 5 -carbohydrate compound in monomeric and/or oligomeric form, and α-hydroxysulfonic acid, the at least one α-hydroxysulfonic acid having the general formula

wherein R1 and R2 are individually hydrogen or hydrocarbyl with up to about 9 carbon atoms;
(c) separating at least a portion of the α-hydroxysulfonic acid from the product stream containing at least one C 5 -carbohydrate compound to provide an acid-removed product stream containing the at least one C 5 -carbohydrate compound and recovering the α-hydroxysulfonic acid in its component form;
(d) separating a liquid stream containing said at least one C 5 -carbohydrate compound and a wet solid stream containing remaining biomass from the acid-removed product;
(e) dehydrating the C 5 -carbohydrate compound in at least a first portion of the liquid stream in the presence of a heterogenous solid acid catalyst capable of catalyzing the dehydration of C5 carbohydrates to furfural and/or its derivatives, 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 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 solid acid catalyst is a solid acid catalyst having total acid site strength higher than 0.05 mmol/g.

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 contact time of the first portion of the liquid stream to the heterogenous solid catalyst is in the range of 1 minute to 24 hours.

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 solid acid catalyst is selected from the group consisting of acidic ion exchange resins, acidic zeolites, layered clay, amorphous silica alumina, gamma alumina, mesoporous silicate and aluminosilicates, aluminum incorporated mesoporous silica, sulfonic acid functionalized metal oxides, and microporous silicoaluminophasphates, perfluorinated ion-exchange materials, sulfonated grapheme oxide, and heteropolyacids.

12. The method of claim 11 wherein the solid acid catalyst is selected from the group consisting of acidic ion exchange resins, acidic zeolites, amorphous silica alumina, and mesoporous silicate and aluminosilicates.

13. The method of claim 12 wherein the solid acid catalyst is acidic ion exchange resin.

14. 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 15 wt %.

15. The method of claim 1 wherein mineral acid is added to step (b) or step (c).

16. 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.

17. 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).

18. 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.

19. The method of claim 1 wherein the α-hydroxysulfonic acid is produced from (a) a carbonyl compound or a precursor to a carbonyl compound having the general formula

where R1 and R2 are individually hydrogen or hydrocarbyl with up to about 9 carbon atoms or a mixture thereof with (b) sulfur dioxide or a precursor to sulfur dioxide and (c) water.

20. The method of claim 1 wherein the α-hydroxysulfonic acid is in-situ generated.

Assignees

• Shell Oil Co

Inventors

• Chheda Juben Nemchand
• Weider Paul Richard
• Blackbourn Robert Lawrence
• Lange Jean Paul Andre Marie Joseph Ghislain

Classifications

• C07D307/50 Primary

  Preparation from natural products · CPC title

• C07D307/46

  Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom · CPC title