Process for producing phenol

Patent metadata

Field	Value
Publication number	US-9388102-B2
Application number	US-201114110859-A
Country	US
Kind code	B2
Filing date	Dec 15, 2011
Priority date	Apr 19, 2011
Publication date	Jul 12, 2016
Grant date	Jul 12, 2016

Abstract

In a process for producing phenol, cyclohexylbenzene is contacted with an oxygen-containing compound in the presence of an oxidation catalyst comprising a cyclic imide under oxidation conditions effective to produce a product comprising cyclohexylbenzene hydroperoxide and unreacted cyclic imide catalyst. Without removing all the unreacted cyclic imide catalyst, at least a portion of the product is contacted with an acidic molecular sieve under conditions effective to adsorb at least a portion of the unreacted cyclic imide and to convert at least part of the cyclohexylbenzene hydroperoxide in the product portion into phenol and cyclohexanone.

First claim

The invention claimed is:

1. A process for producing phenol, the process comprising:
(a) contacting cyclohexylbenzene with an oxygen-containing compound in the presence of an oxidation catalyst comprising a cyclic imide under oxidation conditions effective to produce a product comprising cyclohexylbenzene hydroperoxide and unreacted cyclic imide catalyst; and
(b) contacting at least a portion of the product with an acidic molecular sieve comprising an aluminosilicate FAU-type zeolite having unit cell size less than 24.35 Å under conditions effective to adsorb at least a portion of the unreacted cyclic imide and convert at least a portion of the cyclohexylbenzene hydroperoxide in said product into phenol and cyclohexanone, wherein less than 50 wt % of the unreacted cyclic imide catalyst is removed from the product prior to the contacting step (b).

2. The process of claim 1 , wherein the unreacted cyclic imide catalyst is not deliberately removed from the product prior to the contacting step (b).

3. The process of claim 1 , wherein less than 20 wt % of the unreacted cyclic imide is removed from the product prior to the contacting step (b).

4. The process of claim 1 , wherein less than 5 wt % of the unreacted cyclic imide is removed from the product prior to the contacting step (b).

5. The process of claim 1 , wherein said aluminosilicate FAU-type zeolite has a pore size greater than 7 Å.

6. The process of claim 1 , wherein said FAU type zeolite has a unit cell size less than or equal to 24.30 Å.

7. The process of claim 1 , wherein the cyclic imide catalyst is N-hydroxyphthalimide.

8. The process of claim 1 , wherein said conditions in the contacting step (b) include a temperature of about 20° C. to about 200° C. and a pressure of about 100 kPa to about 2000 kPa.

9. The process of claim 1 , wherein the contacting step (b) is conducted in at least a first reactor and a second reactor connected in series.

10. The process of claim 9 , wherein the first reactor is operated at a temperature of about 20° C. to about 120° C. and a pressure of about 100 kPa to about 500 kPa, and the second reactor is operated at a temperature of about 40° C. to about 180° C. and a pressure of about 100 kPa to about 1000 kPa.

11. The process of claim 1 , wherein the contacting step (b) is conducted in at least one of a plurality of reactors connected in parallel.

12. The process of claim 11 , wherein the acidic molecular sieve is regenerated in a first reactor during operation of the contacting step (b) in a second reactor.

13. The process of claim 12 , wherein acidic molecular sieve regeneration comprises flushing the acidic molecular sieve with a polar organic solvent to remove at least part of the cyclic imide adsorbed on the acidic molecular sieve.

14. The process of claim 1 , wherein the contacting step (b) is at least partly conducted in a continuously stirred tank reactor.

15. The process of claim 12 , wherein the regenerated acidic molecular sieve is returned to the contacting step (b).

16. The process of claim 1 , wherein the acidic molecular sieve is continuously or periodically added to the contacting step (b) to maintain conversion.

17. The process of claim 1 , wherein the contacting step (b) is at least partly conducted in a fixed bed reactor.

18. The process of claim 1 , wherein at least a portion of the phenol is converted to at least one of a phenolic resin, bisphenol A, ε-caprolactam, an adipic acid, or a plasticizer.

19. The process of claim 1 , wherein at least a portion of the cyclohexanone is converted into at least one of adipic acid, a cyclohexanone resin, a cyclohexanone oxime, caprolactam, or nylon.

20. A process for producing phenol, the process comprising:
(a) contacting cyclohexylbenzene with an oxygen-containing compound in the presence of an oxidation catalyst comprising a cyclic imide under oxidation conditions effective to produce a product comprising cyclohexylbenzene hydroperoxide and unreacted cyclic imide catalyst; and
(b) contacting at least a portion of the product containing cyclohexylbenzene hydroperoxide and at least 50 ppmw of the unreacted cyclic imide catalyst with an acidic molecular sieve comprising an aluminosilicate FAU-type zeolite having unit cell size less than 24.35 Å under conditions effective to adsorb at least a portion of the unreacted cyclic imide and to convert at least a portion of the cyclohexylbenzene hydroperoxide in said product portion into phenol and cyclohexanone.

21. The process of claim 20 , wherein at least a portion of the cyclic imide catalyst is desorbed from said acidic molecular sieve and recycled to said contacting step (a).

22. A process for producing phenol, the process comprising:
(a) hydroalkylating benzene with hydrogen in the presence of a hydroalkylation catalyst under conditions effective to produce a hydroalkylation reaction product comprising cyclohexylbenzene;
(b) separating cyclohexylbenzene from said hydroalkylation reaction product;
(c) contacting at least a portion of said cyclohexylbenzene from said separating step (b) with an oxygen-containing compound in the presence of an oxidation catalyst comprising a cyclic imide under oxidation conditions effective to produce a cleavage product comprising cyclohexylbenzene hydroperoxide and unreacted cyclic imide catalyst; and
(d) contacting at least a portion of the product with an acidic molecular sieve comprising an aluminosilicate FAU-type zeolite having unit cell size less than 24.35 Å under conditions effective to adsorb at least part of the cyclic imide and to convert at least part of the cyclohexylbenzene hydroperoxide in said product portion into phenol and cyclohexanone, wherein less than 50 wt % of the unreacted cyclic imide catalyst is removed from the product prior to the contacting step (d).

Assignees

• Wang Kun
• Garcia Roberto
• Dakka Jihad M
• Mozeleski Edmund J
• Exxonmobil Chem Patents Inc

Inventors

• Wang Kun
• Garcia Roberto
• Dakka Jihad M
• Mozeleski Edmund J

Classifications

• C07C409/14

  the carbon atom belonging to a ring other than a six-membered aromatic ring · CPC title

• C07C2/74

  by addition with simultaneous hydrogenation · CPC title

• C07C37/86

  by treatment giving rise to a chemical modification (chemisorption C07C37/82) · CPC title

• C07C49/403

  of a six-membered ring · CPC title

• B01J29/06

  Crystalline aluminosilicate zeolites; Isomorphous compounds thereof · CPC title