Process for preparing 1,3-butadiene from N-butenes by oxidative dehydrogenation

Patent metadata

Field	Value
Publication number	US-9957208-B2
Application number	US-201515503189-A
Country	US
Kind code	B2
Filing date	Aug 11, 2015
Priority date	Aug 12, 2014
Publication date	May 1, 2018
Grant date	May 1, 2018

Abstract

The invention relates to a process for preparing butadiene from n-butenes, comprising the steps of:
A) providing an input gas stream a comprising n-butenes, B) feeding the input gas stream a comprising n-butenes and a gas containing at least oxygen into at least one oxidative dehydrogenation zone and oxidatively dehydrogenating n-butenes to butadiene, giving a product gas stream b comprising butadiene, unconverted n-butenes, water vapor, oxygen, low-boiling hydrocarbons and high-boiling secondary components, with or without carbon oxides and with or without inert gases; Ca) cooling the product gas stream b by contacting with a cooling medium in at least one cooling zone, the cooling medium being at least partly recycled and having an aqueous phase and an organic phase of an organic solvent, wherein the organic solvent is selected from the group consisting of toluene, o-, m- and p-xylene, mesitylene, mono-, di- and triethylbenzene, mono-, di- and triisopropylbenzene and mixtures thereof, and the mass ratio of the aqueous phase to the organic phase in the cooling medium when it is fed into the cooling zones prior to the contacting with the product gas stream being from 0.015:1 to 10:1, Cb) compressing the cooled product gas stream b which may have been depleted of high-boiling secondary components in at least one compression stage, giving at least one aqueous condensate stream c 1 and one gas stream c 2 comprising butadiene, n-butenes, water vapor, oxygen and low-boiling hydrocarbons, with or without carbon oxides and with or without inert gases; D) removing uncondensable and low-boiling gas constituents comprising oxygen and low-boiling hydrocarbons, with or without carbon oxides and with or without inert gases, as gas stream d 2 from the gas stream c 2 by absorbing the C 4 hydrocarbons comprising butadiene and n-butenes in an absorbent, giving an absorbent stream laden with C 4 hydrocarbons and the gas stream d 2 , and then desorbing the C 4 hydrocarbons from the laden absorbent stream, giving a C 4 product gas stream d 1, E) separating the C 4 product stream d 1 by extractive distillation with a butadiene-selective solvent into a stream e 1 comprising butadiene and the selective solvent and a stream e 2 comprising n-butenes; F) distilling the stream e 1 comprising butadiene and the selective solvent into a stream f 1 consisting essentially of the selective solvent and a stream f 2 comprising butadiene.

First claim

The invention claimed is:

1. A process for preparing butadiene from n-butenes, comprising the steps of:
A) providing an input gas stream a comprising n-butenes,
B) feeding the input gas stream a comprising n-butenes and a gas containing at least oxygen into at least one oxidative dehydrogenation zone and oxidatively dehydrogenating n-butenes to butadiene, giving a product gas stream b comprising butadiene, unconverted n-butenes, water vapor, oxygen, low-boiling hydrocarbons and high-boiling secondary components, with or without carbon oxides and with or without inert gases;
Ca) cooling the product gas stream b by contacting with a cooling medium in at least one cooling zone, the cooling medium being at least partly recycled and having an aqueous phase and an organic phase of an organic solvent, wherein the organic solvent is selected from the group consisting of toluene, o-, m- and p-xylene, mesitylene, mono-, di- and triethylbenzene, mono-, di- and triisopropylbenzene and mixtures thereof, and the mass ratio of the aqueous phase to the organic phase in the cooling medium when it is fed into the cooling zones prior to the contacting with the product gas stream being from 0.15:1 to 10:1;
Cb) compressing the cooled product gas stream b which may have been depleted of high-boiling secondary components in at least one compression stage, giving at least one aqueous condensate stream c 1 and one gas stream c 2 comprising butadiene, n-butenes, water vapor, oxygen and low-boiling hydrocarbons, with or without carbon oxides and with or without inert gases;
D) removing uncondensable and low-boiling gas constituents comprising oxygen and low-boiling hydrocarbons, with or without carbon oxides and with or without inert gases, as gas stream d 2 from the gas stream c 2 by absorbing the C 4 hydrocarbons comprising butadiene and n-butenes in an absorbent, giving an absorbent stream laden with C 4 hydrocarbons and the gas stream d 2 , and then desorbing the C 4 hydrocarbons from the laden absorbent stream, giving a C 4 product gas stream d 1 ,
E) separating the C 4 product stream d 1 by extractive distillation with a butadiene-selective solvent into a stream e 1 comprising butadiene and the selective solvent and a stream e 2 comprising n-butenes;
F) distilling the stream e 1 comprising butadiene and the selective solvent into a stream f 1 consisting essentially of the selective solvent and a stream f 2 comprising butadiene.

2. The process according to claim 1 , wherein the mass ratio of the aqueous phase to the organic phase in the cooling medium used in step Ca) is from 0.18:1 to 2:1.

3. The process according to claim 2 , wherein stage Ca) is conducted in three stages Ca 1 ), Ca 2 ) and Ca 3 ) in three cooling zones.

4. The process according to claim 3 , wherein an organic solvent laden with high-boiling secondary components from the second stage Ca 2 ) is conducted into the first stage Ca 1 ), and an organic solvent less heavily laden with high-boiling secondary components from the third stage Ca 3 ) is conducted into the second stage Ca 2 ).

5. The process according to claim 3 , wherein a fresh cooling medium as yet unladen with the high-boiling secondary components is fed into the third cooling stage Ca 3 ) in single pass and in countercurrent into the cooling stage.

6. The process according to claim 3 , wherein the diameter of the cooling stage Ca 3 ) is less than the diameter of the cooling stages Ca 1 ) and Ca 2 ).

7. The process according to claims 3 , wherein the first cooling stage Ca 1 ) has a parallel and interchangeable configuration.

8. The process according to claim 1 , wherein the cooling medium is fed into the cooling zones through one or more nozzles.

9. The process according to claim 8 , wherein a flow is generated in the nozzle(s), in which the Reynolds number Re of the two phases of the cooling medium is at least 100.

10. The process according to claim 1 , wherein the volume-specific power input into the cooling medium is at least 10 3 W/m 3 .

11. The process according to claim 1 , wherein the coefficient of variation for each component of the cooling medium on entry into the cooling zones is less than 1.

12. The process according to claim 1 , wherein stage Cb) comprises at least one compression stage Cba) and at least one cooling stage Cbb).

13. The process according to claim 12 , wherein the coolant in the cooling stage Cbb) comprises the same organic solvent which is used in stage Ca) as the organic phase of the cooling medium.

14. The process according to claim 1 , wherein stage Cb) comprises a plurality of compression stages Cba 1 ) to Cban) and cooling stages Cbb 1 ) to Cbbn).

15. The process according to claim 1 , wherein step D) comprises steps Da) to Dc):
Da) absorbing the C 4 hydrocarbons comprising butadiene and n-butenes in a high-boiling absorbent, giving an absorbent stream laden with C 4 hydrocarbons and the gas stream d 2 ,
Db) removing oxygen from the absorbent stream laden with C 4 hydrocarbons from step Da) by stripping with an uncondensable gas stream, and
Dc) desorbing the C 4 hydrocarbons from the laden absorbent stream, giving a C 4 product gas stream d 1 comprising less than 100 ppm of oxygen.

16. The process according to claim 15 , wherein the high-boiling absorbent used in step Da) is an aromatic hydrocarbon solvent.

Assignees

• Basf Se
• Linde Ag

Inventors

• Grüne Philipp
• Hammen Oliver
• Eckrich Rainer
• Josch Jan Pablo
• Walsdorff Christian
• Biegner Andre
• Bloch Gregor
• Boelt Heinz
• Reyneke Hendrik
• Toegel Christine
• Wenning Ulrike

Classifications

• C07C7/08

  by extractive distillation · CPC title

• C07C7/09

  by fractional condensation · CPC title

• C07C11/167

  1, 3-Butadiene · CPC title

• C07C7/005

  Processes comprising at least two steps in series · CPC title

• C07C5/48 Primary

  with oxygen as an acceptor · CPC title