Hydroalkylating process comprising an activation of the hydroalkylation catalyst and method of making phenol and cyclohexanone

Patent metadata

Field	Value
Publication number	US-9718744-B2
Application number	US-201415023123-A
Country	US
Kind code	B2
Filing date	Sep 26, 2014
Priority date	Oct 18, 2013
Publication date	Aug 1, 2017
Grant date	Aug 1, 2017

Abstract

Disclosed is a hydroalkylation process in which the hydroalkylation catalyst is activated in the presence of a flowing fluid comprising hydrogen and a condensable agent. The presence of the condensable agent enables fast, effective activation of the hydroalkylation catalyst precursor in a cost-effective manner. It also yields superior catalyst performance.

First claim

The invention claimed is:

1. A hydroalkylation process, the process comprising:
(I) providing a catalyst precursor comprising a solid acid and a hydrogenation metal;
(II) treating the catalyst precursor under activation conditions in the presence of hydrogen and a condensable agent comprising a hydrocarbon compound to produce an activated catalyst, wherein the molar ratio of hydrogen to the condensable agent is at least 3.0, wherein the activation conditions comprise treating the catalyst precursor at a temperature in a range from 130° C. to 250° C. for a period in a range from 0.5 hour to 48 hours; and subsequently
(III) contacting the activated catalyst with a first aromatic compound and hydrogen under hydroalkylation conditions to produce a hydroalkylation product comprising an alkylated aromatic compound.

2. The process of claim 1 , wherein in step (II), at least a part of the condensable agent is in liquid state.

3. The process of claim 1 , wherein the hydrocarbon compound in the condensable agent has a structure represented by the following formula (F-I):

where:
R 1 , the same or different at each occurrence, each independently represents a substituted or unsubstituted linear, branched acyclic, or cyclic alkyl or alkenyl group having from 1 to 20 carbon atoms; and
m is an integer from 0 to 5.

4. The process of claim 1 , wherein the condensable agent comprises the first aromatic compound.

5. The process of claim 1 , wherein step (II) comprises treating the catalyst precursor at a temperature in the range from Tmax−20° C. to Tmax for a period in a range from 0.5 hour to 48 hours, where Tmax is the highest temperature the catalyst precursor is subjected to in step (II).

6. The process of claim 5 , wherein Tmax is in a range from 140° C. to 250° C.

7. The process of claim 1 , wherein the molar ratio of hydrogen to the condensable agent in step (II) is at least 4.0.

8. The process of claim 1 , wherein the molar ratio of hydrogen to the first aromatic compound in step (III) is in a range from 0.1 to 0.9.

9. The process of claim 1 , wherein the first aromatic compound has a structure represented by the following formula (F-II):

where:
R 2 , the same or different at each occurrence, each independently represents a substituted or unsubstituted linear, branched acyclic, or cyclic alkyl or alkenyl group having from 1 to 20 carbon atoms; and
n is an integer from 1 to 5.

10. The process of claim 9 , wherein the first aromatic compound is selected from benzene, toluene, ethylbenzene, n-propylbenzene, cumene, n-butylbenzene, 2-phenylbutane, o-xylene, m-xylene, p-xylene, and mixtures thereof.

11. The process of claim 9 , wherein the alkylated aromatic compound has a structure represented by the following formula (F-III):

where:
R 3 and R 4 , the same or different at each occurrence, each independently represents a substituted or unsubstituted linear, branched acyclic, or cyclic alkyl or alkenyl having from 1 to 20 carbon atoms; and
o and p are independently integers from 0 to 5.

12. The process of claim 11 , wherein the alkylated aromatic compound is selected from:
cyclohexylbenzene;
dicyclohexylbenzene;
tricyclohexylbenzene;
methylcyclohexyltoluene;
methylcyclohexyl-ethylbenzene;
ethylcyclohexyl-ethylbenzene;
propylcyclohexyl-propylbenzene;
butylcyclohexyl-butylbenzene;
dimethylcyclohexyl-dimethylbenzene;
diethylcyclohexyl-diethylbenzene;
trimethylcyclohexyl-trimethylbenzene;
isopropylcyclohexylcumene; and
methylethylcyclohexyl-methylethylbenzene.

13. The process of claim 11 , wherein the alkylated aromatic compound is cyclohexylbenzene, and the first aromatic compound is benzene.

14. The process of claim 1 , wherein in step (I), the solid acid comprises a molecular sieve.

15. The process of claim 14 , wherein the molecular sieve is of MCM-22 type.

16. The process of claim 1 , wherein the hydrogenation metal in the catalyst precursor comprises at least one of Re, Ru, Os, Rh, Ir, Ni, Pd, and Pt.

17. The process of claim 1 , wherein the catalyst precursor comprises an inorganic oxide support component.

18. The process of claim 17 , wherein the inorganic oxide support component comprises at least one of alumina, silica, zirconia, and titania.

19. The process of claim 1 , wherein the contacting step (III) is conducted at a temperature in a range from 90° C. to 180° C., and a pressure in a range from 100 kPa to 5000 kPa.

20. The process of claim 1 , wherein in the contacting step (III), at least a portion of the first aromatic compound is in liquid phase.

21. The process of claim 1 , wherein the contacting step (III) is conducted at a space velocity of 0.5 to 15.0 grams of the first aromatic compound per gram of the activated catalyst per hour.

22. A process for making phenol and/or cyclohexanone, the process comprising:
(A) producing cyclohexylbenzene by:
(AI) supplying hydrogen and benzene into a hydroalkylation reactor;
(AII) contacting the hydrogen and benzene with a hydroalkylation catalyst produced by a process according to claim 1 ;

(B) oxidizing at least a portion of the cyclohexylbenzene to obtain an oxidation product comprising cyclohexylbenzene hydroperoxide; and
(C) subjecting at least a portion of the cyclohexylbenzene hydroperoxide in the oxidation product to cleavage to obtain a cleavage product comprising phenol and cyclohexanone.

Assignees

• Exxonmobil Chemical Patents Inc

Inventors

• Kiss Gabor
• Green Thomas E
• Kuechler Keith H

Classifications

• C07C2529/74

  Noble metals · CPC title

• B01J29/7676

  MWW-type, e.g. MCM-22, ERB-1, ITQ-1, PSH-3 or SSZ-25 · CPC title

• B01J2229/186

  not in framework positions · CPC title

• C07C45/53

  of hydroperoxides · CPC title

• B01J38/10

  using elemental hydrogen · CPC title