Multi component catalyst and its use in catalytic cracking

• US 7,326,332 B2
• Filed: 09/25/2003
• Issued: 02/05/2008
• Est. Priority Date: 09/25/2003
• Status: Active Grant

• Current Assignee: ExxonMobil Chemical Patents Inc. (Exxon Mobil Corporation)
• Original Assignee: ExxonMobil Chemical Patents Inc. (Exxon Mobil Corporation)
• Inventors: Ruziska, Philip A., Chen, Tan-Jen, Stern, David L., Keusenkothen, Paul F., Buchanan, John Scott, Henry, Brian Erik
• Primary Examiner(s): Caldarola; Glenn
• Assistant Examiner(s): Singh; Prem C.
• Application Number:
  US10/671,080
• Publication Number:
  US 20050070422A1
• Time in Patent Office: 1,594 Days
• Field of Search: 208/68, 208/114, 208/120.01, 208/113, 585/519, 502/64
• US Class Current: 208/120.01
• CPC Class Codes: B01J 29/005 Mixtures of molecular sieves comprising at least one molecular sieve which is not an aluminosilicate zeolite, e.g. from groups B01J29/03 - B01J29/049 or B01J29/82 - B01J29/89
• CPC Class Codes: B01J 29/40 of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
• CPC Class Codes: B01J 29/85 Silicoaluminophosphates [SAPO compounds]
• CPC Class Codes: C10G 11/05 Crystalline alumino-silicates, e.g. molecular sieves

Abstract

A multi component catalyst and catalytic cracking process for selectively producing C₃ olefins. The catalyst comprises a first molecular sieve having an intermediate pore size, a second molecular sieve and, optionally a third molecular sieve having a large pore size. At least one of the channels of the second molecular sieve has a pore size index that is less than the pore size index of at least one channel of the first molecular sieve. The process is carried out by contacting a feedstock containing hydrocarbons having at least 5 carbon atoms is contacted, under catalytic cracking conditions, with the multi component catalyst. The catalyst finds application in the cracking of naphtha and heavy hydrocarbon feedstocks.

Claims

1. A catalytic cracking process for selectively producing C₃ olefins, said process comprising contacting under catalytic cracking conditions, a feedstock containing hydrocarbons having at least 5 carbon atoms with a catalytic cracking catalyst comprising catalytically effective amounts of a multicomponent catalyst comprising:

(a) a first molecular sieve component having an intermediate pore size; and

(b) a second molecular sieve component having a structure type that is different from said first molecular sieve and a pore size index of at least one channel of said second molecular sieve which is less than the pore size index of at least one channel of said first molecular sieve; and

wherein said multicomponent catalyst provides recovering a higher propylene conversion, by weight percent, than with either said first component or said second component alone.

2. The process recited in claim 1, wherein said feedstock comprises a naphtha having a boiling range of 25°

C. to 225°

C.

3. The process recited in claim 2, wherein the second molecular sieve has a pore diameter greater than about 3.5 Å

.

4. The process recited in claim 2, wherein all of the channels of the second molecular sieve have a pore size index that is less than the pore size index of all of the channels of the first molecular sieve.

5. The process recited in claim 2, wherein said first molecular sieve and said second molecular sieve have one dimensional, non-interconnecting channels.

6. The process recited in claim 2, wherein said first molecular sieve, said second molecular sieve, or both have three-dimensional, interconnecting channels.

7. The process recited in claim 2, wherein said first molecular sieve has a structure selected from the group consisting of ITH, MFI, MEL, MFS MTW, and MWW.

8. The process recited in claim 7, wherein said first molecular sieve is selected from the group consisting of ZSM-5, ZSM-11, ZSM-12, ZSM-57, ITQ-13, and MCM-22.

9. The process recited in claim 7, wherein said second molecular sieve has a structure selected from the group consisting of AEL, AFO, CHA, TON, FER, MTT, and MWW.

10. The process recited in claim 8, wherein said second molecular sieve is selected from the group consisting ECR-42, ZSM-22, ZSM-35, ZSM-23, MCM-22, MCM-49, SAPO-11, SAPO-34, and SAPO-41.

11. The process recited in claim 2, wherein said first molecular sieve is ZSM-5 and said second molecular sieve is SAPO-11.

12. The process recited in claim 11, wherein said naphtha is a thermally or catalytically cracked naphtha boiling in the naphtha range and containing from about 5 wt. % to about 35 wt. % paraffins, and from about 15 wt. % to about 70 wt. % olefins.

13. The process recited in claim 3, wherein the catalytic cracking conditions include a feed residence time in the reaction zone of less than about 10 seconds, temperatures ranging from about 400°

C. to about 700°

C.;

hydrocarbon partial pressures from about 10 to 50 psia; and

a catalyst to feed (wt/wt) ratio from about 3 to 12;

wherein catalyst weight is total weight of said catalytic cracking catalyst composite.

14. The process recited in claim 1, wherein the feedstock comprises a hydrocarbon mixture having an initial boiling point of 200°

C. and said catalytic cracking composition further comprises a third molecular sieve having a large pore size.

15. The process recited in claim 14, wherein all of the channels of the second molecular sieve have a pore size index that is less than the pore size index of all of the channels of the first molecular sieve.

16. The process recited in claim 14, wherein said first molecular sieve and said second molecular sieve have one dimensional, non-interconnecting channels.

17. The process recited in claim 14, wherein said first molecular sieve, said second molecular sieve, or both have three-dimensional, interconnecting channels.

18. The process recited in claim 14, wherein said third molecular sieve has a structure selected from the group consisting of AFI, AFR, LTL, VFI, MAZ, MEI, FAU, EMT, OFF, *BEA, and MOR.

19. The process recited in claim 14, wherein said first molecular sieve has a structure selected from the group consisting of ITH, MFI, MEL, MFS MTW, and MWW.

20. The process recited in claim 19, wherein said first molecular sieve is selected from the group consisting of ZSM-5, ZSM-11, ZSM-12, ZSM-57, ITQ-13, and MCM-22.

21. The process recited in claim 19, wherein said second molecular sieve has a structure selected from the group consisting of AEL, AFO, CHA, TON, FER, MTT, and MWW.

22. The process recited in claim 19, wherein said second molecular sieve is selected from the group consisting ECR-42, ZSM-22, ZSM-35, ZSM-23, MCM-22, MCM-49, SAPO-11, SAPO-34, and SAPO-41.

23. The process recited in claim 14, wherein said first molecular sieve is ZSM-5 and said second molecular sieve is SAPO-11.

24. The process recited in claim 21, wherein said third molecular sieve has a structure selected from the group consisting of AFI, AFR, LTL, VFI, MAZ, MEI, FAU, EMT, OFF, *BEA, and MOR.

25. The process recited in claim 22, wherein said third molecular sieve is selected from the group consisting of faujasite, mazzite, offretite, zeolite L, VPI-5, SAPO-37, zeolite X, omega, Beta, ZSM-3, ZSM-4, ZSM-18, ZSM-20, MCM-9, MCM-41, MCM-41S, MCM-48, zeolite Y, Ultrastable Y, Rare Earth exchanged Y, Rare Earth exchanged USY, Dealuminated Y, and Ultrahydrophobic Y.

26. The process of claim 25, wherein said large pore molecular sieve is selected from the group consisting of REY, USY or REUSY.

27. The process of claim 26, wherein said hydrocarbon mixture has an initial boiling point above 200°

C., a 50% point of at least 260°

C. and an end point of at least 315°

C.

28. The process of claim 27, wherein said hydrocarbon mixture is selected from the group consisting of vacuum gas oils, thermal oils, residual oils, cycle stocks, whole top crudes, tar sand oils, shale oils, synthetic fuels, heavy hydrocarbon fractions derived from the destructive hydrogenation of coal, tar, pitches, asphalts, and hydrotreated products of the foregoing.

29. The process of claim 26, wherein the weight ratio of said third molecular sieve to the first and second molecular sieve is about 0.01 to about 0.1.

30. The process of claim 23, wherein said large pore molecular sieve comprises a zeolite Y.

31. The process recited in claim 23, wherein the product of said catalytic cracking process contains at least 5 percent by weight of C3 olefins based on the total weight of the propylene and butylene produced by the process.

32. The process recited in claim 23, wherein said process is carried out to produce propylene in a propylene to ethylene ratio of at least 4:

1 and a propylene to butylene ratio of at least 1;

1.

33. The process recited in claim 32, further comprising the steps of:

(a) separating the propylene; and

(b) polymerizing or co-polymerizing the separated propylene.