Method for producing 1,3-butadiene from 1,4-butanediol

Patent metadata

Field	Value
Publication number	US-10322978-B2
Application number	US-201615552050-A
Country	US
Kind code	B2
Filing date	Feb 17, 2016
Priority date	Feb 18, 2015
Publication date	Jun 18, 2019
Grant date	Jun 18, 2019

Abstract

A method for producing 1,3-butadiene from a 1,4-butanediol feedstock:
One step for esterification of 1,4-butanediol, One step for pyrolysis of 1,4-butanediol diester, producing butadiene.

First claim

The invention claimed is:

1. A method for conversion of a 1,4-butanediol feedstock, said method comprising at least:
a) esterification of the 1,4-butanediol feedstock and a flow comprising more than 50% by weight part carboxylic acid to produce an effluent, and separating the effluent from the reaction section into at least one 1,4-butanediol diester effluent, a water effluent, and a carboxylic acid effluent in at least one separation section, wherein the esterification in said reaction section is implemented in the presence of an acid catalyst at a pressure of between 0.01 and 1.0 MPa and at a flow rate of moles of diol to moles of catalyst in said reaction section of between 0.05 and 25 h −1 ; and
b) pyrolysis of said at least one 1,4-butanediol diester effluent to produce a pyrolysis effluent, wherein said pyrolysis also comprises at least one separation section wherein said pyrolysis effluent is cooled to a temperature that is less than 100° C. to produce at least one liquid pyrolysis effluent and one vapor pyrolysis effluent, wherein said vapor pyrolysis effluent is compressed and/or cooled to condense 1,3-butadiene into a 1,3-butadiene effluent, and separating the liquid pyrolysis effluent by simple distillation to produce a carboxylic acid flow and a 3-buten-1-ol ester flow as a carboxylic acid/3 buten-1-ol ester azeotrope.

2. The method according to claim 1 , wherein the flow of carboxylic acid comprises the carboxylic acid effluent that is obtained from the separation section of a).

3. The method according to claim 1 , wherein the flow of carboxylic acid comprises external carboxylic acid.

4. The method according to claim 1 , wherein said reaction section of a) is implemented in a reactive distillation column, in which the 1,4-butanediol feedstock is introduced into an upper part of the column, and the carboxylic acid is introduced into a lower part of the column, with the ratio of the molar flow rates of 1,4-butanediol and carboxylic acid being between 2 and 6.

5. The method according to claim 1 , wherein the carboxylic acid is formic acid, acetic acid, propanoic acid, butanoic acid, or benzoic acid.

6. The method according to claim 5 , wherein the carboxylic acid is acetic acid.

7. The method according to claim 6 , wherein said separation in a) comprises heterogeneous azeotropic distillation using a driver.

8. The method according to claim 1 , wherein said 3-buten-1-ol ester flow is recycled to pyrolysis b) with the 1,4-butanediol diester.

9. The method according to claim 1 , wherein a THF effluent is separated from the effluent of said reaction section of a).

10. The method according to claim 9 , further comprising c) converting the THF effluent into 1,4-butanediol diester with an acid anhydride effluent in the presence of an acid catalyst to produce an effluent.

11. The method according to claim 10 , wherein the effluent that is obtained from c) conversion of THF into 1,4-butanediol diester is sent directly to b) pyrolysis of 1,4-butanediol diester or to a dedicated step for pyrolysis producing more butadiene.

12. The method according to claim 10 , wherein the effluent that is obtained from c) conversion of THF into 1,4-butanediol diester is sent back to a) esterification of the 1,4-butanediol feedstock.

13. A method for conversion of a 1,4-butanediol feedstock, said method comprising at least:
a) esterification of the 1,4-butanediol feedstock and a flow comprising more than 50% by weight part carboxylic acid to produce an effluent, and separating the effluent from the reaction section into at least one 1,4-butanediol diester effluent, a water effluent, and a carboxylic acid effluent in at least one separation section, wherein the esterification in said reaction section is implemented in the presence of an acid catalyst at a pressure of between 0.01 and 1.0 MPa and at a flow rate of moles of diol to moles of catalyst in said reaction section of between 0.05 and 25 h −1 ; and
b) pyrolysis of said at least one 1,4-butanediol diester effluent to produce a pyrolysis effluent, wherein said pyrolysis also comprises at least one separation section wherein said pyrolysis effluent is cooled to a temperature that is less than 100° C. to produce at least one liquid pyrolysis effluent and one vapor pyrolysis effluent, wherein said vapor pyrolysis effluent is compressed and/or cooled to condense 1,3-butadiene into a 1,3-butadiene effluent, wherein the liquid pyrolysis effluent is separated by distillation with a change in pressure to produce a carboxylic acid flow and a 3-buten-1-ol ester flow.

14. The method according to claim 1 , wherein the flow of carboxylic acid comprises said carboxylic acid flow that is obtained from the liquid pyrolysis effluent.

Assignees

• Ifp Energies Now
• Michelin & Cie

Inventors

• Richard Romain
• Jacquin Marc
• Dorato Margarita
• Pacheco Nuno
• Rannoux Claire

Classifications

• C07C67/08

  by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds · CPC title

• C07C1/213 Primary

  by splitting of esters · CPC title

• C07C69/16

  of dihydroxylic compounds · CPC title

• Y02P20/127

  Cross-Sectional Technologies · mapped topic

• C07C11/167

  1, 3-Butadiene · CPC title