Use of a catalyst comprising a phosphorous modified zeolite in an alcohol dehydration process

Patent metadata

Field	Value
Publication number	US-9862653-B2
Application number	US-201214236726-A
Country	US
Kind code	B2
Filing date	Jul 25, 2012
Priority date	Aug 3, 2011
Publication date	Jan 9, 2018
Grant date	Jan 9, 2018

Abstract

A catalyst can be used to convert an alcohol in a dehydration process into an olefin having the same number of carbon atoms as the alcohol. The catalyst can include a phosphorus modified zeolite made by providing a zeolite with at least one ten member ring in the structure, steaming the zeolite, mixing the zeolite with binders and shaping additives, and shaping the zeolite. An ion-exchange step can be performed, and the shaped catalyst can be steamed. Phosphorus can be introduced on the catalyst at an amount of at least 0.1 wt %, such as by dry impregnation or chemical vapor deposition. A metal can be introduced. The catalyst can be washed and/or calcinated, and steamed in an equilibration step. 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.

First claim

The invention claimed is:

1. A process comprising:
converting an alcohol in a dehydration process in the presence of a catalyst to make an olefin having the same number of carbon atoms as the alcohol, wherein the catalyst comprises a phosphorus modified zeolite and wherein the method of making the catalyst comprises:
a) providing a zeolite comprising at least one ten member ring in the structure thereof, and optionally steaming the zeolite;
b) mixing the zeolite of step a) with at least a component selected among one or more binders and shaping additives, and then shaping the mixture to form a shaped catalyst precursor;
c) optionally making a ion-exchange;
d) optionally steaming the shaped mixture, optionally before step c), wherein at least one of the steaming of step d) or the steaming of step a) is mandatory;
e) introducing phosphorus on the shaped catalyst precursor to introduce at least 0.1 wt % of the phosphorus to form a phosphated catalyst, wherein the introduction is made by incipient wetness impregnation;
f) introducing an alkaline earth metal, M, to the phosphated catalyst by incipient wetness impregnation to form an M-containing and phosphated catalyst, optionally simultaneously with step e);
g) optionally washing the catalyst;
h) optionally calcinating the catalyst; and
i) steaming the M-containing and phosphated catalyst at a temperature of 625° C. or above.

2. The process of claim 1 , wherein the steaming of step i) is performed at a temperature ranging from 700 to 800° C.

3. The process of claim 1 , wherein the steaming of step i) is performed at a temperature ranging from 720 to 800° C.

4. The process of claim 1 , wherein the shaped zeolite of step b) contains less than 100 wppm of sodium.

5. The process of claim 1 , wherein the shaped zeolite of step b) contains less than 100 wppm of sodium, less than 100 wppm of potassium and less than 500 wppm of iron.

6. The process of claim 1 , wherein the alcohol is ethanol, propanol, butanol or phenylethanol.

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

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

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

10. The process of claim 1 , wherein, at step e), the amount of phosphorus on the catalyst is from 0.5 to 30 wt %.

11. The process of claim 10 , wherein an amount of phosphorus on the catalyst is from 0.5 to 9 w %.

12. The process of claim 1 , wherein the alkaline earth metal is Mg, Ca, Sr, Ba, or combinations thereof.

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

14. A process comprising:
converting an alcohol in a dehydration process in the presence of a catalyst to make an olefin having the same number of carbon atoms as the alcohol, wherein the catalyst comprises a phosphorus modified zeolite and wherein the method of making the catalyst comprises:
a) providing a zeolite comprising at least one ten member ring in the structure, and optionally steaming the zeolite;
b) mixing the zeolite of step a) with at least a component selected among one or more binders and shaping additives, and then shaping said mixture to form a shaped catalyst precursor;
c) optionally making a ion-exchange;
d) optionally steaming the shaped catalyst precursor, optionally before step c), wherein at least one of the steaming of step d) or the steaming of step a) is mandatory;
e) introducing phosphorus on the shaped catalyst precursor to introduce at least 0.1 wt % of the phosphorus to form a phosphated catalyst, wherein the introduction is made by incipient wetness impregnation;
f) introducing an alkaline earth metal M to the phosphated catalyst by incipient wetness impregnation to form an M-containing and phosphated catalyst, optionally simultaneously with step e);

g) optionally washing the M-containing and phosphated catalyst;
h) optionally calcinating the M-containing and phosphated catalyst;
i) steaming the M-containing and phosphated catalyst at a steaming severity (X) of at least about 2 and at a temperature of 625° C. or above.

15. The process of claim 14 , wherein the steaming of step i) is performed at a temperature ranging from 700 to 800° C.

16. The process of claim 14 , wherein the steaming of step i) is performed at a temperature ranging from 720 to 800° C.

17. The process of claim 14 , wherein the shaped zeolite of step b) contains less than 100 wppm of sodium.

18. The process of claim 14 , wherein the shaped zeolite of step b) contains less than 100 wppm of sodium, less than 100 wppm of potassium and less than 500 wppm of iron.

19. The process of claim 14 , wherein the alcohol is ethanol, propanol, butanol or phenylethanol.

20. The process of claim 14 , wherein the zeolite is MFI, MTT, FER, MEL, TON, MWW, EUO, or MFS.

21. The process of claim 14 , 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.

22. The process of claim 14 , wherein the zeolite is MFI with Si/Al atomic ratio ranging from 30 to 200.

23. The process of claim 14 , wherein, at step e), an amount of phosphorus on the catalyst is from 0.5 to 30 wt %.

24. The process of claim 23 , wherein the amount of phosphorus on the catalyst is from 0.5 to 9 w %.

25. The process of claim 14 , wherein the alkaline earth metal is Mg, Ca, Sr, Ba, or combinations thereof.

26. The process of claim 14 , wherein the catalyst has a volume of pores between 30 Å and 1000 Å of at least 0.25 cc/g.

Assignees

• Nesterenko Nikolai
• Minoux Delphine
• Adam Cindy
• Dath Jean-Pierre
• Lopez Joseph
• Euzen Patrick
• Ifp Energies Now
• Total Res & Technology Feluy

Inventors

• Nesterenko Nikolai
• Minoux Delphine
• Adam Cindy
• Dath Jean-Pierre
• Lopez Joseph
• Euzen Patrick

Classifications

• B01J37/10

  in the presence of water, e.g. steam · CPC title

• C07C2529/06

  Crystalline aluminosilicate zeolites; Isomorphous compounds thereof · CPC title

• C07C2527/14

  Phosphorus; Compounds thereof · CPC title

• Y02P20/52

  using catalysts, e.g. selective catalysts · CPC title

• C07C2529/40

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