Method for making a catalyst comprising a phosphorous modified zeolite and use of said zeolite

Patent metadata

Field	Value
Publication number	US-10300467-B2
Application number	US-201214236736-A
Country	US
Kind code	B2
Filing date	Jul 25, 2012
Priority date	Aug 3, 2011
Publication date	May 28, 2019
Grant date	May 28, 2019

Abstract

A method to make a phosphorus modified zeolite can include providing a zeolite including at least one ten member ring in the structure, steaming the zeolite, mixing the zeolite with one or more binders and shaping additives, and then shaping the mixture. The method can include making a ion-exchange. The shaped mixture can be steamed. Phosphorous can be introduced on the catalyst to introduce at least 0.1 wt % of phosphorus, such as be dry impregnation or chemical vapor deposition. A metal, such as calcium, can be introduced. The catalyst can be washed, calcinated, and then steamed. The steaming severity (X) can be at least about 2. The catalyst can be steamed at a temperature above 625° C., such as a temperature ranging from 700 to 800° C. The catalyst can be used in alcohol dehydration, olefin cracking, MTO processes, and alkylation of aromatics by alcohols with olefins and/or alcohols.

First claim

What is claimed:

1. A method to make a phosphorus modified zeolite comprising:
(a) providing a zeolite comprising at least one ten member ring in the structure thereof;
(b) mixing the zeolite of step a) with at least one binder and/or shaping additive, and then shaping the mixture to form a catalyst precursor;
(c) calcining the catalyst precursor of step (b);
(d) performing steaming on at least one of: the zeolite before step (b), the catalyst precursor before step (c), the catalyst precursor after step (c), or combinations thereof, wherein 60 to 95% of the tetrahedral aluminum is retained in the zeolite or catalyst precursor after steaming, and wherein the zeolite or catalyst precursor is not leached with acid;
(e) introducing phosphorus on the catalyst precursor to introduce at least 0.1 wt % of the phosphorus to form a phosphate catalyst, wherein the introduction is made by incipient wetness impregnation at 30 to 100° C.;
(f) introducing calcium on to the phosphate catalyst by incipient wetness impregnation, wherein the calcium is introduced to the phosphate catalyst in a solubilized form, optionally simultaneously with step (e); and
(g) steaming the catalyst at a temperature ranging from 700 to 800° C.

2. The method of claim 1 , wherein the steaming of step (g) is performed at a temperature ranging from 720 to 800° C.

3. The method of claim 1 , wherein the catalyst precursor of step (b) comprises less than 100 wppm of sodium.

4. The method of claim 1 , wherein the catalyst precursor of step (b) comprises less than 100 wppm of sodium, less than 100 wppm of potassium and less than 500 wppm of iron.

5. The method of claim 1 , wherein the catalyst precursor of step (b) comprises less than 1000 wppm of sodium.

6. The method of claim 1 , wherein the catalyst precursor of step (b) than 1000 wppm of iron.

7. The method of claim 1 , wherein the zeolite is MFI, MTT, FER, MEL, TON, MWW, EUO, or MFS.

8. The method of claim 1 , wherein the zeolite is ZSM-5 with Si/Al atomic ratio ranging from 11 to 30, and wherein the zeolite has been made without direct addition of organic template.

9. The method of claim 1 , wherein the zeolite is MFI with Si/Al atomic ratio ranging from 30 to 200.

10. The method of claim 1 , wherein the amount of phosphorus on the catalyst is from 0.5 to 30 wt %.

11. The method of claim 10 , wherein the amount of phosphorus on the catalyst is from 0.5 to 9 wt %.

12. The method of claim 1 , wherein the catalyst has a volume of pores between 30 Å and 1000 Å of at least 0.25 cc/g.

13. A method comprising using the catalyst made according the method of claim 1 in a process, wherein the catalyst is operated in the presence of steam at temperature above 300° C. and up to 800° C.

14. A process comprising cracking olefins to make lighter olefins, wherein the cracking performed in the presence of the catalyst made according to the method of claim 1 .

15. A process comprising cracking of methanol or dimethylether to produce light olefins, wherein the cracking is performed in the presence of the catalyst made according to the method of claim 1 .

16. The process of claim 15 , wherein the light olefins comprise ethylene and propylene.

17. A process comprising alkylation of aromatics by alcohols or olefins, wherein the alkylation is performed in the presence of the catalyst made according to the method of claim 1 .

18. A method to make a phosphorus modified zeolite comprising:
(a) providing a zeolite comprising at least one ten member ring in the structure thereof;
(b) mixing the zeolite of step a) with at least one binder and/or shaping additive, and then shaping the mixture to form a catalyst precursor;
(c) calcining the catalyst precursor of step (b);
(d) performing steaming on at least one of: the zeolite before step (b), the catalyst precursor before step (c), the catalyst precursor after step (c), or combinations thereof, wherein 60 to 95% of the tetrahedral aluminum is retained in the zeolite or catalyst precursor after steaming, wherein the zeolite or catalyst precursor is not leached with acid;
(e) introducing phosphorus on the catalyst precursor to introduce at least 0.1 wt % of the phosphorus to form a phosphate catalyst, wherein the introduction is made by incipient wetness impregnation at 30 to 100° C.;
(f) introducing calcium on to the phosphate catalyst by incipient wetness impregnation, wherein the calcium is introduced to the phosphate catalyst in a solubilized form, optionally simultaneously with step e); and
(g) steaming the catalyst, wherein the steaming in step (d), step (g), or both is performed at a steaming severity (X) of at least about 2.

19. The method of claim 18 , wherein the steaming of step (g) is performed at a steaming severity of at least 40.

20. The method of claim 18 , wherein the steaming of step (g) is performed at a steaming severity of at least 45.

21. The method of claim 18 , wherein the steaming of step (g) is performed at a steaming severity of at least 80.

22. The method of claim 18 , wherein the catalyst precursor of step (b) comprises less than 100 wppm of sodium.

23. The method of claim 18 , wherein the catalyst precursor of step (b) comprises less than 100 wppm of sodium, less than 100 wppm of potassium and less than 500 wppm of iron.

24. The method of claim 18 , wherein the catalyst precursor of step (b) comprises less than 1000 wppm of sodium.

25. The method of claim 18 , wherein the catalyst precursor of step (b) comprises less than 1000 wppm of sodium, less than 1000 wppm of potassium and less than 1000 wppm of iron.

26. The method of claim 18 , wherein the zeolite is MFI, MTT, FER, MEL, TON, MWW, EUO, or MFS.

27. The method of claim 18 , wherein the zeolite is ZSM-5 with Si/Al atomic ratio ranging from 11 to 30, and wherein the zeolite has been made without direct addition of organic template.

28. The method of claim 18 , wherein the zeolite is MFI with Si/Al atomic ratio ranging from 30 to 200.

29. The method of claim 18 , wherein the amount of phosphorus on the catalyst is from 0.5 to 30 wt %.

30. The method of claim 18 , wherein the amount of phosphorus on the catalyst is from 0.5 to 9 wt %.

31. The method of claim 18 , wherein the catalyst has a volume of pores between 30 Å and 1000 Å of at least 0.25 cc/g.

32. A method of comprising using the catalyst made according the method of claim 18 in a process, wherein the catalyst is operated in the presence of steam at temperature ranging from 300° C. to 800° C.

33. A process comprising cracking olefins to make lighter olefins, wherein the cracking performed in the presence of the catalyst made according to the method of claim 18 .

34. A process comprising cracking of methanol or dimethylether to produce light olefins, wherein the cracking is performed in the presence of the catalyst made according to the method of claim 18 .

35. The process of claim 34 , wherein the light olefins comprise ethylene and propylene.

36. A process comprising alkylation of aromatics by alcohols or olefins, wherein the alkylation is performed in the presence of the catalyst made according to the method of claim 18 .

Assignees

• Nesterenko Nikolai
• Minoux Delphine
• Adam Cindy
• Dath Jean Pierre
• Total Res & Technology Feluy

Inventors

• Nesterenko Nikolai
• Minoux Delphine
• Adam Cindy
• Dath Jean-Pierre

Classifications

• C07C2527/14

  Phosphorus; Compounds thereof · CPC title

• C10G3/49

  containing crystalline aluminosilicates, e.g. molecular sieves · CPC title

• B01J29/7026

  MFS-type, e.g. ZSM-57 · CPC title

• B01J37/0009

  Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst · CPC title

• C07C2529/65

  of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38 · CPC title