Use of light gas by-products in the production of paraxylene by the methylation of toluene and or benzene

Patent metadata

Field	Value
Publication number	US-10961168-B2
Application number	US-201716335581-A
Country	US
Kind code	B2
Filing date	Aug 2, 2017
Priority date	Sep 22, 2016
Publication date	Mar 30, 2021
Grant date	Mar 30, 2021

Abstract

A process for producing paraxylene by the catalytic alkylation of benzene and/or toluene with methanol, which produces a para-rich mixture of xylene isomers, together with water and some light organic by-products, particularly dimethyl ether and C 4 − olefins. The off-gas stream, containing the C 4− olefins, may be recycled back to the reaction to be co-injected with methanol to reduce the methanol self-decomposition and the reaction of methanol to olefins or to fluidize catalyst particles recovered by a reactor cyclone. By using recycled off-gas rather than water or steam, the deleterious effects of water and/or steam on the catalyst aging and activity rates and the size of downstream equipment necessary to recover olefin by-products may be reduced.

First claim

What we claim:

1. A process for alkylation of toluene and/or benzene to produce paraxylene (PX) comprising contact of said toluene and/or benzene with an alkylating agent selected from methanol, dimethyl ether, and mixtures thereof, in the absence of intentionally co-fed molecular hydrogen, in the presence of an alkylation catalyst in a fluidized bed alkylation reactor under conditions effective to produce an alkylation effluent comprising PX and olefins, wherein the alkylation effluent is separated into a stream comprising PX and a light gas stream comprising olefins, the process comprising recycling at least a portion of the light gas stream, including olefins and substantially free of molecular hydrogen, to the alkylation reactor for injection with the alkylating agent, fluidizing particles of the alkylation catalyst that are recovered from the alkylation effluent in the alkylation reactor, or both.

2. The process of claim 1 , wherein the light gas stream further comprises oxygenates, unreacted alkylating agent, and contaminants, and is treated to remove at least one of the oxygenates, alkylating agent, and contaminants prior to recycling the light gas stream to the alkylation reactor.

3. The process of claim 1 , wherein the alkylating agent is methanol.

4. The process of claim 3 , wherein the methanol and recycled light gas stream is injected in multiple stages axially along the alkylation reactor.

5. The process of claim 2 , wherein a molar ratio of light gas stream to methanol is maintained in a range of 0.01:1 to 20:1.

6. The process of claim 1 , wherein the alkylation reactor comprises at least one internal cyclone with a dipleg for separating particles of the alkylation catalyst from the alkylation effluent, and the light gas stream is used to fluidize the catalyst particles being discharged from the dipleg.

7. The process of claim 1 , wherein the alkylation catalyst is a porous crystalline material having a Diffusion Parameter for 2,2 dimethylbutane of about 0.1-15 sec −1 when measured at a temperature of 120° C. and a 2,2 dimethylbutane pressure of 60 torr (8 kPa).

8. The process of claim 7 , wherein the alkylation catalyst is a medium-pore size aluminosilicate zeolite selected from the group consisting of ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35, and ZSM-48, optionally composited with an inorganic oxide matrix.

9. A process for producing paraxylene (PX), the process comprising:
(a) contacting toluene and/or benzene with methanol in the presence of an alkylation catalyst in an alkylation reactor in the absence of intentionally co-fed molecular hydrogen under conditions effective to produce an alkylation effluent comprising PX and olefins;
(b) separating the alkylation effluent into a product stream containing PX and a light gas stream containing olefins;
(c) recovering PX from the product stream; and
(d) recycling at least a portion of the light gas stream, including olefins and substantially free of molecular hydrogen, to the alkylation reactor for at least one of the following:
(i) injection with the methanol, or
(ii) fluidizing particles of the alkylation catalyst that are recovered from the alkylation effluent in the alkylation reactor.

10. The process of claim 9 , wherein the light gas stream further comprises oxygenates, unreacted alkylating agent, and contaminants, and is treated to remove at least one of the oxygenates, alkylating agent, and contaminants prior to recycling the light gas stream to the alkylation reactor.

11. The process of claim 9 , wherein the methanol and recycled light gas stream is injected in multiple stages axially along the alkylation reactor.

12. The process of claim 9 , wherein a molar ratio of light gas to methanol is maintained in a range of 0.01:1 to 20:1.

13. The process of claim 9 , wherein the alkylation reactor comprises at least one cyclone with a dipleg for separating particles of the alkylation catalyst from the alkylation effluent, and the light gas stream is used to fluidize the catalyst particles being discharged from the dipleg.

14. The process of claim 9 , wherein the alkylation catalyst is a porous crystalline material having a Diffusion Parameter for 2,2 dimethylbutane of about 0.1-15 sec −1 when measured at a temperature of 120° C. and a 2,2 dimethylbutane pressure of 60 torr (8 kPa).

15. The process of claim 14 , wherein the alkylation catalyst is a medium-pore size aluminosilicate zeolite selected from the group consisting of ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35, and ZSM-48, optionally composited with an inorganic oxide matrix.

Assignees

• Exxonmobil Chemical Patents Inc

Inventors

• Detjen Todd E
• Tinger Robert G

Classifications

• C07C2/864 Primary

  the non-hydrocarbon is an alcohol · CPC title

• C07C2529/65

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

• B01J8/0055

  using cyclones · CPC title

• C07C2529/40

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

• B01J8/1827

  the fluidising gas being a reactant · CPC title