Cyclohexanone dehydrogenation catalyst and process

• US 9,061,270 B2
• Filed: 12/17/2010
• Issued: 06/23/2015
• Est. Priority Date: 02/05/2010
• Status: Active Grant

• Current Assignee: ExxonMobil Chemical Patents Inc. (Exxon Mobil Corporation)
• Original Assignee: ExxonMobil Chemical Patents Inc. (Exxon Mobil Corporation)
• Inventors: Xu, Teng, Helton, Terry E., Dakka, Jihad M., Chen, Tan-Jen, Miseo, Sabato, Decaul, Lorenzo C., Lemon, Edward A. Jr.
• Primary Examiner(s): Zucker, Paul A
• Assistant Examiner(s): LUDERER, MARK R
• Application Number:
  US13/520,467
• Publication Number:
  US 20130090499A1
• Time in Patent Office: 1,649 Days
• Field of Search: 568/798, 568/799, 585/430
• US Class Current: 1/1
• CPC Class Codes: B01J 21/08 Silica
• CPC Class Codes: B01J 23/58 with alkali- or alkaline earth metals
• CPC Class Codes: B01J 37/0205 in several steps
• CPC Class Codes: B01J 37/12 Oxidising
• 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 2529/70 of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65
• CPC Class Codes: C07C 2601/14 The ring being saturated
• CPC Class Codes: C07C 37/06 by conversion of non-aromatic six-membered rings or of such rings formed in situ into aromatic six-membered rings, e.g. by dehydrogenation
• 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

A catalyst composition comprising: (i) a support; (ii) a first component comprising at least one metal component selected from Group 1 and Group 2 of the Periodic Table of Elements; and (iii) a second component comprising at least one metal component selected from Groups 6 to 10 of the Periodic Table of Elements, wherein the catalyst composition exhibits an oxygen chemisorption of greater than 50%.

Claims

1. A process for the dehydrogenation of at least one dehydrogenatable compound selected from a ketone and a hydrocarbon consisting of hydrogen and carbon, the process comprising contacting a feed comprising the at least one dehydrogenatable compound with a catalyst comprising an inorganic oxide support, a first component comprising at least one metal component selected from Group 1 and Group 2 of the Periodic Table of Elements, and a second component comprising at least one metal component selected from Groups 6 to 10 of the Periodic Table of Elements under dehydrogenation conditions effective to convert at least part of the at least one dehydrogenatable compound in the feed, wherein the catalyst is produced by a method comprising:

(a) treating the support with the first component;

(b) calcining the treated support at a temperature of about 100°

C. to about 700°

C.;

(c) impregnating the support with the second component; and

(d) calcining the impregnated support at a temperature of about 100°

C. to about 700°

C.,

wherein the impregnating (c) is effected after or at the same time as the treating (a).

2. The process of claim 1, wherein the inorganic support is at least one material selected from silica, a silicate, and an aluminosilicate.

3. The process of claim 1, wherein the inorganic support comprises silica.

4. The process of claim 1, wherein the second component comprises at least one metal component selected from platinum and palladium.

5. The process of claim 1, wherein the first component comprises a metal component comprising potassium.

6. The process of claim 1, wherein the calcining (b) is conducted in an oxygen-containing atmosphere.

7. The process of claim 1, wherein the calcining (d) is conducted in an oxygen-containing atmosphere.

8. The process of claim 1, 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-containing feed molar ratio of about 2 to about 20.

19. The process of claim 1, wherein the at least one dehydrogenatable compound is selected from:

cyclopropane, cyclopentane, methyl cyclopentane, cyclobutane, cyclopentene, cyclodecane, cyclohexane, methylcyclohexane, cyclododecane, cyclohexane, and cyclohexanone.

9. A process for producing phenol from benzene, the process comprising:

(i) contacting benzene and hydrogen with a catalyst under hydroalkylation conditions to produce cyclohexylbenzene;

(ii) oxidizing cyclohexylbenzene from the contacting (i) to produce cyclohexylbenzene hydroperoxide;

(iii) converting cyclohexylbenzene hydroperoxide from the oxidizing (ii) to produce an effluent steam comprising phenol and cyclohexanone; and

(iv) contacting at least a portion of the effluent stream with a catalyst comprising an inorganic oxide support, a first component comprising at least one metal component selected from Group 1 and Group 2 of the Periodic Table of Elements, and a second component comprising at least one metal component selected from Groups 6 to 10 of the Periodic Table of Elements under dehydrogenation conditions effective to convert at least part of the cyclohexanone in the feed into phenol and hydrogen, wherein the catalyst is produced by a method comprising;

(a) treating the support with the first component;

(b) calcining the treated support at a temperature of about 100°

C. to about 700°

C.;

(c) impregnating the support with the second component; and

(d) calcining the impregnated support at a temperature of about 100°

C. to about 700°

C.,

wherein the impregnating (c) is effected after or at the same time as the treating (a).

10. The process of claim 9, wherein the inorganic support is selected from at least one material selected from silica, a silicate, and an aluminosilicate.

11. The process of claim 9, wherein the inorganic support comprises silica.

12. The process of claim 9, wherein the second component comprises at least one metal component selected from platinum and palladium.

13. The process of claim 9, wherein the first component comprises a metal component comprising potassium.

14. The process of claim 9, wherein the calcining (b) is conducted in an oxygen-containing atmosphere.

15. The process of claim 9, wherein the calcining (d) is conducted in an oxygen-containing atmosphere.

16. The process of claim 9, 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 about 50 hr<sup>−

1</sup>, and a hydrogen to cyclohexanone-containing feed molar ratio of about 2 to about 20.

17. The process of claim 9, wherein the effluent portion also comprises at least one compound selected from cyclohexanol, cyclohexenol, cyclohexenone and phenol.

18. The process of claim 9, and further comprising:

(v) recycling at least part of the hydrogen produced in the contacting (iv) to the contacting (i).