Closed-loop production of furfural from biomass

• US 10,005,749 B2
• Filed: 08/13/2015
• Issued: 06/26/2018
• 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
• Primary Examiner(s): Oh, Taylor V
• Application Number:
  US15/502,808
• Publication Number:
  US 20170233360A1
• Time in Patent Office: 1,048 Days
• Field of Search: 549489
• CPC Class Codes: C07D 307/48 Furfural
• CPC Class Codes: C07D 307/50 Preparation from natural products
• CPC Class Codes: Y02E 50/10 Biofuels, e.g. bio-diesel

Abstract

Methods and processes for the production of valuable organic products and alcohols from biomass material using a closed-loop process having numerous advantages over prior production methods are described. In the process, the biomass is subjected to acid-catalyzed digestion, followed by a separation of the digestion product stream into a solid product stream and a liquid product stream, the liquid product stream thereafter undergoing acid-catalyzed dehydration in the presence of an organic solvent, and thereafter separating the organic products in the organic layer from the aqueous layer. During the process, aqueous and organic fluid streams are fed back into various portions of the production process to increase the concentration of active portions and maximize product recovery.

Claims

1. A closed-loop process for converting biomass into furfural, the process comprising the steps of:

(a) providing a pentosan-containing biomass material;

(b) subjecting the pentosan-containing biomass material to an acid catalyzed digestion process in a digestion vessel at a temperature greater than about 100 °

C. for a period of time sufficient to produce a digested product stream comprising C₅-carbohydrates and solids comprising cellulose;

(c) separating the digested product stream into a liquid product stream and a solid product stream, the liquid product stream comprising carbohydrate compounds, of which carbohydrate compounds at least 50 wt % are C₅- carbohydrate compounds, based on the weight of carbohydrate compounds in the liquid product stream, and the solid product stream comprising solids comprising cellulose;

(d) subjecting the C₅-carbohydrate in the liquid product stream to a dehydration reaction in a reaction vessel at a temperature in the range of from about 100 °

C. to about 250 °

C. in the presence of an acid catalyst and a biphasic mixture comprising an aqueous phase and a water-immiscible organic phase, which comprises an organic solvent, for a period of time sufficient to produce furfural or a furan derivative comprising tetrahydrofuran (THF), furan, and 2-methyl THF;

(e) retrieving from the reaction vessel a dehydration product stream comprising water, organic solvent and comprising furfural and separating the dehydration product stream into an aqueous recycle stream and an organic product stream comprising furfural;

(f) recycling the aqueous recycle stream back into the digestion vessel in step (b); and

(g) extracting the furfural from the organic product stream by at least one separation process.

2. The process of claim 1, wherein the aqueous recycle stream comprises the acid catalyst.

5. The process of claim 1, wherein the acid catalyst in the digestion process, the dehydration process, or both is selected from the group consisting of inorganic acids and organic acids.

6. The process of claim 1, wherein the acid catalyst in the digestion process, the dehydration process, or both, is a mineral acid selected from the group consisting of HCl, HNO₃, H₂SO₄, H₃PO₄, and H₃BO₃.

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

8. The process of claim 7, wherein the liquid product stream comprises C₅ carbohydrates in a concentration ranging from about 0.2 wt % to about 10 wt %.

9. The process of claim 1, wherein the aqueous recycle stream in step (f) comprises salts and the aqueous recycle stream is treated to remove at least part of the salts.

10. The process of claim 1, wherein the solid product stream comprises C₅-carbohydrate and at least part of the aqueous recycle stream from step (f) is contacted with the solid product stream to extract at least part of the C₅-carbohydrate.

11. The process of claim 1, wherein part of the liquid product stream from step (f) is directly recycled to the digestion vessel in step (b).

12. The process of claim 1, wherein part of the organic product stream comprising furfural or the furan derivative from step (e) is directly recycled to the dehydration reaction of step (d).

13. The process of claim 1, wherein solids in the solid product stream are converted into alcohol by hydrolysis and fermentation, glycol by hydrolysis or catalytic conversion, acid by fermentation or chemical conversion, power or energy by burning or otherwise treating the solids in a power plant or similar power production facility, or a fuel gas by gasification methods.

3. The process of 1, wherein the mixture comprising pentosan containing biomass material and water has a solid-to-liquid weight ratio ranging from about 1:

3 to about 1;

30.

4. The process of claim 3, wherein the mixture comprising pentosan containing biomass material and water has a solid-to-liquid ratio ranging from about 1:

6 to about 1;

10.