Process for the manufacture of furural and furfural derivatives

• US 10,087,160 B2
• Filed: 08/13/2015
• Issued: 10/02/2018
• Est. Priority Date: 08/14/2014
• Status: Expired due to Fees

• Current Assignee: Shell Oil Company (Shell Plc)
• Original Assignee: Shell Oil Company (Shell Plc)
• Inventors: Chheda, Juben Nemchand, Lange, Jean Paul Andre Marie Joseph Ghislain
• Primary Examiner(s): Rozof, Timothy R
• Application Number:
  US15/502,828
• Publication Number:
  US 20170233361A1
• Time in Patent Office: 1,146 Days
• CPC Class Codes: B01J 21/02 Boron or aluminium; Oxides or hydroxides thereof
• CPC Class Codes: B01J 2208/027 Beds
• CPC Class Codes: B01J 23/02 of the alkali- or alkaline earth metals or beryllium
• CPC Class Codes: B01J 23/06 of zinc, cadmium or mercury
• CPC Class Codes: B01J 23/26 Chromium
• CPC Class Codes: B01J 23/34 Manganese
• CPC Class Codes: B01J 23/72 Copper
• CPC Class Codes: B01J 23/755 Nickel
• CPC Class Codes: B01J 8/0278 Feeding reactive fluids for solid material B01J8/0015
• CPC Class Codes: C07D 307/50 Preparation from natural products
• CPC Class Codes: C10L 1/18 containing oxygen
• CPC Class Codes: C10L 1/1857 Aldehydes; Ketones
• CPC Class Codes: Y02P 20/582 Recycling of unreacted starting or intermediate materials

Abstract

The present invention provides a process for preparing furfural and furfural derivatives using a furfural-derived solvent.

Claims

1. A process for preparing furfural and/or furfural derivatives, comprising:

(a) providing an aqueous C₅ sugar-containing feed stream;

(b) contacting an aqueous phase comprising the aqueous C₅ sugar-containing feed stream with an organic phase comprising organic solvent at a temperature in the range of about 100°

C. to about 300°

C. for a time sufficient to effect a dehydration reaction to convert C₅ sugar to furfural, wherein at least part of the furfural dissolves in the organic solvent phase to form a furfural-containing organic phase;

(c) separating the furfural-containing organic phase from the aqueous phase;

(d) separating furfural from the furfural-containing organic phase;

(e) converting at least part of the furfural to a tetrahydrofuranic derivative to obtain tetrahydrofuranic derivative-containing product; and

(f) providing at least part of the tetrahydrofuranic derivative to step (b) as organic solvent.

2. The process of claim 1, wherein the tetrahydrofuranic derivative is of the general formula (1):

4. The process of claim 1, wherein the furfural is converted to 2-methyltetrahydrofuran by hydrogenating part of the furfural in the presence of a reactor bed comprising at least a first catalyst to obtain 2-methyltetrahydrofuran-containing product;

and wherein in step (e) a least part of the 2-methyltetrahydrofuran is provided to step (b) as organic solvent.

5. The process of claim 4, wherein the hydrogenation is carried out in one stage.

6. The process of claim 4, wherein the first catalyst comprises copper.

7. The process of claim 4, wherein the first catalyst further comprises at least one element selected from the group consisting of chromium, manganese, zinc, aluminum and barium.

8. The process of claim 4, further comprising a second catalyst in the hydrogenating step, the second catalyst comprising at least one element selected from the group consisting of group 8 metals, group 9 metals and group 10 metals of the periodic table.

9. The process of claim 8, wherein the second catalyst comprises nickel.

10. The process of claim 8, wherein the second catalyst further comprises at least one element of the periodic table selected from the group consisting of a group 1 to 7 and group 11 to 15.

11. The process of claim 4, wherein the first catalyst and optionally the second catalyst is supported on a support material comprising at least one material selected form the group consisting of activated carbon, aluminum oxide, silicon dioxide, silicon carbide, calcium oxide, titanium dioxide, and zirconium dioxide.

12. The process of claim 4, further comprising in step (e), wherein at least part of the 2-methyltetrahydrofuran-containing product is condensed to obtain a first phase having a water content of at least about 90% by weight and a second phase having a 2-methyltetrahydrofuran content of at least about 80% by weight and at least part of the second phase is provided as organic solvent to step (b).

13. The process of claim 4, wherein the hydrogenation in step (d) is performed in the presence of a 2-methyltetrahydrofuran derivative.

14. The process of claim 1, wherein in the range of from 1 to 100 wt % of the organic solvent organic phase in step (b) is a tetrahydrofuranic derivative.

15. The process of claim 1, wherein the aqueous C₅ sugar-containing feed stream is prepared by:

(a1) providing a feedstock comprising at least one of i) a lignocellulosic feedstock containing glucan and xylan, ii) hemicellulosic material, and iii) C₅ sugar monomers, C₅ oligomers and C₅ polymers;

(a2) contacting the feedstock with an aqueous medium to form a reaction mixture;

(a3) heating the reaction mixture to an elevated temperature with at least one acid for a period of time sufficient to digest at least part the feedstock and form the aqueous C₅ sugar-containing feed stream and a residual product; and

(a4) separating the aqueous C₅ sugar-containing feed stream from the residual product.

16. The process of claim 1, wherein at least part of the tetrahydrofuranic derivative in the tetrahydrofuranic derivative-containing product is used as a chemical intermediate, fuel additive, or solvent.

17. The process of claim 1, wherein the organic phase comprises at least one water-immiscible organic solvent.

3. The process of claim, wherein the furfural is converted to a tetrahydrofuranic derivative by one or a combination of:

i) a hydrogenation of the furfural, optionally followed by an alkylation;

ii) an aldol-condensation;

or

iii) an etherification.