Catalyst coating and process for the conversion of oxygenates to olefins

Patent metadata

Field	Value
Publication number	US-10005702-B2
Application number	US-201313927751-A
Country	US
Kind code	B2
Filing date	Jun 26, 2013
Priority date	Jun 29, 2012
Publication date	Jun 26, 2018
Grant date	Jun 26, 2018

Abstract

The present invention relates to a catalyst for the conversion of oxygenates to olefins, comprising
a support substrate and a layer applied to the substrate,

wherein the layer comprises one or more zeolites of the MFI, MEL and/or MWW structure type, the one or more zeolites comprising one or more alkaline earth metals, to the preparation and use thereof, and to a process for converting oxygenates to olefins using the catalyst.

First claim

The invention claimed is:

1. A catalyst for the conversion of oxygenates to olefins, comprising
a honeycomb monolith support substrate including cordierite, and
a layer applied to the monolith substrate,

wherein the layer comprises one or more zeolites of the MFI structure type and a binder, wherein the one or more zeolites are present as a total loading of 0.08 g/cm 3 to 0.8 g/cm 3 , based on the volume of the coated support substrate, and comprise Mg in a range from 2% to 7% by weight, based on the total weight of the one or more zeolites and Mg, and calculated as the metal;
wherein the binder comprises SiO 2 .

2. A process for preparing a catalyst according to claim 1 , comprising
(i) providing the monolith support substrate and the one or more zeolites of the MFI structure type;
(ii) impregnating the one or more zeolites of the MFI structure type with a solution comprising Mg;
(iii) optionally drying the one or more impregnated zeolites obtained in (ii);
(iv) optionally calcining the one or more impregnated zeolites obtained in (ii) or (iii);
(v) preparing a mixture comprising the one or more impregnated and optionally dried and/or calcined zeolites and one or more solvents;
(vi) homogenizing the mixture obtained in (v) and adding a binder;
(vii) coating the monolith support substrate with the homogenized mixture obtained in (vi);
(viii) optionally drying the coated support substrate obtained in (vii);
(ix) optionally calcining the coated support substrate obtained in (vii) or (viii).

3. The process according to claim 2 , wherein the impregnation in step (ii) or the preparation of the mixture in step (v), or in step (vi) of the homogenizing of the mixture obtained in (v), is followed by bringing of the one or more impregnated zeolites of the MFI structure type to a particle size D 50 in the range from 0.01 to 200 μm.

4. The process according to claim 2 , wherein the impregnation in step (ii) or the preparation of the mixture in step (v), or in step (vi) of the homogenizing of the mixture obtained in (v), is followed by bringing of the one or more impregnated zeolites of the MFI structure type to a particle size D 90 in the range from 0.5 to 50 μm.

5. The process according to claim 2 , wherein the drying in (iii) and/or (viii) is effected at a temperature in the range from 50 to 220° C.

6. The process according to claim 2 , wherein the calcining in (iv) and/or (ix) is effected at a temperature in the range from 300 to 850° C.

7. The process according to claim 2 , wherein the solution used in (ii) and/or the mixture prepared in (v) comprises one or more solvents selected from the group consisting of
a. alcohols,
b. water,
c. mixtures of two or more alcohols, and
d. mixtures of water and one or more alcohols.

8. The process according to claim 2 , wherein the solids concentration of the mixture prepared in (v) is in the range from 5 to 50% by weight.

9. The process according to claim 2 , wherein the homogenizing in (vi) is effected by stirring, kneading, agitating, vibrating or combinations of two or more thereof.

10. The process according to claim 2 , wherein the coating in (vii) is effected by spray coating and/or wash coating.

11. The process according to claim 2 , wherein step (vii) is repeated once or more than once.

12. A catalyst for the conversion of oxygenates to olefins, obtained by the process according to claim 2 .

13. A process for converting oxygenates to olefins, comprising
(1) providing a gas stream comprising one or more oxygenates; and
(2) contacting the gas stream with the catalyst according to claim 1 .

14. The process according to claim 13 , wherein the gas stream according to (1) comprises one or more oxygenates selected from the group consisting of aliphatic alcohols, ethers, carbonyl compounds and mixtures of two or more thereof.

15. The process according to claim 12 , wherein the content of oxygenates in the gas stream according to (1) is in the range from 30 to 100% by volume based on the total volume.

16. The process according to claim 12 , wherein the water content in the gas stream according to (1) is in the range from 5 to 60% by volume based on the total volume.

17. The process according to claim 12 , wherein the contacting according to (2) is effected at a temperature in the range from 200 to 700° C., and a pressure in the range from 0.1 to 10 bar.

18. The process according to claim 12 , wherein the process is a continuous process.

19. The process according to claim 18 , in which the space velocity in the contacting according to (2) is in the range from 0.5 to 50 h −1 .

20. The process according to claim 19 , in which the service life of the coated support substrate as a catalyst during which the continuous process is performed without interruption is in the range from 15 to 400 h.

21. A catalyst for the conversion of oxygenates to olefins, comprising
a honeycomb, monolith cordierite support, and
a layer applied to the monolith substrate, wherein the layer comprises one or more zeolites of the MFI structure type in a total loading of 0.08 to 0.2 g/cm 3 , based on the volume of the coated substrate, and a binder, wherein the one or more zeolites includes Mg, which is present in a range from 2 to 7% by weight, based on the total weight of the one or more zeolites of the MFI structure type and Mg, and calculated as the metal, wherein the catalyst has a relative propylene to ethylene selectivity of 78.8% to 89.3%, based on 100% by weight oxygenate conversion to propylene and ethylene;

wherein the binder comprises SiO 2 .

22. The catalyst according to claim 21 , wherein in the process for the conversion of oxygenates to olefins the catalyst has a service life of 90 to 220 hr at a space velocity in a range from 3 to 25 hr −1 .

23. The catalyst according to claim 21 , wherein the catalyst has a relative propylene to butylene selectivity of 58.5% to 62%, based on 100% by weight oxygenate conversion to propylene and butylene.

Assignees

• Basf Se

Inventors

• Spannhoff Kirsten
• Patcas Florina Corina
• Schwab Ekkehard
• Weck Alexander
• Bay Kerem
• Mielke Matthias
• Seel Oliver

Classifications

• C07C2529/80

  Mixtures of different zeolites · CPC title

• C07C2529/40

  of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11 · CPC title

• C07C1/22 Primary

  by reduction · CPC title

• B01J38/02

  Heat treatment · CPC title

• B01J29/90

  Regeneration or reactivation · CPC title