Hydroalkylation processes

Patent metadata

Field	Value
Publication number	US-9233889-B2
Application number	US-201113640503-A
Country	US
Kind code	B2
Filing date	Apr 4, 2011
Priority date	May 20, 2010
Publication date	Jan 12, 2016
Grant date	Jan 12, 2016

Abstract

The invention relates to hydroalkylation processes. In the processes, a hydrogen stream comprising hydrogen and an impurity is treated to reduce the amount of the impurity in the hydrogen stream. The hydrogen is then hydroalkylated with benzene to form at least some cyclohexylbenzene. The processes also relate to treating a benzene stream comprising benzene and an impurity with an adsorbent to reduce the amount of the impurity in the benzene stream. The hydroalkylation processes described herein may be used as part of a process to make phenol.

First claim

The invention claimed is:

1. A hydroalkylation process comprising:
(a) treating a hydrogen stream comprising hydrogen and an impurity having the general formula CO x , wherein the treating (a) reduces the amount of the impurity to about 0.1 ppm or less in the hydrogen stream;
(b) pretreating a benzene stream comprising benzene and a benzene impurity to remove the benzene impurity in the benzene stream to about 0.1 ppm or less; and
(c) contacting the pretreated benzene stream with the treated hydrogen stream in the presence of a hydroalkylation catalyst to form cyclohexylbenzene;
wherein the hydroalkylation catalyst comprises a molecular sieve selected from the group consisting of MCM-22, EMM-10, EMM-11, EMM-12, EMM-13, MCM-49, MCM-56, isotypes of MCM-49 and MCM-56, and any combination thereof.

2. The process of claim 1 , wherein the impurity is one or more of carbon monoxide and carbon dioxide.

3. The process of claim 2 , wherein the treating (a) comprises contacting the hydrogen stream with a methanation catalyst under methanation conditions to convert a portion of or all of the impurity and the hydrogen to methane and water.

4. The process of claim 3 , wherein the methanation catalyst comprises at least one Group 8-10 metal and a support.

5. The process of claim 3 , wherein the methanation catalyst comprises nickel and a support.

6. The process of claim 5 , wherein the support comprises one or more of aluminum oxide, silica, silicate and aluminosilicate.

7. The process of claim 3 , wherein the methanation conditions comprise a temperature of about 200° C. to about 500° C. and a pressure of about 0.1 MPa, gauge to about 2.0 MPa, gauge.

8. The process of claim 1 , wherein the hydrogen stream further comprises a second impurity selected from the group consisting of hydrogen sulfide, diphenylsulfide, carbonyl sulfide, and any combination thereof; and wherein the treating (a) further reduces the amount of the second impurity to about 100 ppm or less.

9. The process of claim 8 , wherein the treating (a) comprises scrubbing the hydrogen stream with an amine to at least partially remove the second impurity.

10. The process of claim 9 , wherein the amine is one or more of monoethanolamine, diethanolamine, triethanolamine, methylamine, dimethylamine and trimethylamine.

11. The process of claim 8 , wherein the treating (a) comprises scrubbing the hydrogen stream with a caustic.

12. The process of claim 11 , wherein the caustic is one or more of sodium hydroxide and potassium hydroxide.

13. The process of claim 8 , wherein the treating (a) comprises contacting the hydrogen stream with an adsorbent.

14. The process of claim 13 , wherein the adsorbent is one or more of activated alumina, zinc and a copper/zinc compound.

15. The process of claim 1 , wherein the contacting (c) is conducted in the presence of a hydroalkylation catalyst comprising a molecular sieve and a hydrogenation metal.

16. The process of claim 15 , wherein the hydrogenation metal comprises one or more of palladium, cobalt and nickel.

17. The process of claim 1 , wherein the treating (a) reduces the amount of the impurity in the hydrogen stream to about 0.01 ppm or less.

18. The process of claim 1 , wherein the benzene impurity is nitrogen.

19. The process of claim 1 , wherein the pretreating comprises contacting the benzene with an adsorbent.

20. The process of claim 19 , wherein the adsorbent comprises at least a first silica-alumina molecular sieve and a second silica-alumina molecular sieve, wherein the first silica-alumina molecular sieve has a silica/alumina molar ratio of less than 5 and the second silica-alumina molecular sieve has a silica/alumina molar ratio of greater than 5.

21. The process of claim 1 , further comprising:
(d) oxidizing a portion or all of the cyclohexylbenzene to form cyclohexylbenzene hydroperoxide;
(e) cleaving a portion or all of the cyclohexylbenzene hydroperoxide to form phenol and cyclohexanone;
(f) dehydrogenating a portion or all of the cyclohexanone to form phenol and hydrogen; and
(g) recycling a portion or all of the hydrogen formed during dehydrogenation to the hydrogen stream at a point prior to the treating (a) such that the hydrogen stream comprises the portion or all of the hydrogen formed during dehydrogenation.

22. The process of claim 21 , wherein the treating (a) reduces the amount of the impurity in the hydrogen stream, to about 0.01 ppm or less.

23. A hydroalkylation process comprising:
(a) treating a hydrogen stream comprising hydrogen, a first impurity having the general formula CO x , and a second impurity comprising one or more sulfur-containing compounds,
wherein the treating (a) reduces the amount of the first impurity in the hydrogen stream to less than 0.1 ppm,
wherein the treating (a) comprises contacting the first impurity with a methanation catalyst under methanation conditions to convert some or all of the first impurity and a portion of the hydrogen to methane and water,
wherein the treating (a) further comprises one or more of:
i) contacting the hydrogen stream with one or more of an amine and a caustic; and
ii) contacting the hydrogen stream with an adsorbent;

(b) pretreating a benzene stream comprising benzene and a benzene impurity to remove the benzene impurity in the benzene stream to about 0.1 ppm or less; and
(c) contacting the pretreated benzene stream with the treated hydrogen stream in the presence of a hydroalkylation catalyst to form at least some cyclohexylbenzene;
wherein the hydroalkylation catalyst comprises a molecular sieve selected from the group consisting of MCM-22, EMM-10, EMM-11, EMM-12, EMM-13, MCM-49, MCM-56, isotypes of MCM-49 and MCM-56, and any combination of the foregoing.

24. The process of claim 18 , wherein pretreating the benzene reduces the amount of the benzene impurity in the benzene to about 0.01 ppm or less.

Assignees

• Chen Tan-Jen
• Xu Teng
• Helton Terry E
• Benitez Francisco M
• Smith Charles M
• Exxonmobil Chem Patents Inc

Inventors

• Chen Tan-Jen
• Xu Teng
• Helton Terry E
• Benitez Francisco M
• Smith Charles M

Classifications

• C07C2521/02

  Boron or aluminium; Oxides or hydroxides thereof · CPC title

• C07C39/04

  Phenol · CPC title

• C07C2/74 Primary

  by addition with simultaneous hydrogenation · CPC title

• C07C2101/14

  Chemistry & Metallurgy · mapped topic

• C07C2523/44

  Palladium · CPC title