Process for making phenol and/or cyclohexanone

Patent metadata

Field	Value
Publication number	US-9334218-B2
Application number	US-201314443175-A
Country	US
Kind code	B2
Filing date	Dec 6, 2013
Priority date	Dec 20, 2012
Publication date	May 10, 2016
Grant date	May 10, 2016

Abstract

A cleavage process for making phenol and/or cyclohexanone, the process comprising: (A) providing a feed comprising cyclohexylbenzene hydroperoxide; (B) contacting the feed with a catalyst under cleavage reaction conditions effective to produce a cleavage effluent comprising phenol and cyclohexanone, the catalyst having a collidine uptake of at least 20 μmol per gram of the catalyst and comprising an aluminosilicate molecular sieve of the FAU-type, an oxide binder, and a clay.

First claim

The invention claimed is:

1. A process for making phenol and/or cyclohexanone, the process comprising:
(A) providing a feed comprising cyclohexylbenzene hydroperoxide;
(B) contacting the feed with a catalyst under cleavage reaction conditions effective to produce a cleavage effluent comprising phenol and cyclohexanone, the catalyst having a collidine uptake of at least 20 μmol per gram of the catalyst and comprising an aluminosilicate molecular sieve of the FAU-type, an oxide binder, and a clay.

2. The process of claim 1 , wherein the catalyst comprises the molecular sieve of the FAU-type in a range from 20 wt % to 60 wt %, the oxide binder in a range from 10 wt % to 40 wt %, and the clay in a range from 5 wt % to 30 wt %, all percentages based on the total weight of the catalyst.

3. The process of claim 1 , wherein the catalyst has an n-hexane uptake of at least 20 mg per gram of the catalyst.

4. The process of claim 1 , wherein the catalyst has a maximal TPAD temperature of at least 260° C.

5. The process of claim 1 , wherein the molecular sieve of the FAU-type in the catalyst has a unit cell size in a range from 24.24 to 24.68.

6. The process of claim 1 , wherein the catalyst comprises a FCC catalyst.

7. The process of claim 6 , wherein the catalyst comprises a spent FCC catalyst.

8. The process of claim 7 , wherein before contacting the feed with the catalyst, the catalyst is calcined at a temperature in a range from 500° C. to 1000° C. in an O 2 -containing atmosphere for a period of at least 5 minutes.

9. The process of claim 1 , wherein the catalyst meets at least one of the following requirements:
(r1) comprising vanadium in a range from 0.05 wt % to 1.0 wt %,
(r2) comprising nickel in a range from 0.01 wt % to 0.5 wt %, and
(r3) comprising iron in a range from 0.05 wt % to 1.0 wt %,
where all percentages are based on the total weight of the catalyst.

10. The process of claim 1 , wherein the catalyst comprises a plurality of particles having an average size in a range from 20 μm to 200 μm.

11. The process of claim 10 , wherein at least 50% of the plurality of particles are spheroidal and/or spherical, the percentages based on the total number of the particles.

12. The process of claim 1 , wherein the catalyst is made by a process comprising a spray drying step.

13. The process of claim 1 , wherein the FAU-type molecular sieve has a SiO 2 to Al 2 O 3 molar ratio in a range from 5 to 900.

14. The process of claim 1 , wherein step (B) comprises:
(B-I) mixing the feed with a plurality of particles of the catalyst in a cleavage reactor to obtain a slurry; and
(B-II) separating at least a portion of the slurry to obtain the cleavage effluent and a particle stream comprising the catalyst.

15. The process of claim 14 , wherein step (B) further comprises:
(B-III) recycling at least a portion of the particle stream into step (B-I) as a portion of the source of the plurality of particles of the catalyst.

16. The process of claim 14 , wherein the catalyst has a durability such that at most 2.0 wt % of the catalyst particles having a size over 20 μm are broken down to a size below 20 μm after a continuous operation of 24 hours.

17. The process of claim 14 , wherein step (B) further comprises:
(B-IV) regenerating at least a portion of the catalyst in the particle stream.

18. The process of claim 17 , wherein step (B) further comprises:
(B-V) recycling at least a portion of the regenerated catalyst to step (B-I).

19. The process of claim 17 , wherein step (B-IV) comprises heating the catalyst at a temperature in a range from 400° C. to 800° C. in an O 2 -containing atmosphere.

20. The process of claim 1 , wherein in step (B), the phenol selectivity is Sel(Phen), and the cyclohexanone selectivity is Sel(CHXN), where 0.01≦|(Sel(Phen)−Sel(CHXN))|/Sel(Phen)≦0.10.

21. The process of claim 1 , wherein step (A) comprises:
(A-I) contacting benzene with cyclohexene in the presence of an alkylation catalyst under alkylation conditions effective to produce an alkylation reaction effluent comprising cyclohexylbenzene;
(A-II) contacting at least a portion of the cyclohexylbenzene with an O 2 -containing atmosphere under oxidation conditions effective to produce an oxidation reaction effluent comprising cyclohexylbenzene hydroperoxide; and
(A-III) obtaining the feed from the oxidation reaction effluent.

22. The process of claim 21 , wherein step (A-I) comprises contacting benzene with hydrogen in the presence of a hydroalkylation catalyst under a hydroalkylation condition effective to produce the alkylation reaction effluent.

23. The process of claim 1 , wherein in step (B), the amount of the catalyst is in a range from 0.1 wt % to 20 wt % based on the weight of the feed.

Assignees

• Exxonmobil Chem Patents Inc

Inventors

• Wang Kun
• Garcia Roberto
• Helton Terry E
• Nair Hari
• Smith Charles Morris

Classifications

• C07C407/00

  Preparation of peroxy compounds · CPC title

• C07C37/08 Primary

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

• C07C2601/14

  The ring being saturated · CPC title

• C07C45/53 Primary

  of hydroperoxides · CPC title

• C07C2/74

  by addition with simultaneous hydrogenation · CPC title