Process for producing phenol

• US 8,884,075 B2
• Filed: 08/25/2011
• Issued: 11/11/2014
• Est. Priority Date: 10/11/2010
• Status: Expired due to Fees

• Current Assignee: ExxonMobil Chemical Patents Inc. (Exxon Mobil Corporation)
• Original Assignee: ExxonMobil Chemical Patents Inc. (Exxon Mobil Corporation)
• Inventors: Xu, Teng, Gamble, George Harry, Dakka, Jihad Mohammed, DeCaul, Lorenzo Cophard
• Primary Examiner(s): Davis, Brian J
• Application Number:
  US13/822,033
• Publication Number:
  US 20140148620A1
• Time in Patent Office: 1,174 Days
• Field of Search: 568/799
• US Class Current: 568/799
• CPC Class Codes: B01J 23/38 of noble metals
• CPC Class Codes: B01J 23/40 of the platinum group metals
• CPC Class Codes: B01J 23/58 with alkali- or alkaline earth metals
• CPC Class Codes: B01J 35/40 characterised by dimensions, e.g. grain size in a colloidal state B01J35/23; crystallite size B01J35/77
• CPC Class Codes: B01J 37/0201 Impregnation
• CPC Class Codes: C07C 13/28 Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof
• CPC Class Codes: C07C 2/74 by addition with simultaneous hydrogenation
• CPC Class Codes: C07C 2601/14 The ring being saturated
• CPC Class Codes: C07C 37/07 with simultaneous reduction of C=O group in that ring
• CPC Class Codes: C07C 37/08 by decomposition of hydroperoxides, e.g. cumene hydroperoxide
• CPC Class Codes: C07C 39/04 Phenol
• CPC Class Codes: C07C 407/00 Preparation of peroxy compounds
• CPC Class Codes: C07C 409/14 the carbon atom belonging to a ring other than a six-membered aromatic ring
• CPC Class Codes: C07C 45/53 of hydroperoxides
• CPC Class Codes: C07C 49/403 of a six-membered ring
• CPC Class Codes: Y02P 20/52 using catalysts, e.g. selective catalysts

Abstract

In a process for the dehydrogenation of cyclohexanone to produce phenol, cyclohexanone is contacted in a reaction zone under dehydrogenation conditions with a dehydrogenation catalyst comprising (i) a support comprising silica; and (ii) a dehydrogenation component comprising at least one metal selected from Group 10 of Periodic Table of Elements. Contact of the dehydrogenation catalyst with the cyclohexanone is then terminated and the dehydrogenation catalyst is contacted with an inert gas and/or hydrogen at a temperature of at least 300° C. Contact of the dehydrogenation catalyst with additional cyclohexanone is subsequently reestablished.

Claims

1. A process for the dehydrogenation of cyclohexanone to produce phenol, the process comprising:

(a) contacting cyclohexanone in a reaction zone under dehydrogenation conditions with a dehydrogenation catalyst comprising (i) a support comprising silica; and

(ii) a dehydrogenation component comprising at least one metal selected from Group 10 of the Periodic Table of Elements, wherein the dehydrogenation conditions include a temperature of about 250°

C. to about 500°

C., a pressure of about 100 to about 3550 kPa, a weight hourly space velocity of about 0.2 to 50 hr<sup>−

1</sup>, and a hydrogen to cyclohexanone molar ratio of about 2 to about 20;

(b) terminating contact of the dehydrogenation catalyst with the cyclohexanone;

then

(c) supplying at least one interim gas to the reaction zone wherein the interim gas is selected from an inert gas or hydrogen gas and wherein the interim gas contacts the dehydrogenation catalyst at temperatures above about 300°

C.; and

then

(d) recontacting the dehydrogenation catalyst with additional cyclohexanone.

2. The process of claim 1, wherein the contacting step (c) occurs for a period of at least one hour.

3. The process of claim 1, wherein the majority of the contacting step (c) occurs at temperatures between about 350°

C. to about 500°

C. based on contacting time.

4. The process of claim 1, wherein the majority of the contacting step (c) occurs at a temperature of less than 400°

C. and at a pressure of less than 500 kPa and causes at least partial reactivation of the dehydrogenation catalyst.

5. The process of claim 1, wherein the contacting step (c) is conducted at a pressure of from 100 to 1480 kPa for a time of at least 0.5 hours.

6. The process of claim 1, wherein the interim gas is selected from helium gas, nitrogen gas, and argon gas.

7. The process of claim 1, wherein the at least one interim gas is hydrogen gas and wherein the interim gas comprises at least 10 mol % hydrogen.

8. The process of claim 1, wherein the at least one interim gas comprises at least 10 mol % inert gas.

9. The process of claim 1, wherein the process occurs in the absence of oxygen.

10. The process of claim 1, wherein the contacting step (c) is with hydrogen and causes at least partial reactivation of the dehydrogenation catalyst.

11. The process of claim 1, wherein the contacting step (c) causes the activity of the dehydrogenation catalyst to be maintained.

12. The process of claim 1, wherein the dehydrogenation catalyst further comprises at least 0.1 wt % of a metal promoter comprising at least one metal component selected from Group 1 and 2 of Periodic Table of Elements.

13. The process of claim 1, wherein the dehydrogenation catalyst has an oxygen chemisorption of greater than 50%.

14. The process of claim 1, wherein the dehydrogenation component comprises palladium and/or platinum.

15. The process of claim 1 and further comprising:

(e) contacting benzene and hydrogen with a hydroalkylation catalyst under hydroalkylation conditions to convert at least part of the benzene to cyclohexylbenzene;

(f) oxidizing at least part of the cyclohexylbenzene from contacting step (e) to produce cyclohexylbenzene hydroperoxide;

(g) cleaving at least part of the cyclohexylbenzene hydroperoxide from oxidizing step (f) to produce phenol and cyclohexanone; and

(h) feeding at least part of the cyclohexanone and at least part of the phenol from cleaving step (g) to the reaction zone.

16. A process for the dehydrogenation of cyclohexanone to produce phenol, the process comprising:

(a) contacting cyclohexanone in a reaction zone under dehydrogenation conditions with a dehydrogenation catalyst comprising (i) a support comprising silica; and

(ii) a dehydrogenation component comprising at least one metal selected from Group 10 of the Periodic Table of Elements;

(b) terminating contact of the dehydrogenation catalyst with additional cyclohexanone;

then

(c) contacting the dehydrogenation catalyst with hydrogen gas at a temperature of at least 300°

C., a pressure of about 100 to about 3550 kPa, a weight hourly space velocity of about 0.2 to 50 hr<sup>−

1</sup>, and a hydrogen to cyclohexanone molar ratio of about 2 to about 20; and

then

(d) recontacting the dehydrogenation catalyst with additional cyclohexanone.

17. A process for the dehydrogenation of cyclohexanone to produce phenol, the process consisting of:

(a) contacting cyclohexanone in a reaction zone under dehydrogenation conditions with a dehydrogenation catalyst comprising (i) a support comprising silica; and

(ii) a dehydrogenation component comprising at least one metal selected from Group 10 of the Periodic Table of Elements;

(b) terminating contact of the dehydrogenation catalyst with additional cyclohexanone;

then

(c) contacting the dehydrogenation catalyst with hydrogen gas at a temperature of at least 300°

C., a pressure of about 100 to about 3550 kPa, a weight hourly space velocity of about 0.2 to 50 hr<sup>−

1</sup>, and a hydrogen to cyclohexanone molar ratio of about 2 to about 20; and

then

(d) recontacting the dehydrogenation catalyst with additional cyclohexanone.