Dehydrogenation process

Patent metadata

Field	Value
Publication number	US-9469580-B2
Application number	US-201314435670-A
Country	US
Kind code	B2
Filing date	Nov 18, 2013
Priority date	Dec 17, 2010
Publication date	Oct 18, 2016
Grant date	Oct 18, 2016

Abstract

Disclosed herein is a process for dehydrogenating a hydrocarbon with a dehydrogenation catalyst comprising a step of activating the catalyst precursor in a H 2 -containing atmosphere. A particularly advantageous activation process includes heating the catalyst precursor to a temperature in a range from 400° C. to 600° C. The process of the present disclosure is particularly advantageous for dehydrogenating cyclohexane to make benzene.

First claim

The invention claimed is:

1. A dehydrogenation process, the process comprising:
(1A) providing a catalyst precursor comprising (i) an inorganic support, and (ii) 0.01 wt % to 10.0 wt % of a first metal selected from the Groups 6 to 10 metals of the Periodic Table of Elements based on the total weight of the catalyst precursor;
(1B) obtaining an activated dehydrogenation catalyst by treating the catalyst precursor at a temperature in a range from 450° C. to 600° C. for a period of at least 15 minutes in a H 2 -containing atmosphere; and
(1C) contacting a first composition comprising cyclohexane with the activated dehydrogenation catalyst in a dehydrogenation reactor under a dehydrogenation condition to convert at least a portion of the cyclohexane to benzene and obtain a dehydrogenation reaction product.

2. The process of claim 1 , wherein the temperature of step (1B) is in a range from 450° C. to 550° C.

3. The process of claim 1 , wherein the first composition in step (1C) is obtained by:
(1Ba) contacting benzene and hydrogen with a hydroalkylation catalyst under a hydroalkylation condition to form a hydroalkylation reaction mixture comprising cyclohexylbenzene, cyclohexane, methylcyclopentane, and benzene; and
(1Bb) obtaining from at least a portion of the hydroalkylation reaction mixture (i) a first composition that has a higher concentration of at least one of benzene and cyclohexane than cyclohexylbenzene; and (ii) a second composition that has a higher concentration of cyclohexylbenzene than benzene and cyclohexane.

4. The process of claim 3 , further comprising:
(1D) recycling at least a portion of the benzene in the dehydrogenation reaction product to step (1Ba).

5. The process of claim 1 , wherein the first metal comprises Pt and/or Pd.

6. The process of claim 1 , wherein at least a portion of the first metal in the catalyst precursor in step (1A) is in an oxidation state higher than zero.

7. The process of claim 1 , wherein the catalyst precursor further comprises at least one of: (iii) from 0.01 wt % to 5.0 wt % of a second metal selected from Group 14 of the Periodic Table of Elements; and (iv) from 0.01 wt % to 10.0 wt % of a third metal selected from the Groups 1 and 2 metals of the Periodic Table of Elements.

8. The process of claim 7 , wherein the second metal comprises Sn and the third metal comprises K.

9. The process of claim 1 , wherein in step (1B), the H 2 -containing atmosphere comprises at least 90 wt % of hydrogen.

10. The process of claim 1 , wherein step (1B) comprises treating the catalyst precursor in a flowing stream of H 2 -containing atmosphere.

11. The process of claim 1 , wherein the H 2 -containing atmosphere in step (1B) has a benzene concentration of at most 1 wt %, based on the total weight of the H 2 -containing atmosphere.

12. The process of claim 3 , wherein in step (1Bb) the first composition further comprises hydrogen, and in step (1B) the H 2 -containing atmosphere is the first composition.

13. The process of claim 1 , wherein after step (1B) but before step (1C), the activated dehydrogenation catalyst is protected by a protective atmosphere free of O 2 .

14. The process of claim 13 , wherein the protective atmosphere comprises at least one of H 2 and CH 4 .

15. The process of claim 1 , wherein step (1A) comprises:
(1A-1) providing the inorganic support;
(1A-2) impregnating the inorganic support with a solution of a salt of the first metal to obtain an impregnated support; and
(1A-3) calcining the impregnated support at a temperature in a range from 300° C. to 1000° C.

16. The process of claim 1 , wherein steps (1B) and (1C) are both conducted in the dehydrogenation reactor.

17. The process of claim 1 , wherein in step (1Ba) the first composition comprises benzene and hydrogen.

18. The process of claim 1 , wherein in step (1C), the first composition comprises 0.01 wt % to 5.0 wt % methylcyclopentane based on the total weight of the first composition, and at least a portion of the methylcyclopentane is converted into a paraffin.

19. The process of claim 1 , wherein in step (1C), the dehydrogenation condition comprises a temperature in a range from 300° C. to 600° C.

20. A process for making phenol and/or cyclohexanone, the process comprising:
(2A) producing cyclohexylbenzene from the second composition obtained in step (1Bb) according to the process of claim 3 ;
(2B) oxidizing at least a portion of the cyclohexylbenene to obtain an oxidation reaction product comprising cyclohexylbenzene hydroperoxide; and
(2C) cleaving at least a portion of the cyclohexylbenzene hydroperoxide to produce a cleavage reaction product comprising phenol and cyclohexanone.

Assignees

• Exxonmobil Chemical Patents Inc

Inventors

• Chen Tan-Jen
• Becker Christopher L
• Nair Hari
• Benitez Francisco M
• Smith Charles Morris

Classifications

• C07C2523/14

  of germanium, tin or lead · CPC title

• C07C37/08

  by decomposition of hydroperoxides, e.g. cumene hydroperoxide · CPC title

• C07C5/367 Primary

  Formation of an aromatic six-membered ring from an existing six-membered ring, e.g. dehydrogenation of ethylcyclohexane to ethylbenzene · CPC title

• C07C37/60

  by oxidation reactions introducing directly hydroxy groups on a =CH-group belonging to a six-membered aromatic ring with the aid of other oxidants than molecular oxygen or their mixtures with molecular oxygen · CPC title

• C07C407/00

  Preparation of peroxy compounds · CPC title