Process for converting oxygenates to aromatic hydrocarbons

Patent metadata

Field	Value
Publication number	US-9783460-B2
Application number	US-201414560850-A
Country	US
Kind code	B2
Filing date	Dec 4, 2014
Priority date	Dec 20, 2013
Publication date	Oct 10, 2017
Grant date	Oct 10, 2017

Abstract

Embodiments of the invention provide processes for catalytically converting oxygenates to hydrocarbon products having an increased C 6 -C 8 aromatics content therein. Particular processes include (a) providing a first mixture comprising ≧10.0 wt. % of at least one oxygenate, based on the weight of the first mixture; (b) contacting the first mixture with a catalyst to convert the first mixture to a product stream including water, one or more hydrocarbons, hydrogen, and one or more oxygenates, wherein the catalyst comprises at least one molecular sieve and at least one element selected from Groups 2-14 of the Periodic Table and the hydrocarbons comprise ≧30.0 wt. % of aromatics, based on the weight of the hydrocarbons in the product stream; and (c) separating from the product stream at least one water-rich stream, at least one aromatic-rich hydrocarbon stream, and at least one aromatic-depleted hydrocarbon stream.

First claim

What is claimed is:

1. An aromatic production process, comprising:
(a) providing a first mixture comprising ≧10.0 wt. % of at least one oxygenate, based on the weight of the first mixture;
(b) contacting the first mixture with a catalyst to convert the first mixture to a product stream comprising water, one or more hydrocarbons, hydrogen, and one or more oxygenates, wherein:
(1) the catalyst comprises at least one molecular sieve and at least one element selected from Groups 2-14 of the Periodic Table; and
(2) the one or more hydrocarbons comprise ≧30.0 wt. % of aromatics, based on the weight of the one or more hydrocarbons in the product stream;

(c) separating from the product stream (i) a water-rich stream, (ii) an aromatic-rich hydrocarbon stream, and (iii) an aromatic-depleted hydrocarbon stream;
(d) separating from the aromatic-rich hydrocarbon stream (i) a first stream comprising C 6 and/or C 7 aromatics, (ii) a second stream comprising C 8 aromatics, and (iii) a third stream comprising C 9+ aromatics; and
(e) separating an oxygenate stream from at least one of the first stream, the second stream, or the third stream.

2. The process of claim 1 , wherein the first mixture comprises ≧90.0 wt. % of methanol and/or dimethylether.

3. The process of claim 2 , further comprising contacting at least a portion of the first stream with the catalyst in step (b).

4. The process of claim 2 , wherein the separating in (e) comprises separating from the first stream a first oxygenate stream and a second aromatics-rich stream, the second aromatics-rich stream comprising C 6 and/or C 7 aromatics.

5. The process of claim 4 , further comprising recovering benzene and/or toluene from the second aromatics-rich stream.

6. The process of claim 4 , further comprising sending at least a portion of the second aromatics-rich stream to a toluene alkylation, toluene disproportionation or transalkylation unit to produce xylenes.

7. The process of claim 4 , further comprising contacting at least a portion of the first oxygenate stream with the catalyst in step (b).

8. The process of claim 2 , wherein the separating in (e) comprises separating from the second stream a second oxygenate stream and a third aromatics-rich stream, the third aromatics-rich stream comprising C 8+ aromatics.

9. The process of claim 8 , further comprising recovering para-xylene and a para-xylene depleted stream from the third aromatics-rich stream.

10. The process of claim 9 , further comprising sending at least a portion of the para-xylene depleted stream to a xylenes isomerization unit to produce a mixed xylenes stream and recovering para-xylene from the mixed xylenes stream.

11. The process of claim 8 , further comprising contacting at least a portion of the second oxygenate stream with the catalyst in step (b).

12. The process of claim 2 , wherein the separating in (e) comprises separating from the third stream a third oxygenate stream and a fourth aromatics-rich stream, the fourth aromatics-rich stream comprising C 9+ aromatics.

13. The process of claim 12 , further comprising transalkylating at least a portion of the fourth aromatics-rich stream to produce xylenes.

14. The process of claim 12 , further comprising contacting at least a portion of the third oxygenate stream with the catalyst in step (b).

15. The process of claim 1 , further comprising contacting at least a portion of the aromatic-depleted hydrocarbon stream with the catalyst in step (b).

16. The process of claim 1 , further comprising recovering oxygenates from the aromatic-depleted hydrocarbon stream.

17. The process of claim 16 , comprising contacting the catalyst in step (b) with at least a portion of the recovered oxygenates.

18. The process of claim 16 , further comprising recovering at least one of ethylene, propylene, and butylenes from at least a portion of the aromatic-depleted hydrocarbon stream.

19. The process of claim 1 , wherein the molecular sieve comprises ZSM-5, and the element comprises Zn.

20. An oxygenate conversion process, the process comprising:
(a) providing a first mixture, the first mixture comprising ≧10.0 wt. % oxygenate based on the weight of the first mixture;
(b) contacting the first mixture with a catalyst at a temperature ≧400° C. and a pressure ≧2 bar absolute to convert ≧90.0 wt. % of the first mixture's oxygenate to (i) water, (ii) hydrocarbon, and (iii) ≦1.0 wt. % carbon monoxide, the weight percents being based on the weight of oxygenate in the first mixture, wherein:
(1) the catalyst comprises ≧10.0 wt. % of at least one molecular sieve and ≧0.1 wt. % of at least one element selected from Groups 2-14 of the Periodic Table, the weight percents being based on the weight of the catalyst; and
(2) the hydrocarbon comprises ≧50.0 wt. % of aromatics, based on the weight of the hydrocarbon;

(c) separating from the hydrocarbon (i) an aromatic-rich hydrocarbon stream, and (ii) an aromatic-depleted hydrocarbon stream;
(d) separating from the aromatic-rich hydrocarbon stream (i) a first stream comprising C 6 and/or C 7 aromatics, (ii) a second stream comprising C 8 aromatics, and (iii) a third stream comprising C 9+ aromatics; and
(e) separating an oxygenate stream from at least one of the first stream, the second stream, or the third stream.

21. The process of claim 20 , wherein (i) the first mixture comprises ≧25.0 wt. % oxygenate, based on the weight of the first mixture, and (ii) the oxygenate in the first mixture comprises ≧90.0 wt. % based on the weight of the oxygenate of one or more of alcohol, ether, carboxylic acid, carbon monoxide, or carbon dioxide.

22. The process of claim 21 , wherein the oxygenate in the first mixture comprises ≧99.0 wt. % of methanol and/or dimethylether.

23. The process of claim 22 , wherein the oxygenate in the first mixture comprises ≧99.0 wt. % of methanol, the contacting of step (b) is conducted at a weight hourly space velocity in the range of from 0.5 to 12 hr −1 , the hydrocarbon comprises ≧80.0 wt. % of aromatics, based on the weight of the hydrocarbon, and ≦30.0 wt. % of the aromatics comprise durene, based on the weight of the aromatics.

24. The process of claim 20 , wherein the first mixture further comprises ≧10.0 wt. % aromatics, based on the weight of the first mixture.

25. The process of claim 20 , further comprising recycling at least a portion of aromatics in the aromatic-rich hydrocarbon stream to step (a), wherein ≧50.0 wt. % of the first mixture's aromatics are recycled from the aromatic-rich hydrocarbon stream.

26. The process of claim 20 , wherein the molecular sieve comprises ZSM-5, and the element comprises Zn.

Assignees

• Exxonmobil Chemical Patents Inc

Inventors

• Ou John D
• Mertens Machteld M
• Jacob Linelle T
• Mccarthy Stephen J
• Vijay Rohit
• Abichandani Jeevan S

Classifications

• C10G3/49 Primary

  containing crystalline aluminosilicates, e.g. molecular sieves · CPC title

• C07C1/24

  by elimination of water · CPC title

• C07C5/2729

  Changing the branching point of an open chain or the point of substitution on a ring · CPC title

• C07C6/06

  at a cyclic carbon-to-carbon double bond · CPC title

• Y02P30/42

  Cross-Sectional Technologies · mapped topic