Catalyst composite comprising an alkaline earth metal containing CHA zeolite and use thereof in a process for the conversion of oxygenates to olefins

Patent metadata

Field	Value
Publication number	US-11529618-B2
Application number	US-201716462408-A
Country	US
Kind code	B2
Filing date	Nov 28, 2017
Priority date	Nov 28, 2016
Publication date	Dec 20, 2022
Grant date	Dec 20, 2022

Abstract

The present invention relates to catalyst comprising one or more metal oxides and/or metalloid oxides and a zeolitic material having the CHA framework structure comprising YO 2 and X 2 O 3 , wherein Y is a tetravalent element and X is a trivalent element, wherein the zeolitic material comprises one or more alkaline earth metals selected from the group consisting of Mg, Ca, Sr, Ba, and combinations of two or more thereof, and wherein the framework of the zeolitic material comprised in the catalyst contains substantially no phosphorous, as well as to a process for the preparation of a catalyst comprising one or more alkaline earth metals selected from the group consisting of Mg, Ca, Sr, Ba, and combinations of two or more thereof and to a catalyst obtainable therefrom. Furthermore, the present invention relates to a method for the conversion of oxygenates to olefins employing the inventive catalyst, as well as to the use of the inventive catalyst in specific applications.

First claim

The invention claimed is:

1. A catalyst comprising
one or more metal oxides and/or metalloid oxides and
a zeolitic material having the CHA framework structure comprising YO 2 and X 2 O 3 ,
wherein Y is Si and X is Al, wherein the zeolitic material comprises Mg and wherein the framework of the zeolitic material comprised in the catalyst contains substantially no phosphorous; wherein the one or more metal oxides and/or metalloid oxides comprises, Al 2 O 3 and/or SiO 2 and wherein the zeolitic material comprised in the catalyst contains Mg in an amount in the range of from 2 to 7 wt. % calculated as the element and based on 100 wt. % of the YO 2 in the zeolitic material and wherein the zeolitic material contains substantially no phosphorous and
wherein the catalyst is in the form of a shaped body in the form of granulates and/or extrudates.

2. The catalyst of claim 1 , wherein the zeolite material and the metal oxide and/or metalloid oxide is calcined and the catalyst displays a MO:zeolite weight ratio of the one or more metal oxides and/or metalloid oxides (MO) to the zeolitic material in the range of from 0.05 to 3 as calculated based on the weight of the calcined metal oxides and/or metalloid oxides and of the calcinated zeolitic material.

3. A process for the preparation of the catalyst as claimed in claim 1 , comprising YO 2 and X 2 O 3 , wherein Y is Si and X is Al,
(B) mixing the zeolitic material provided in claim 1 with one or more metal oxides and/or metalloid oxides and with a solvent system;
(C) optionally homogenizing the mixture obtained in (B);
(D) molding of the mixture obtained in (B) or (C);
(E) optional drying of the molding obtained in (D);
(F) optional calcining of the molding obtained in (D) or (E);
(G) impregnation of the molding obtained in (D), (E), or (F) with a solution containing one or more salts of Mg;
(H) optional drying of the molding obtained in (G); and
(I) optional calcining of the molding obtained in (G) or (H).

4. A catalyst comprising Mg obtained according to the process of claim 3 .

5. A method for the conversion of oxygenates to olefins comprising
(i) providing the catalyst according to claim 1 ;
(ii) providing a gas stream comprising one or more oxygenates;
(iii) contacting the catalyst provided in (i) with the gas stream provided in (ii) and converting one or more oxygenates to one or more olefins.

6. The method of claim 5 , wherein the gas stream provided in (ii) comprises one or more oxygenates selected from the group consisting of aliphatic alcohols, ethers, carbonyl compounds and mixtures of two or more thereof.

7. The method of claim 5 , wherein the water content in the gas stream provided in (ii) is in the range from 5 to 60% by volume.

8. The method of claim 5 , wherein the contacting according to (iii) is effected at a temperature in the range from 200 to 700° C.

9. A process comprising:
(i) preparing the catalyst according to claim 1 ,
(ii) providing the catalyst of step (i) to a process selected from the group consisting of
conversion of oxygenates to olefins,
a methanol-to-olefin process (MTO process),
a dimethylether to olefin process (DTO process),
methanol-to-gasoline process (MTG process),
a methanol-to-hydrocarbon process,
a biomass to olefins and/or biomass to aromatics process,
a methane to benzene process, and
for alkylation of aromatics.

10. The catalyst of claim 1 , wherein the catalyst comprises a composite of the zeolitic material and the one or more metalloid oxides.

11. The catalyst of claim 1 , wherein the one or more metal oxides and/or metalloid oxides comprises Al 2 O 3 .

12. The catalyst of claim 1 , wherein the one or more metal oxides and/or metalloid oxides comprises SiO 2 .

13. The catalyst of claim 1 , wherein the one or more metal oxides and/or metalloid oxides comprises Al 2 O 3 and SiO 2 .

14. The catalyst of claim 1 , wherein the catalyst contains Mg in an amount in the range of from 3.5 to 5.5 wt. % calculated as the element and based on 100 wt. % of the YO 2 .

15. The catalyst of claim 1 , wherein the catalyst contains Mg in an amount in the range of from 4.3 to 4.9 wt. % calculated as the element and based on 100 wt. % of the YO 2 .

16. The catalyst of claim 1 , wherein the Mg is present in the catalyst as extra-framework ions.

17. The catalyst of claim 1 , wherein the specific surface area of the catalyst is in the range of from 250 to 500 m 2 /g.

18. The catalyst of claim 1 , wherein the specific pore volume of the catalyst is in the range of from 0.2 to 0.5 ml/g.

19. The catalyst of claim 1 , wherein
the specific surface area of the catalyst is in the range of from 350 to 375 m 2 /g,
the specific pore volume of the catalyst is in the range of from 0.36 to 0.37 ml/g and
the catalyst is in the form of a shaped body in the form of extrudates.

Assignees

• Basf Se

Inventors

• Mcguire Robert
• Janke Christiane
• Mueller Ulrich
• Schwab Ekkehard

Classifications

• Y02P30/40

  Ethylene production · CPC title

• B01J29/047

  Germanosilicates; Aluminogermanosilicates (B01J29/005 takes precedence) · CPC title

• C07C2529/89

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

• C07C2529/78

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

• B01J2229/186

  not in framework positions · CPC title