Process For The Preparation Of Butadiene

Patent metadata

Field	Value
Publication number	US-2016145171-A1
Application number	US-201414897379-A
Country	US
Kind code	A1
Filing date	Jun 13, 2014
Priority date	Jun 13, 2013
Publication date	May 26, 2016
Grant date	—

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

1 . 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.

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 of 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 X stands for one or more trivalent, tetravalent, and/or pentavalent elements, wherein the one or more elements X.

8 . The process of claim 1 , wherein Y is selected from the group consisting of Si, Sn, Ti, Zr, Ge, and combinations of two or more thereof.

9 . The process of claim 1 , wherein the catalyst comprises a zeolitic material having a framework structure selected from the group consisting of BEA, MWW, MFI, MEL, MOR, RUT, DOH, MTN, FER, FAU, CDO, LEV, CHA, and combinations of two or more thereof.

10 . The process of claim 9 , wherein the catalyst comprises isomorphously substituted zeolite beta and/or Sn-MWW and/or Ta-MWW.

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

12 . The process of claim 11 , wherein the zeolitic material further comprises Zn as non-framework element.

13 . The process of claim 1 , wherein the catalyst comprises a zeolitic material according to claim 33 to 37 .

14 . 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.

15 . 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.

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

17 . The process of claim 1 , wherein contacting the gas stream G-1 with the catalyst is carried out in one ore more reactors, wherein the one ore more reactors contain the catalyst in the form of a fixed bed.

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

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

20 . The process of claim 19 , wherein the catalyst is activated by heating to a temperature in the range of from 300 to 450° C.

21 . The process of claim 19 , wherein the catalyst is heated with a temperature ramp in the range of from 0.5 to 10 K/min.

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

23 . The process of claim 19 , wherein during heating the catalyst is flushed with an inert gas.

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

25 . 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.

26 . 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 and recycling the separated diethyl ether to the gas-phase process for the preparation of butadiene.

27 . The process of claim 26 , wherein the gas stream G-2 contains the diethyl ether in an amount of from 1 to 65 vol-% based on the total volume of the gas stream G-2.

28 . The process of claim 26 , further comprising hydrolyzing at least a portion of the separated diethyl ether to ethanol prior to its recycling to the gas-phase process for the preparation of butadiene.

29 . The process of claim 28 , wherein the separated diethyl ether is hydrolyzed under acidic conditions.

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

31 . The process of claim 30 , wherein the gas stream G-2 contains the crotonaldehyde in an amount of from 0.1 to 15 vol-%, based on the total volume of the gas stream G-2.

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

33 . 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, and wherein the zeolitic material has 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.

34 . The zeolitic material of claim 33 , wherein the molar ratio of Y:X in the framework structure ranges from 100:1 to 700:1.

35 . The zeolitic material of claim 33 , wherein X stands for one or more trivalent, tetravalent, and/or pentavalent elements.

36 . The zeolitic material of claim 33 , wherein Y is selected from the group consisting of Si, Sn, Ti, Zr, Ge and combinations of two or more thereof.

37 . The zeolitic material of claim 33 , wherein the zeolitic material has a BET specific s

Assignees

• Basf Se

Inventors

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

Classifications

• C01B39/085

  Group IVB- metallosilicates · CPC title

• B01J37/0045

  Drying a slurry, e.g. spray drying · CPC title

• C07C1/2076

  by a transformation in which at least one -C(=O)- moiety is eliminated · CPC title

• C07C2529/89

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

• C07C2529/86

  Borosilicates; Aluminoborosilicates · CPC title