Alkylaromatics production

• US 7,868,218 B2
• Filed: 06/09/2010
• Issued: 01/11/2011
• Est. Priority Date: 05/10/2006
• Status: Active Grant

• Current Assignee: ExxonMobil Chemical Patents Inc. (Exxon Mobil Corporation), Badger Licensing LLC (TechnipFMC, plc)
• Original Assignee: ExxonMobil Chemical Patents Inc. (Exxon Mobil Corporation), Badger Licensing LLC (TechnipFMC, plc)
• Inventors: Maerz, Brian, Clark, Michael C.
• Primary Examiner(s): DANG, THUAN D
• Application Number:
  US12/797,115
• Publication Number:
  US 20100249472A1
• Time in Patent Office: 216 Days
• Field of Search: 585/449, 585/467
• US Class Current: 585/449
• CPC Class Codes: C07C 15/02 Monocyclic hydrocarbons
• CPC Class Codes: C07C 15/073 Ethylbenzene
• CPC Class Codes: C07C 15/085 Isopropylbenzene
• CPC Class Codes: C07C 2/66 Catalytic processes
• CPC Class Codes: C07C 6/126 of more than one hydrocarbon
• CPC Class Codes: C10G 2400/30 Aromatics

Abstract

A process is described for producing an alkylaromatic compound in a multistage reaction system comprising at least first and second series-connected alkylation reaction zones each containing an alkylation catalyst. A first feed comprising an alkylatable aromatic compound and a second feed comprising an alkene and one or more alkanes are introduced into said first alkylation reaction zone, having operating conditions, e.g., temperature and pressure, which are controlled effective to cause the alkylatable aromatic compound to be partly in the vapor phase and partly in the liquid phase with the ratio of liquid volume to vapor volume of the feed in each zone to be from about 0.5 to about 10. The aromatic compound and the alkene are reacted in the presence of the alkylation catalyst to form an effluent comprising the alkylaromatic compound, unreacted alkylatable aromatic compound, any unreacted alkene and the alkane, which is withdrawn and then supplied to the second alkylation reaction zone without removal of the alkane.

Claims

1. A process for producing an alkylaromatic compound in a multistage reaction system comprising at least first and second series-connected alkylation reaction zones each containing an alkylation catalyst and having operating conditions, the process comprising the steps of:

(a) introducing a first feed comprising an alkylatable aromatic compound and a second feed comprising an alkene and one or more alkanes into said first alkylation reaction zone to form a first feedstock;

(b) controlling said operating conditions of said first alkylation reaction zone by adjusting temperature or pressure effective to cause (i) part of said alkylatable aromatic compound to be in the vapor phase and part of said alkylatable aromatic compound to be in the liquid phase, and (ii) the ratio of the volume of liquid to the volume of vapor of said first feedstock in said first reaction zone to be from about 0.5 to about 10 to maintain a dialkylaromatic/alkylaromatic weight ratio of less than 15%;

(c) alkylating said alkylatable aromatic compound with said alkene in the presence of said alkylation catalyst to form a first effluent;

(d) withdrawing said first effluent from said first alkylation reaction zone, said first effluent comprising said alkylaromatic compound, unreacted alkylatable aromatic compound, any unreacted alkene and said alkane;

(e) without removing said alkane from said first effluent, supplying a second feedstock comprising said first effluent and said alkene to the second alkylation reaction zone;

(f) controlling said operating conditions of said second alkylation reaction zone by adjusting temperature or pressure effective to cause (i) part of said alkylatable aromatic compound to be in the vapor phase and part of said alkylatable aromatic compound to be in the liquid phase, and (ii) the ratio of the volume of liquid of said second feedstock to the volume of vapor of said second feedstock in said second reaction zone to be from about 0.5 to about 10 to maintain a dialkylaromatic/alkylaromatic weight ratio of less than 15%; and

(g) alkylating said alkylatable aromatic compound with said alkene in the presence of said alkylation catalyst to form a second effluent comprising additional alkylaromatic compound, unreacted alkylatable aromatic compound, polyalkylated aromatic compound, any unreacted alkene and said alkane, wherein said alkylation catalysts in each of said first and second alkylation reaction zones comprise a molecular sieve independently selected from the group consisting of zeolite Beta, faujacite, zeolite Y, Ultrastable Y (USY), Dealuminized Y (Deal Y), mordenite, TEA-mordenite, ZSM-3, ZSM-4, ZSM-5, ZSM-18, and ZSM-20, and mixtures thereof.

2. The process of claim 1, wherein the operating conditions in steps (b) and (f) are such that the ratio of the volume of liquid to the volume of vapor in each of said first and second reaction zones is from about 0.5 to about 5.

3. The process of claim 1, wherein the operating conditions in steps (b) and (f) are such that the ratio of the volume of liquid to the volume of vapor in each of said first and second reaction zones is from about 0.5 to about 2.

4. The process of claim 1, wherein the operating conditions in steps (b) and (f) are such that the ratio of the volume of liquid to the volume of vapor in each of said first and second reaction zones is from about 0.5 to about 1.

5. The process of claim 1, wherein said second feed comprises at least 20 wt. % of said alkene.

6. The process of claim 1, wherein said second feed comprises about 20 to about 80 wt. % of said alkene.

7. The process of claim 1, wherein said second feed comprises about 60 to about 80 wt. % of said alkene.

8. The process of claim 1, wherein said alkane in said second feed has the same number, or less, carbon atoms as said alkene.

9. The process of claim 1, wherein said alkene comprises ethylene, said alkylatable aromatic compound comprises benzene and said alkylaromatic compound comprises ethylbenzene.

10. The process of claim 9, wherein said operating conditions in step (b), and optionally step (f), include a temperature of about 120 to about 270°

C. or a pressure of about 675 to about 8300 kPa.

11. The process of claim 1, wherein said alkene comprises propylene, said alkylatable aromatic compound comprises benzene and said alkylaromatic compound comprises cumene.

12. The process of claim 11, wherein said operating conditions in step (b), and optionally step (f), include a temperature of about 80 to about 180°

C. or a pressure of about 675 to about 4000 kPa.

13. The process of claim 1, wherein said alkene comprises 1-butene and/or 2-butene, said alkylatable aromatic compound comprises benzene and said alkylaromatic compound comprises sec-butylbenzene.

14. The process of claim 13, wherein said operating conditions in step (b), and optionally step (f), include a temperature of about 50 to about 250°

C. or a pressure of about 355 to about 3550 kPa.

15. The process of claim 1, further comprising the steps of:

(h) separating said polyalkylated aromatic compounds from said second effluent of said second alkylation reaction zone, and

(i) contacting at least portion of said polyalkylated aromatic compounds with additional said alkylatable aromatic compound in the presence of a transalkylation catalyst under transalkylating conditions, to form additional monoalkylaromatic compound.

16. The process of claim 1, further comprising the step of contacting said feed with said alkylation catalyst in a by-passable pre-reactor separate from and upstream of said series-connected, multistage reaction system.

17. The process of claim 1, further comprising the step of contacting unreacted alkylatable aromatic compound and unreacted alkene from said multistage reaction system under alkylation conditions with said alkylation catalyst in a finishing reactor separate from and downstream of said multistage reaction system.

18. A process for producing ethylbenzene from a feed comprising benzene, ethylene and ethane in a multistage reaction system, said reaction system comprising at least first and second series-connected alkylation reaction zones each containing an alkylation catalyst and having operating conditions, and at least one transalkylation reaction zone comprising a transalkylation catalyst, the process comprising the steps of:

(a) controlling said operating conditions of said first alkylation reaction zone by adjusting temperature or pressure effective to cause (i) part of said benzene of said feed to be in the vapor phase and part of said benzene of said feed to be in the liquid phase, and (ii) the ratio of the volume of liquid to the volume of vapor in said first reaction zone is from about 0.5 to about 10 to maintain a diethylbenzene/ethylbenzene weight ratio of less than 15%;

(b) reacting said benzene and said ethylene of said feed in the presence of said alkylation catalyst to form a first effluent, said first effluent comprising said ethylbenzene, unreacted benzene, any unreacted ethylene, polyethylbenzene, and said ethane;

(c) withdrawing said first effluent from said first alkylation reaction zone and without removing said ethane from said first effluent, supplying said first effluent to said second alkylation reaction zone;

(d) controlling said operating conditions of said second alkylation reaction zone by adjusting temperature or pressure effective to cause (i) part of said benzene of said first effluent to be in the vapor phase and part of said benzene of said first effluent to be in the liquid phase, and (ii) the ratio of the volume of vapor in said second reaction zone is from about 0.5 to about 10 to maintain a diethylbenzene/ethylbenzene weight ratio of less than 15%;

(e) reacting said benzene and said ethylene of said first effluent in the presence of said alkylation catalyst to form a second effluent comprising additional ethylbenzene, unreacted benzene, any unreacted ethylene, polyethylbenzene, and said ethane, wherein said alkylation catalysts in each of said first and second alkylation reaction zones comprise a molecular sieve independently selected from the group consisting of zeolite Beta, faujacite, zeolite Y, Ultrastable Y (USY), Dealuminized Y (Deal Y), mordenite, TEA-mordenite, ZSM-3, ZSM-4, ZSM-5, ZSM-18, and ZSM-20, and mixtures thereof;

(f) separating said polyethylbenzene from said second effluent, and

(g) contacting at least portion of said polyethylbenzene with additional benzene in the presence of a transalkylation catalyst under transalkylating conditions in said transalkylation zone, to form additional ethylbenzene, said transalkylation catalyst comprises a molecular sieve selected from the group consisting of MCM-22, PSH-3, SSZ-25, ERB-1, ITQ-1, ITQ-2, MCM-36, MCM-49, MCM-56, and mixtures thereof.

19. A process for producing cumene from a feed comprising benzene, propylene and propane in a multistage reaction system, said reaction system comprising at least first and second series-connected alkylation reaction zones each containing an alkylation catalyst and having operating conditions, and at least one transalkylation reaction zone comprising a transalkylation catalyst, the process comprising the steps of:

(a) controlling said operating conditions of said first alkylation reaction zone by adjusting temperature or pressure effective to cause (i) part of said benzene to be in the vapor phase and part of said benzene to be in the liquid phase, and (ii) the ratio of the volume of liquid to the volume of vapor in said first reaction zone is from about 0.5 to about 10 to maintain a di-isopropylbenzene/isopropylbenzene weight ratio of less than 15%;

(b) reacting said benzene and said propylene of said feed in the presence of said alkylation catalyst to form a first effluent, said first effluent comprising said cumene, unreacted benzene, any unreacted propylene, polyisopropylbenzene, and said propane;

(c) withdrawing said first effluent from said first alkylation reaction zone and without removing said propane from said first effluent, supplying said first effluent to said second alkylation reaction zone;

(d) controlling said operating conditions of said second alkylation reaction zone by adjusting temperature or pressure effective to cause (i) part of said benzene to be in the vapor phase and part of said benzene to be in the liquid phase, and (ii) the ratio of the volume of vapor in said second reaction zone is from about 0.5 to about 10 to maintain a di-isopropylbenzene/isopropylbenzene weight ratio of less than 15%;

(e) reacting said benzene and said propylene of said first effluent in the presence of said alkylation catalyst to form a second effluent, wherein said alkylation catalyst in each of said first and second alkylation reaction zones comprise a molecular sieve independently selected from the group consisting of_zeolite Beta, faujacite, zeolite Y, Ultrastable Y (USY), Dealuminized Y (Deal Y), mordenite, TEA-mordenite, ZSM-3, ZSM-4, ZSM-5, ZSM-18, and ZSM-20;

(f) separating said polyisopropylbenzene from said second effluent, and

(g) contacting at least portion of said polyisopropylbenzene with additional benzene in the presence of a transalkylation catalyst under transalkylating conditions in said transalkylation zone, to form additional cumene, said transalkylation catalyst comprises a molecular sieve selected from the group consisting of MCM-22, PSH-3, SSZ-25, ERB-1, ITQ-1, ITQ-2, MCM-36, MCM-49, MCM-56, and mixtures thereof.

20. A process for producing sec-butylbenzene from a feed comprising benzene, 1-butene or 2-butene and butane in a multistage reaction system, said reaction system comprising at least first and second series-connected alkylation reaction zones each containing an alkylation catalyst and having operating conditions, and at least one transalkylation reaction zone comprising a transalkylation catalyst, the process comprising the steps of:

(a) controlling said operating condition of said first alkylation reaction zone by adjusting temperature or pressure effective to cause (i) part of said benzene of said feed to be in the vapor phase and part of said benzene of said feed to be in the liquid phase, and (ii) the ratio of the volume of liquid to the volume of vapor in said first reaction zone is from about 0.5 to about 10 to maintain a di-sec-butylbenzene/sec-butylbenzene weight ratio of less than 15%;

(b) reacting said benzene and said 1-butene or 2-butene of said feed in the presence of said alkylation catalyst to form a first effluent, said first effluent comprising said sec-butylbenzene, unreacted benzene, any unreacted 1-butene or 2-butene, polybutylbenzene, and said butane;

(c) withdrawing said first effluent from said first alkylation reaction zone and without removing said butane from said first effluent, supplying said first effluent and said 1-butene or 2-butene to said second alkylation reaction zone; and

(d) controlling said operating conditions of said second alkylation reaction zone by adjusting temperature or pressure effective to cause (i) part of said benzene of said first effluent to be in the vapor phase and part of said benzene of said first effluent to be in the liquid phase, and (ii) the ratio of the volume of liquid to the volume of vapor in said second reaction zone is from about 0.5 to about 10 to maintain a di-sec-butylbenzene/sec-butylbenzene weight ratio of less than 15%;

(e) reacting said benzene and said 1-butene or 2-butene of said first effluent in the presence of said alkylation catalyst to form a second effluent comprising additional sec-butylbenzene, unreacted benzene, and any unreacted 1-butene or 2-butene, polybutylbenzene, and said propane, wherein said alkylation catalysts in each of said first and second alkylation reaction zones comprise a molecular sieve independently selected from the group consisting of zeolite Beta, faujacite, zeolite Y, Ultrastable Y (USY), Dealuminized Y (Deal Y), mordenite, TEA-mordenite, ZSM-3, ZSM-4, ZSM-5, ZSM-18, and ZSM-20, and mixtures thereof;

(f) separating said polybutylbenzene from said second effluent of said second alkylation reaction zone, and

(g) contacting at least portion of said polybutylbenzene with additional benzene in the presence of a transalkylation catalyst under transalkylating conditions in said transalkylation reaction zone, to form additional sec-butylbenzene, said transalkylation catalyst comprises a molecular sieve selected from the group consisting of MCM-22, PSH-3, SSZ-25, ERB-1, ITQ-1, ITQ-2, MCM-36, MCM-49, MCM-56, and mixtures thereof.