# US 10,308,623 B2 · Method for producing tetrahydrofurane, 1,4-butanediol or gamma-butyrolactone

> Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt

- Number: US 10,308,623 B2
- Document ID: US10308623B2
- Status: Granted
- Kind: B2
- Application number: 15/541,960
- Filed: 2016-01-08
- Published: 2018-01-04
- Granted: 2019-06-04
- Earliest claimed: 2015-01-09
- Assignees: BASF SE
- Applicants: BASF SE
- Inventors: Alexander Duefert; Rolf Pinkos; Wolf-Steffen Weissker
- Web page: https://patentgrep.com/patent/US10308623B2

## CPC

- C07D 307/08: Preparation of tetrahydrofuran
- C07C 29/149: with hydrogen or hydrogen-containing gases
- C07D 307/33: in position 2, the oxygen atom being in its keto or unsubstituted enol form
- C12P 7/18: polyhydric
- C12P 17/04: containing a five-membered hetero ring, e.g. griseofulvin {, vitamin C}
- Y02P 20/10: Process efficiency
- C07D: HETEROCYCLIC COMPOUNDS (macromolecular compounds C08)
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C12P: FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE {(brewing of beer C12C; producing vinegar C12J; producing specific peptides or proteins C07K; producing enzymes C12N9/00; DNA or RNA concerning genetic engineering, vectors, e.g. plasmids, or their isolation, preparation or purification C12N15/00; measuring or testing processes involving enzymes or microorganisms C12Q; measuring or testing processes involving nucleic acid amplification reactions C12Q1/6844; fermentation processes to form a food composition, A21 or A23; compounds in general, see the relevant compound class, e.g. C01, C07)}
- Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS

## Abstract

Processes for preparing tetrahydrofuran and/or butane-1,4-diol and/or gamma-butyrolactone are provided, including a process for preparing tetrahydrofuran (THF) from succinic acid that has been obtained by conversion of biomass, by conversion of the succinic acid to succinic anhydride, and hydrogenation of the succinic anhydride, with removal of certain secondary components.

## Claims

### Claim 1

A process for preparing at least one of tetrahydrofuran, butane-1,4-diol, and gamma-butyrolactone, the process comprising the steps of:
a) fermentatively preparing succinic acid,
b) converting the succinic acid to succinic anhydride with elimination of water and removal of water,
c) converting the succinic anhydride to the gas phase,
d) removing sulfur compounds from the succinic anhydride by passing the gaseous succinic anhydride through a fixed guard bed that absorbs the sulfur compounds,
e) hydrogenating the gaseous succinic anhydride in the presence of free hydrogen over a metallic catalyst to give the at least one of tetrahydrofuran, butane-1,4-diol, and gamma-butyrolactone.

### Claim 2 (depends on 1)

The process according to claim 1, wherein fermentatively preparing succinic acid comprises:
fermenting from at least one carbon source;
removing biomass from fermentation broth; and
converting the biomass to acid form by acidification.

### Claim 3 (depends on 2)

The process according to claim 2, further comprising transferring the succinic acid without any further purification steps.

### Claim 4 (depends on 1)

The process according to claim 1, wherein step b) is conducted in at least one evaporation apparatus at a pressure in a range from 0.05 to 1 bar and a bottom temperature in a range from 100 to 250° C.

### Claim 5 (depends on 1)

The process according to claim 1, wherein step c) is conducted in at least one distillation apparatus at a top pressure in a range from 0.02 to 2 bar and a bottom temperature in a range from 100 to 300° C. and further comprises removing high boilers via a bottom of the at least one distillation apparatus.

### Claim 6 (depends on 5)

The process according to claim 5, wherein step c) is conducted at a lower pressure than step b) and further comprises:
removing water and any low boilers overhead; and
obtaining the gaseous succinic anhydride via a side draw.

### Claim 7 (depends on 1)

The process according to claim 1, wherein step b) and step c) are combined and are conducted in at least one distillation apparatus at a top pressure in a range from 0.02 to 2 bar and a bottom temperature in a range from 100 to 200° C., and wherein the combined step b) and step c) further comprises:
removing high boilers via a bottom of the at least one distillation apparatus;
removing water overhead; and
recovering the gaseous succinic anhydride via a side draw.

### Claim 8 (depends on 1)

The process according to claim 1, wherein step e) is conducted at a pressure in a range from 1 to 65 bar and a temperature in a range from 150 to 350° C.

### Claim 9 (depends on 1)

The process according to claim 1, wherein a hydrogenation metal in the metallic catalyst is selected from the group consisting of Ru, Re, Co, Cu and mixtures thereof.

### Claim 10 (depends on 1)

The process according to claim 1, wherein the metallic catalyst is a supported catalyst in which a support material of the support catalyst comprises at least one of carbon, at least one oxide of B, at least one oxide of Al, at least one oxide of Si, at least one oxide of Ti, at least one oxide of Ze, at least one oxide of La, at least one oxide of Ce, and at least one oxide of Cr.

### Claim 11 (depends on 1)

The process according to claim 1, wherein the fixed guard bed includes a sulfur-binding metal selected from the group consisting of Ru, Re, Co, Cu and mixtures thereof.

### Claim 12 (depends on 1)

The process according to claim 1, further comprising, after step e), the following step f):
f) distillatively separating water and high boilers from the at least one of tetrahydrofuran, butane-1,4-diol, and gamma-butyrolactone.

### Claim 13 (depends on 12)

The process according to claim 12, wherein step f) is conducted in preparation of tetrahydrofuran in at least three distillation columns, wherein
f1) in a first distillation column of the least three distillation columns, high boilers are removed in a bottom of the first distillation column and a first tetrahydrofuran/water azeotrope is obtained overhead,
f2) the first tetrahydrofuran/water azeotrope from step f1) is separated in a second distillation column of the at least three distillation columns, which is operated at a higher pressure than the first distillation column, into a second tetrahydrofuran/water azeotrope that is removed overhead and tetrahydrofuran that is obtained via a bottom of the second distillation column,
f3) the tetrahydrofuran obtained via the bottom in step f2) is freed in a third distillation column of the at least three distillation columns, the third distillation column including high boilers that are discharged via a bottom of the third distillation column.

### Claim 14 (depends on 11)

The process according to claim 11, wherein the fixed guard bed has at least one of the same ingredients and the same composition as the metallic catalyst.

### Claim 15 (depends on 13)

The process according to claim 13, wherein the second tetrahydrofuran/water azeotrope removed from the second distillation column is recycled into the first distillation column.