Separation, recovery and upgrading of biomass derived 2,3-butanediol

Patent metadata

Field	Value
Publication number	US-11565989-B2
Application number	US-202017087841-A
Country	US
Kind code	B2
Filing date	Nov 3, 2020
Priority date	Nov 3, 2020
Publication date	Jan 31, 2023
Grant date	Jan 31, 2023

Abstract

The invention relates to a two-way approach to isolate, recover and upgrade 2,3-Butanediol (2,3-BDO) from fermentation broth. A complete separation and recovery process for 2,3-BDO using acetalization and trans-acetalization sequence. Acetalization with butyraldehyde using heterogeneous catalysts, either Amberlyst-15® or Nafion NR50®, efficiently isolates 2,3-BDO as phase-separated protected dioxolane. The approach provides significant process advantages with easy product recovery and high recyclability of the catalyst. Trans-acetalization of dioxolane with methanol (methanolysis) followed by distillation of acetal, yielded very high purity 2,3-BDO with about 90% isolated yield. Alternatively, dioxolane is used in a process direct to methyl ethyl ketone (MEK) as a BDO synthon allowing for recovery of the aldehyde.

First claim

The invention claimed is:

1. A solvent free method for separation and recovery of 2,3-butanediol (2,3-BDO) from fermentation broth, said process comprising the steps of:
a) acetalization of fermentation broth with an aldehyde in the presence of a catalyst forming cyclic acetal; wherein the catalyst is selected from the group consisting of ZSM-5 with silicon/aluminum, Nafion NR50® and Amberlyst-15®;
said step (a) conducted at a temperature that is selected from room temperature and about 40° C., for about 3-5 hours,
b) isolating 2,3-BDO as phase-separated cyclic acetal; wherein the cyclic acetal is dioxolane;
c) transacetalization of phase-separated dioxolane with methanol followed by distillation of acetal, to obtain high purity 2,3-BDO and butyraldehyde dimethyl acetal;
d) distilling off butyraldehyde dimethyl acetal;
e) recovering high purity 2,3-BDO; and
f) recycling and reusing the catalyst; wherein the catalyst is reactive after about 10 cycles.

2. The method according to claim 1 , wherein the catalyst is ZSM-5 with silicon/aluminum.

3. The method according to claim 1 , wherein the aldehyde is selected from the group consisting of butanal, hexanal, octanal, 2-ethylbutanal and 2-ethyl hexanal.

4. The method according to claim 1 , wherein the catalyst is selected from the group consisting of Nafion NR50® and Amberlyst-15®.

5. The method according to claim 4 , wherein the amount of the catalyst is about 10% to about 30% by weight.

6. The method according to claim 1 , wherein the fermentation broth is selected from the group consisting of aqueous butanediol, butanediol broth mimic and actual fermentation broths.

7. The method according to claim 6 , wherein the fermentation broth comprises pure sugar and hydrolysate broth.

8. The method according to claim 1 , wherein the isolation yield of pure 2,3-BDO is about 90%.

9. The method according to claim 1 wherein the catalyst performed at a conversion level of more than 95%.

10. The method according to claim 1 wherein the aldehyde employed is selected from butanal and hexanal.

11. The method according to claim 7 wherein the fermentation broth further comprises components selected from glucose, xylose, arabinose, acetoin, glycerol, xylitol, lactic acid, ethanol, and acetic acid.

12. An integrated solvent free method for separation and recovery of 2,3-butanediol (2,3-BDO) from fermentation broth, said process comprising the steps of:
a) acetalization of fermentation broth with an aldehyde in the presence of a catalyst forming cyclic acetal; wherein the catalyst is selected from the group consisting of aluminum oxide, aluminum phosphate, ZSM-5 with silicon/aluminum, Nafion NR50® and Amberlyst-15®;
b) isolating 2,3-BDO as phase-separated cyclic acetal; wherein the cyclic acetal is dioxolane;
c) upgrading methyl ethyl ketone (MEK) synthesis by cleavage of dioxolane with a catalyst to form methyl ethyl ketone (MEK) and butanal;
d) recycling butanal by adding the resulting product of MEK and butanal to the said fermentation broth.

13. The method according to claim 12 , wherein the method was conducted in the presence of a catalyst selected from aluminum oxide, aluminum phosphate, and ZSM-5 with silicon/aluminum.

14. The method according to claim 12 wherein the catalyst is ZSM-5 with silicon/aluminum.

15. The method according to claim 12 wherein the catalyst is selected from the group consisting of Nafion NR50® and Amberlyst-15®.

16. The method according to claim 12 wherein the wherein the amount of the catalyst is about 50% by weight to about 60% by weight.

17. The method according to claim 14 wherein the catalyst is ZSM-5 with Si/Al: 80.

18. The method according to claim 13 , wherein the amount of the catalyst is about 40% by weight to about 50% by weight.

19. The method according to claim 12 , wherein step (c) of the method was conducted at a temperature of about 290° C. to about 325° C.

20. A solvent free method for separation and recovery of 2,3-butanediol (2,3-BDO) from fermentation broth, said process comprising the steps of:
a) acetalization of fermentation broth with an aldehyde in the presence of a catalyst forming cyclic acetal; wherein the catalyst is selected from the group consisting of ZSM-5 with silicon/aluminum, Nafion NR50® and Amberlyst-15®;
said step (a) conducted at a temperature that is selected from room temperature and about 40° C., for about 3-5 hours;

a) isolating 2,3-BDO as phase-separated cyclic acetal; wherein the cyclic acetal is dioxolane;
b) transacetalization of phase-separated dioxolane with methanol followed by distillation of acetal, to obtain high purity 2,3-BDO and butyraldehyde dimethyl acetal;
c) distilling off butyraldehyde dimethyl acetal;
d) recovering high purity 2,3-BDO;
e) recycling and reusing the catalyst; wherein the catalyst is reactive after about 10 cycles;
f) upgrading methyl ethyl ketone (MEK) synthesis by cleavage of dioxolane obtained from step (a) with an acid catalyst to form methyl ethyl ketone (MEK) and butanal; and
g) recycling butanal by adding the resulting product of MEK and butanal to the said fermentation broth.

Assignees

• Us Dept Energy

Inventors

• Moore Cameron
• Rajale Trideep
• Ramasamy Karthikeyan K
• Sutton Andrew

Classifications

• C07C29/92 Primary

  by a consecutive conversion and reconstruction · CPC title

• C07C31/207

  1,4-Butanediol; 1,3-Butanediol; 1,2-Butanediol; 2,3-Butanediol · CPC title

• C07C2531/025

  Sulfonic acids · CPC title

• C07C2521/12

  Silica and alumina · CPC title

• Y02E50/10

  Biofuels, e.g. bio-diesel · CPC title