Process for the preparation of butadiene

Patent metadata

Field	Value
Publication number	US-9878965-B2
Application number	US-201414897379-A
Country	US
Kind code	B2
Filing date	Jun 13, 2014
Priority date	Jun 13, 2013
Publication date	Jan 30, 2018
Grant date	Jan 30, 2018

Abstract

The present invention relates to a gas-phase process for the preparation of butadiene comprising
(i) providing a gas stream G-1 comprising ethanol; (ii) contacting the gas stream G-1 comprising ethanol with a catalyst, thereby obtaining a gas stream G-2 comprising butadiene, wherein the catalyst comprises a zeolitic material having a framework structure comprising YO 2 , Y standing for one or more tetravalent elements, wherein at least a portion of Y comprised in the framework structure is isomorphously substituted by one or more elements X, as well as to a zeolitic material having a framework structure comprising YO 2 , Y standing for one or more tetravalent elements, wherein at least a portion of Y comprised in the framework structure is isomorphously substituted by one or more elements X, wherein the zeolitic material displays a specific X-ray powder diffraction pattern, and to its use.

First claim

The invention claimed is:

1. A gas-phase process for the preparation of butadiene comprising:
(i) providing a gas stream G-1 comprising ethanol; and
(ii) contacting the gas stream G-1 comprising ethanol with a catalyst, thereby obtaining a gas stream G-2 comprising butadiene,
wherein the catalyst comprises a zeolitic material having a MWW framework structure comprising YO 2 , and
wherein at least a portion of Y comprised in the framework structure is isomorphously substituted by one or more elements X,
wherein Y is selected from the group consisting of Si, Sn, Ti, Zr, Ge, and combinations of two or more thereof, and
wherein X is selected from the group consisting of Zr, Ti, Sn, Ga, Nb, Ta, Sc, Ge, Al, B, Fe, and combinations of two or more thereof.

2. The process of claim 1 , wherein the gas stream G-1 additionally comprises acetaldehyde.

3. The process of claim 2 , wherein the molar ratio of ethanol to acetaldehyde in the gas stream G-1 is in the range of from 1:1 to 6:1.

4. The process of claim 2 , wherein 80 vol.-% or more of the gas stream G-1 comprises ethanol or a mixture of ethanol and acetaldehyde.

5. The process of claim 1 , wherein the molar ratio of Y:X in the framework structure ranges from 10:1 to 150:1.

6. The process of claim 1 , wherein the molar ratio of Y:X in the framework structure ranges from 50:1 to 700:1.

7. The process of claim 1 , wherein the catalyst comprises Sn-MWW and/or Ta-MWW.

8. The process of claim 1 , wherein the zeolitic material comprised in the catalyst has an MWW framework structure, and wherein Y is Si and X is Ti.

9. The process of claim 8 , wherein the zeolitic material further comprises Zn as a non-framework element.

10. The process of claim 1 , wherein the catalyst comprises a zeolitic material having an X-ray powder diffraction pattern comprising at least the following reflections:

Intensity (%)
Diffraction angle 2θ/° [Cu K(alpha 1)]

67.0-87.0
15.16 ± 0.3

79.8-99.8
15.82 ± 0.3

45.3-65.3
22.47 ± 0.3

100
23.88 ± 0.3

52.3-72.3
27.06 ± 0.3

75.0-95.0
27.21 ± 0.3

wherein 100% relates to the intensity of the maximum peak in the X-ray powder diffraction pattern.

11. The process of claim 1 , wherein contacting the gas stream G-1 with the catalyst is carried out at a temperature in the range of from 300 to 500° C.

12. The process of claim 1 , wherein contacting the gas stream G-1 with the catalyst is carried out at a pressure in the range of from 1 to 5 bar.

13. The process of claim 1 , wherein contacting gas stream G-1 with the catalyst is carried out in a continuous mode.

14. The process of claim 1 , wherein contacting the gas stream G-1 with the catalyst is carried out in one or more reactors, and wherein the one or more reactors comprise the catalyst in the form of a fixed bed.

15. The process of claim 1 , wherein prior to contacting the gas stream G-1 with the catalyst, the gas stream G-1 is heated.

16. The process of claim 1 , wherein prior to contacting the gas stream G-1 with the catalyst, the catalyst is activated.

17. The process of claim 16 , wherein the catalyst is activated by heating to a temperature in the range of from 300 to 450° C.

18. The process of claim 16 , wherein the catalyst is heated with a temperature ramp in the range of from 0.5 to 10 K/min.

19. The process of claim 16 , wherein the catalyst is activated in one or more reactors.

20. The process of claim 16 , wherein during heating the catalyst is flushed with an inert gas.

21. The process of claim 1 , wherein the gas stream G-2 comprises the butadiene in an amount of from 10 to 90 vol-%, based on the total volume of the gas stream G-2.

22. The process of claim 1 , further comprising
(iii) separating butadiene from the gas stream G-2, thereby obtaining a purified gas stream G-3 comprising butadiene.

23. The process of claim 1 , wherein the gas stream G-2 further comprises diethyl ether, and wherein the diethyl ether is separated from the gas stream G-2 to be recycled in the gas-phase process for the preparation of butadiene.

24. The process of claim 23 , wherein the gas stream G-2 comprises the diethyl ether in an amount of from 1 to 65 vol-% based on the total volume of the gas stream G-2.

25. The process of claim 23 , further comprising hydrolyzing at least a portion of separated diethyl ether to ethanol prior to its recycling to the gas-phase process for the preparation of butadiene.

26. The process of claim 25 , wherein the separated diethyl ether is hydrolyzed under acidic conditions.

27. The process of claim 1 , wherein the gas stream G-2 further comprises crotonaldehyde.

28. The process of claim 27 , wherein the gas stream G-2 comprises the crotonaldehyde in an amount of from 0.1 to 15 vol-%, based on the total volume of the gas stream G-2.

29. The process of claim 1 , further comprising regenerating the catalyst.

30. The method of claim 1 , wherein a selectivity of the process relative to butadiene is at least 10%.

Assignees

• Basf Se

Inventors

• Spannhoff Kirsten
• Parvulescu Andrei-Nicolae
• Lange De Oliveira Armin
• Marx Stefan
• Feyen Mathias
• Müller Ulrich
• Schwab Ekkehard

Classifications

• C07C2529/89

  Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium · CPC title

• C07C2529/86

  Borosilicates; Aluminoborosilicates · CPC title

• C07C2529/78

  containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium · CPC title

• C07C2529/70

  of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65 · CPC title

• C01P2006/12

  Surface area · CPC title