Activation of dehydrogenation catalysts

Patent metadata

Field	Value
Publication number	US-9758447-B2
Application number	US-201514878753-A
Country	US
Kind code	B2
Filing date	Oct 8, 2015
Priority date	Oct 24, 2014
Publication date	Sep 12, 2017
Grant date	Sep 12, 2017

Abstract

In a process for dehydrogenating cyclohexylbenzene and/or alkyl-substituted cyclohexylbenzene compounds, a dehydrogenation catalyst comprising at least one Group 10 metal compound on a support is heated in the presence of hydrogen from a first temperature from 0° C. to 200° C. to a second, higher temperature from 60° C. to 500° C. at a ramp rate no more than 100° C./hour. The dehydrogenation catalyst is contacted with hydrogen at the second temperature for a time from 3 to 300 hours to produce an activated dehydrogenation catalyst. A feed comprising cyclohexylbenzene and/or an alkyl-substituted cyclohexylbenzene compound is then contacted with hydrogen in the presence of the activated dehydrogenation catalyst under conditions effective to produce a dehydrogenation reaction product comprising biphenyl and/or an alkyl-substituted biphenyl compound.

First claim

What is claimed is:

1. A process for dehydrogenating cyclohexylbenzene and/or alkyl-substituted cyclohexylbenzene compounds, the process comprising:
(a) providing a dehydrogenation catalyst comprising at least one Group 10 metal compound on a support;
(b) heating the dehydrogenation catalyst in the presence of hydrogen from a first temperature from 0° C. to 200° C. to a second, higher temperature from 60° C. to 500° C. at a ramp rate of no more than 100° C./hour;
(c) contacting the dehydrogenation catalyst with hydrogen at the second temperature for a time from 3 to 300 hours to produce an activated dehydrogenation catalyst; and
(d) contacting a feed comprising cyclohexylbenzene and/or an alkyl-substituted cyclohexylbenzene compound with hydrogen in the presence of the activated dehydrogenation catalyst under conditions effective to produce a dehydrogenation reaction product comprising biphenyl and/or an alkyl-substituted biphenyl compound.

2. The process of claim 1 , wherein the at least one Group 10 metal comprises platinum.

3. The process of claim 1 , wherein the dehydrogenation catalyst comprises from 0.1 to 5wt % of elemental platinum.

4. The process of claim 1 , wherein the dehydrogenation catalyst further comprises a tin compound.

5. The process of claim 4 , wherein the tin compound comprises tin chloride or tin tartrate.

6. The process of claim 1 , wherein the dehydrogenation catalyst comprises from 0.1 to 5 wt % of elemental tin.

7. The process of claim 1 further comprising the following steps prior to the providing (a):
(i) treating the support with a solution containing the Group 10 metal compound in a solvent; and
(ii) removing the solvent from the treated support to produce the hydrogenation catalyst on the support provided in (a).

8. The process of claim 1 , wherein the ramp rate during the heating (b) is from 0.5° C./hour to 100° C./hour.

9. The process of claim 1 , wherein the ramp rate during the heating (b) is from 0.5° C./hour to 50° C./hour.

10. The process of claim 1 , wherein the ramp rate during the heating (b) is from 1° C./hour to 20° C./hour.

11. The process of claim 1 , wherein hydrogen is supplied to the dehydrogenation catalyst at least during the contacting (c) at a rate of 10 to 300 sccm/g of catalyst.

12. The process of claim 1 , wherein the conditions in the contacting (d) include a hydrogen to hydrocarbon molar ratio in excess of 2.

13. The process of claim 1 , wherein the conditions in the contacting (d) include a temperature from 200° C. to 500° C. and a pressure from 100 kPa to 1600 kPa-a.

14. The process of claim 1 , wherein the feed comprises less than 0.1 wt % of dicyclohexylbenzene compounds.

15. The process of claim 1 , wherein the feed comprises cyclohexylbenzene produced by the hydroalkylation of benzene.

16. The process of claim 1 , wherein the feed comprises (methylcyclohexyl)toluene produced by the hydroalkylation of toluene.

17. The process of claim 1 , wherein the feed comprises dimethylcyclohexylxylenes from the hydroalkylation of xylenes.

18. The process of claim 1 , wherein the feed comprises methylcyclohexylbenzene and/or cyclohexyltoluene produced from the hydroalkylation of toluene and benzene or the transalkylation of cyclohexylbenzene with toluene.

19. The process of claim 1 , wherein the feed also contains up to 90 wt % benzene or cyclohexane.

20. The process of claim 1 , wherein the feed also contains up to 90 wt % alkylated benzene or alkylated cyclohexane.

21. The process of claim 1 , wherein the feed also contains up to 90 wt % toluene and/or methylcyclohexane.

22. The process of claim 1 , wherein the second temperature is at least 100° C. higher than the first temperature in (b).

23. The process of claim 1 , wherein the support is selected from the group consisting of alumina, silica, silica-alumina, titania, calcium oxide, strontium oxide, barium oxide, magnesium oxide, carbon, zirconia, diatomaceous earth, lanthanide oxides including cerium oxide, lanthanum oxide, neodynium oxide, yttrium oxide and praesodynium oxide, oxides of chromium, thorium, uranium, niobium and tantalum, tin oxide, zinc oxide, and aluminum phosphate.

24. The process of claim 1 , wherein the conditions in the contacting (d) include a hydrogen to hydrocarbon molar ratio of at least 4.

25. The process of claim 1 , wherein the feed of (d) comprises less than 0.1 wt % of dicyclohexylbenzene.

Assignees

• Exxonmobil Chemical Patents Inc

Inventors

• Dakka Jihad M
• Decaul Lorenzo C
• De Martin Gregory J
• Salciccioli Michael
• Sangar Neeraj
• Pavlish Aaron B
• Kheir Ali A
• Mohr Gary D

Classifications

• C07C2523/14

  of germanium, tin or lead · CPC title

• C07C2521/04

  Alumina · 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

• C07C2529/74

  Noble metals · CPC title

• B01J2229/186

  not in framework positions · CPC title