Multi-phase alkylation process

• US 6,376,729 B1
• Filed: 12/04/2000
• Issued: 04/23/2002
• Est. Priority Date: 12/04/2000
• Status: Expired due to Fees

• Current Assignee: Fina Technology, Inc. (Totalenergies Se)
• Original Assignee: Fina Technology, Inc. (Totalenergies Se)
• Inventors: Butler, James R., Merrill, James T.
• Primary Examiner(s): Griffin, Walter D.
• Assistant Examiner(s): Dang, Thuan D.
• Application Number:
  US09/729,032
• Time in Patent Office: 505 Days
• Field of Search: 585/444, 585/467, 585/323, 585/470
• US Class Current: 585/449
• CPC Class Codes: C07C 15/073 Ethylbenzene
• CPC Class Codes: C07C 2/66 Catalytic processes
• CPC Class Codes: C07C 2529/035 Crystalline silica polymorphs, e.g. silicalites
• CPC Class Codes: C07C 2529/08 of the faujasite type, e.g. type X or Y
• CPC Class Codes: C07C 2529/70 of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65
• CPC Class Codes: Y02P 20/54 using solvents, e.g. supercritical solvents or ionic liquids

Abstract

A process for the production of ethylbenzene by the gas phase alkylation of benzene over a molecular sieve aromatic alkylation catalyst followed by liquid phase alkylation of the product of the gas phase alkylation. A feedstock containing benzene and ethylene is supplied to a first alkylation reaction zone containing a molecular sieve aromatic alkylation catalyst. The reaction zone is operated at temperature and pressure conditions to cause gas phase ethylation of the benzene with the production of an alkylation product comprising a mixture of ethylbenzene and polyalkylated aromatic components including diethylbenzene. The output from the first alkylation reaction zone is supplied, at least in part, to a second alkylation zone which is operated in the liquid phase or in the supercritical region followed by supply to an intermediate recovery zone for the separation and recovery of ethylbenzene and a polyalkylated aromatic compound component including diethylbenzene.

Claims

1. In the production of ethylbenzene, the method comprising:

(a) providing a first alkylation reaction zone containing a molecular sieve aromatic alkylation catalyst;

(b) supplying a feedstock containing benzene and ethylene to said first alkylation reaction zone;

(c) operating said first alkylation reaction zone at temperature and pressure conditions in which benzene is in the gaseous phase to cause gas-phase ethylation of said benzene in the presence of said molecular sieve catalyst to produce an alkylation product comprising a mixture of benzene and ethylbenzene;

(d) recovering said alkylation product from said first reaction zone and supplying at least a portion of said product from said first reaction zone to a second alkylation reaction zone containing a molecular sieve aromatic alkylation catalyst;

(e) supplying ethylene to said second alkylation reaction zone;

(f) operating said second alkylation reaction zone at temperature and pressure conditions in which benzene is in the liquid phase or in the supercritical phase to cause ethylation of said benzene in the presence of said second molecular sieve to produce an alkylation product comprising a mixture of benzene and ethylbenzene;

(g) recovering the alkylation product from said second alkylation reaction zone and supplying said product from said second alkylation reaction zone to a recovery zone for the separation of benzene and the separation and recovery of ethylbenzene from the alkylation product; and

(h) recycling benzene recovered from said recovery zone to at least one of said first and second alkylation reaction zones.

2. The method of claim 1 wherein substantially all of the alkylation product recovered from said first alkylation reaction zone is supplied to said second alkylation reaction zone.

3. The method of claim 1 wherein a first portion of said product from said first alkylation reaction zone is supplied to said second alkylation reaction zone and a second portion of said product from said first alkylation reaction zone bypasses said second alkylation reaction zone and is supplied directly to said recovery zone.

4. The method of claim 1 wherein the molecular sieve catalyst in said first alkylation reaction zone is a small to intermediate pore size molecular sieve and the molecular sieve catalyst in said second aromatic alkylation zone is an intermediate pore size molecular sieve having an effective pore size greater than the effective pore size of the catalyst in said first alkylation reaction zone.

5. The method of claim 4 wherein said catalyst in said second alkylation reaction zone is zeolite beta or zeolite La-Beta.

6. The method of claim 1 wherein the molecular sieve catalyst in said first alkylation reaction zone is monoclinic silicalite having a silica/alumina ratio greater than 250 and the catalyst in said second alkylation reaction zone is selected from the group consisting of zeolite Y, zeolite omega, zeolite beta, and zeolite lanthanum beta.

7. The method of claim 1 wherein at least a major portion of said recycled benzene is recycled to said first alkylation reaction zone.

8. The method of claim 1 wherein said catalyst in said first alkylation reaction zone is silicalite having a silica/alumina ratio of at least 275.

9. The method of claim 8 wherein said silicalite catalyst is monoclinic silicalite having an average crystal size of less than one micron.

10. The method of claim 9 wherein said monoclinic silicalite alkylation catalyst has an average crystal size of about 0.5 microns or less and is formulated with an alumna binder to provide catalyst particles having a surface area/volume ratio of at least 50 in.⁻

1.

11. In the production of ethylbenzene and the separate transalkylation of polyethylbenzene, the method comprising:

(a) providing a first alkylation reaction zone containing a molecular sieve aromatic alkylation catalyst;

(b) supplying a feedstock containing benzene and ethylene to said first alkylation reaction zone;

(c) operating said first alkylation reaction zone at temperature and pressure conditions in which benzene is in the gaseous phase to cause gas-phase ethylation of said benzene in the presence of said molecular sieve catalyst to produce an alkylation product comprising a mixture of benzene, ethylbenzene, and a polyalkylated aromatic component;

(d) recovering said alkylation product from said first reaction zone and supplying at least a portion of said product from said first reaction zone to a second alkylation reaction zone containing a molecular sieve aromatic alkylation catalyst;

(e) supplying ethylene to said second alkylation reaction zone;

(f) operating said second alkylation reaction zone at temperature and pressure conditions in which benzene is in the liquid phase or in the supercritical phase to cause ethylation of said benzene in the presence of said second molecular sieve to produce an alkylation product comprising a mixture of benzene, ethylbenzene, and a polyalkylated aromatic component;

(g) recovering the alkylation product from said second alkylation reaction zone and supplying at least a portion said product from said second alkylation reaction zone to an intermediate recovery zone for the separation and recovery of ethylbenzene from the alkylation product and the separation and recovery of a polyalkylated aromatic component including diethylbenzene;

(h) supplying at least a portion of said polyalkylated aromatic component including diethylbenzene in said polyalkylated component to a transalkylation zone containing a molecular sieve transalkylation catalyst;

(i) supplying benzene to said transalkylation reaction zone;

(j) operating said transalkylation reaction zone under temperature and pressure conditions to cause disproportionation of said polyalkylated aromatic fraction to produce a disproportionation product containing unreacted benzene and having a reduced diethylbenzene content and an enhanced ethylbenzene content.

12. The method of claim 11 wherein at least a portion of said disproportionation product is supplied to said intermediate recovery zone.

13. The method of claim 11 wherein the molecular sieve catalyst in said first alkylation reaction zone is a small to intermediate pore size molecular sieve and the molecular sieve catalyst in said second aromatic alkylation zone and the molecular sieve catalyst in said transalkylation reaction zone are each an intermediate pore size molecular sieve having an effective pore size greater than the effective pore size of the catalyst in said first alkylation reaction zone.

14. The method of claim 11 wherein the molecular sieve catalyst in said first alkylation reaction zone is monoclinic silicalite having a silica/alumina ratio greater than 250 and the catalyst in said second alkylation reaction zone is selected from the group consisting of zeolite Y, zeolite beta, and zeolite lanthanum beta.

15. The process of claim 14 wherein said transalkylation reaction zone contains a zeolite Y transalkylation catalyst and is operated under temperature and pressure conditions effective to maintain the feed stock in said transalkylation zone in the liquid phase.

16. The process of claim 15 wherein said second alkylation zone contains zeolite beta or zeolite La-Beta.

17. In the production of ethylbenzene, the method comprising:

(a) providing a first alkylation reaction zone containing a molecular sieve aromatic alkylation catalyst comprising monoclinic silicalite having an average crystal size of less than one micron and a silica/alumina ratio of at least 250;

(b) supplying a feedstock containing benzene and ethylene to said first alkylation reaction zone;

(c) operating said first alkylation reaction zone at temperature and pressure conditions in which benzene is in the gaseous phase to cause gas-phase ethylation of said benzene in the presence of said molecular sieve catalyst to produce an alkylation product comprising a mixture of benzene and ethylbenzene;

(d) recovering said first alkylation product from said first reaction zone and supplying at least a portion of said product from said first reaction zone to a second alkylation reaction zone containing an intermediate molecular sieve aromatic alkylation catalyst having an effective pore size greater than the effective pore size of said silicalite in said first alkylation reaction zone;

(e) supplying ethylene to said second alkylation reaction zone;

(f) operating said second alkylation reaction zone at temperature and pressure conditions in which benzene is in the liquid phase or in the supercritical phase to cause ethylation of said benzene in the presence of said second molecular sieve to produce an alkylation product comprising a mixture of benzene and ethylbenzene; and

(g) recovering the alkylation product from said second alkylation reaction zone and supplying said product from said second alkylation reaction zone to a recovery zone for the separation and recovery of ethylbenzene from the alkylation product;

(h) recycling benzene recovered from said recovery zone to at least one of said first and second alkylation reaction zones.

18. The method of claim 17 wherein the catalyst in said second alkylation reaction zone is selected from the group consisting of zeolite Y, zeolite beta, and zeolite lanthanum beta.

19. The method of claim 18 wherein said catalyst in said second alkylation reaction zone is zeolite beta or zeolite La-Beta.

20. The method of claim 19 wherein said silicalite alkylation catalyst has an average crystal size of about 0.5 microns or less and is formulated with an alumina binder to provide catalyst particles having a surface area/volume ratio of at least 50 in.⁻

1.