Process for co-production of mixed xylenes and high octane C9+ aromatics

Patent metadata

Field	Value
Publication number	US-11053176-B2
Application number	US-201916979751-A
Country	US
Kind code	B2
Filing date	Mar 15, 2019
Priority date	Mar 30, 2018
Publication date	Jul 6, 2021
Grant date	Jul 6, 2021

Abstract

Disclosed is a process for producing mixed xylenes and C 9+ hydrocarbons in which an aromatic hydrocarbon feedstock comprising benzene and/or toluene is contacted with an alkylating agent comprising methanol and/or dimethyl ether under alkylation conditions in the presence of an alkylation catalyst to produce an alkylated aromatic product stream comprising the mixed xylenes and C 9+ hydrocarbons. The mixed xylenes are subsequently converted to para-xylene, and the C 9+ hydrocarbons and its components may be supplied as motor fuels blending components. The alkylation catalyst comprises a molecular sieve having a Constraint Index in the range from greater than zero up to about 3. The molar ratio of aromatic hydrocarbon to alkylating agent is in the range of greater than 1:1 to less than 4:1.

First claim

The invention claimed is:

1. A process for producing a mixed xylenes stream and a C 9+ aromatic hydrocarbon stream, the process comprising the steps of:
(a) contacting an aromatic hydrocarbon feed with an alkylating agent feed in the presence of an alkylation catalyst under alkylation conditions to produce an alkylated aromatic product stream which comprises said mixed xylenes and of said C 9+ aromatic hydrocarbons,
wherein said aromatic hydrocarbon comprises benzene and/or toluene, said alkylating agent comprises methanol and/or dimethyl ether, said alkylation catalyst comprises a molecular sieve having a Constraint Index in the range from greater than zero up to about 3 and alkylation conditions comprises a temperature of less than 500° C., and
wherein the molar ratio of aromatic hydrocarbon feed to alkylating agent feed is in the range of greater than 1:1 to less than 4:1;
(b) recovering streams comprising said mixed xylenes and said C 9+ aromatic hydrocarbon from said alkylated aromatic product stream;
(c) supplying said mixed xylenes stream to a xylenes isomerization unit to produce para-xylene; and
(d) supplying said C 9+ aromatic hydrocarbon stream to a separation unit to recover at least a C 9 aromatic hydrocarbon stream, wherein said C 9 aromatic hydrocarbon stream comprises a mixture of trimethylbenzenes and a mixture of ethylmethylbenzenes;
(e) supplying said C 9 aromatic hydrocarbon stream to a separation unit to recover a stream comprising said mixture of trimethylbenzenes and/or said stream comprising a mixture of ethylmethylbenzenes; and
(f) supplying said stream comprising said mixture of trimethylbenzenes and/or said stream comprising a mixture of ethylmethylbenzenes as motor fuels blending component(s).

2. The process of claim 1 , wherein said molecular sieve has a MTW, a BEA*, a FAU or a MOR framework structure.

3. The process of claim 2 , wherein said molecular sieve having said MTW framework structure is ZSM-12.

4. The process of claim 1 , wherein said alkylated aromatic product stream comprises at least about 75 wt % of said mixed xylenes and/or at least about 21 wt % of said C 9+ aromatic hydrocarbons, each wt % based on the weight of said alkylated aromatic product stream.

5. The process of claim 2 , wherein said molecular sieve having said BEA* framework structure is zeolite Beta.

6. The process of claim 2 , wherein said molecular sieve having said FAU framework structure is selected from the group consisting of faujasite, zeolite Y, Ultrastable Y (USY), Dealuminized Y (Deal Y), Rare Earth Y(REY), Ultrahydrophobic Y and mixtures thereof.

7. The process of claim 2 , wherein said molecular sieve having said MOR framework structure is selected from the group consisting of natural Mordenite, TEA-Mordenite and mixtures thereof.

8. The process of claim 1 , wherein said molecular sieve is selected from the group consisting of ZSM-3, ZSM-4, ZSM-14, ZSM-18, ZSM-20, ZSM-38 and mixtures thereof.

9. The process of claim 1 , wherein the alkylation conditions comprise a temperature in the range from 300° C. to 450° C., a pressure in the range from 700 kPa-a to 7000 kPa-a, and a weight hourly space velocity based on the aromatic hydrocarbon feed of 50 hr −1 to 0.5 hr −1 .

10. A process for producing a C 9 aromatic hydrocarbon stream and a C 10 aromatic hydrocarbon stream, the process comprising the steps of:
(a) contacting an aromatic hydrocarbon feed comprising benzene and/or toluene with a feed comprising methanol and/or dimethyl ether in the presence of an alkylation catalyst comprising ZSM-12 under alkylation conditions to produce an alkylated aromatic product stream which comprises said C 9 aromatic hydrocarbons and C 10 aromatic hydrocarbons;
wherein the molar ratio of aromatic hydrocarbon feed to feed comprising methanol is in the range of greater than about 1:1 to about 4:1 and said alkylation conditions comprises a temperature in the range of 300° C. to 450° C., a pressure in the range of from 700 kPa-a to 7000 kPa-a, and a weight hourly space velocity based on the aromatic hydrocarbon feed of 50 hr −1 to 0.5 hr −1 ;
(b) separating said alkylated aromatic product stream to recover said C 9 aromatic hydrocarbon stream and said C 10 aromatic hydrocarbon stream, wherein said C 9 aromatic hydrocarbon stream comprises a mixture of trimethylbenzenes and a mixture of ethylmethylbenzenes;
(c) supplying said C 9 aromatic hydrocarbon stream to a separation unit to recover a stream comprising said mixture of trimethylbenzenes and/or said stream comprising a mixture of ethylmethylbenzenes; and
(d) supplying said stream comprising said mixture of trimethylbenzenes and/or said stream comprising a mixture of ethylmethylbenzenes as a motor fuels blending component(s).

11. The process of claim 10 , further comprising the step of:
(e) supplying said C 10 aromatic hydrocarbon stream as a motor fuels blending component(s).

12. The process of claim 10 , wherein said mixture of trimethylbenzenes comprises 1,2,4-trimethylbenzene, 1,3,5-trimethylbenzene and 1,2,3-trimethylbenzene.

13. The process of claim 10 , further comprising the step of:
(e) supplying said stream comprising said mixture of trimethylbenzenes to said separation unit to recover separate streams comprising 1,2,4-trimethylbenzene, 1,3,5-trimethylbenzene and 1,2,3-trimethylbenzene.

14. The process of claim 13 , further comprising the step of:
(f) supplying each of said separate trimethylbenzene streams as a motor fuels blending component.

15. The process of claim 10 , wherein said mixture of ethylmethylbenzenes comprises 1-ethyl, 2-methylbenzene and 1-ethyl, 3-methylbenzene.

16. The process of claim 15 , further comprising the step of:
(e) supplying said stream comprising said mixture of ethylmethylbenzene to said separation unit to recover separate streams comprising 1-ethyl, 2-methylbenzene and 1-ethyl, 3-methylbenzene.

17. The process of claim 16 , further comprising the step of:
(f) supplying each of said separate streams comprising 1-ethyl, 2-methylbenzene and 1-ethyl, 3-methylbenzene as a motor fuels blending component.

18. The process of claim 1 , wherein the alkylation catalyst is present in a fixed bed.

19. The process of claim 10 , wherein the alkylation catalyst is present in a fixed bed.

Assignees

• Exxonmobil Chemical Patents Inc

Inventors

• Chen Tan-Jen
• Lai Wenyih F
• Go Anthony

Classifications

• B01J19/18

  Stationary reactors having moving elements inside (B01J19/08, B01J19/26 take precedence) · CPC title

• B01J35/70

  characterised by their crystalline properties, e.g. semi-crystalline (catalysts comprising carbon B01J21/18; molecular sieves B01J29/00) · CPC title

• C07C5/2737

  with crystalline alumino-silicates, e.g. molecular sieves · CPC title

• B01J2235/30

  Scanning electron microscopy; Transmission electron microscopy · CPC title

• B01J2235/15

  X-ray diffraction · CPC title