Process and apparatus for making phenol and/or cyclohexanone

Patent metadata

Field	Value
Publication number	US-9409841-B2
Application number	US-201414779131-A
Country	US
Kind code	B2
Filing date	Mar 24, 2014
Priority date	Apr 2, 2013
Publication date	Aug 9, 2016
Grant date	Aug 9, 2016

Abstract

A process for producing phenol and/or cyclohexanone by cleaving cyclohexylbenzene hydroperoxide in a loop cleavage reactor comprising multiple reaction zones connected in series. In desirable embodiments, fresh cyclohexylbenzene hydroperoxide feed(s) are supplied to reaction zones the final reaction zone, and fresh acid catalyst is supplied only to the final reaction zone. In desirable embodiments, a portion of the effluent exiting the final reaction zone is recycled to the first reaction zone. Each reaction zone is equipped with a heat exchanger downstream of the feed port to extract heat generated from the cleavage reaction.

First claim

The invention claimed is:

1. A process for making phenol and/or cyclohexanone, the process comprising:
(A) providing a cleavage reactor having a plurality of reaction zones connected in series, the reaction zones comprising a first reaction zone, a final reaction zone and optionally one or more intermediate reaction zone(s) between the first reaction zone and the final reaction zone; wherein:
each of the reaction zones comprises a processed feed port, a fresh feed port, a heat exchanger at least partly downstream of the processed feed port and the fresh feed port in the same reaction zone, and an effluent port, except that the heat exchanger for the final reaction zone is optional;
the effluent port of any given reaction zone other than the final reaction zone is in fluid communication with the processed feed port of the immediately following reaction zone in the series; and
the effluent port of the final reaction zone is in fluid communication with the processed feed port of the first reaction zone;
(B) supplying a fresh reaction feed comprising cyclohexylbenzene hydroperoxide to each reaction zone other than the final reaction zone via the fresh feed port of the reaction zone and producing an effluent at the effluent port of the reaction zone;
(C) supplying at least a portion of the effluent exiting the effluent port of each of the reaction zones other than the final reaction zone to the processed feed port of the immediately following reaction zone in the series;
(D) supplying an acid catalyst feed to the final reaction zone via the fresh feed port of the final reaction zone and producing a final effluent exiting the effluent port of the final reaction zone;
(E) recycling a portion of the final effluent to the first reaction zone via the processed feed port of the first reaction zone; and
(F) obtaining phenol and/or cyclohexanone from a portion of the final effluent.

2. The process of claim 1 , wherein all of the acid catalyst present in all of the reaction zones other than the final reaction zone is supplied from the final effluent.

3. The process of claim 1 , wherein all of the cyclohexylbenzene hydroperoxide in the final reaction zone is supplied from the effluent from the reaction zone immediately preceding the final reaction zone.

4. The process of claim 1 , wherein the final reaction zone comprises a final heat exchanger at least partly downstream of the processed feed port and the fresh feed port in the same reaction zone.

5. The process of claim 1 , wherein in step (B), the fresh reaction feed comprises 10-90 wt % cyclohexylbenzene hydroperoxide, 0-30% phenol, 0-30% cyclohexanone, and 0-40 wt % cyclohexylbenzene, all percentages being based on the total weight of the fresh reaction feed.

6. The process of claim 1 , wherein the final effluent comprises at most 1000 ppm of cyclohexylbenzene hydroperoxide.

7. The process of claim 1 , wherein in the effluent exiting any given reaction zones, the concentration of the acid catalyst is from 5 to 1000 ppm based on the total weight of the effluent of the given reaction zone.

8. The process of claim 1 , wherein the effluent exiting any given reaction zone independently has a phenol concentration in the range from 10 wt % to 50 wt % and a cyclohexanone concentration in the range from 10 wt % to 50 wt %, the percentages being based on the total weight of the effluent exiting the given reaction zone.

9. The process of claim 1 , wherein the effluent exiting the reaction zone immediately preceding the final reaction zone has a cyclohexylbenzene hydroperoxide concentration of from 1 to 1000 ppm, based on the total weight of the effluent of the reaction zone.

10. The process of claim 1 , wherein the final effluent has a cyclohexylbenzene hydroperoxide concentration in the range from 1 to 100 ppm, based on the total weight of the effluent exiting the given reaction zone.

11. The process of claim 1 , wherein the effluent exiting any given reaction zone independently has a phenol to cyclohexanone molar ratio in the range from 0.80 to 8.00.

12. The process of claim 1 , wherein the cleavage reactor comprises from 3 to 50 reaction zones.

13. The process of claim 1 , wherein the temperature of the reaction medium in any given reaction zone is controlled within the range from 15° C. to 80° C.

14. The process of claim 1 , wherein the temperature variation of the reaction medium at a given point of time in any given reaction zone is ΔT ° C., where ΔT≦20.

15. The process of claim 1 , wherein in a given period time, the weight of the portion of the final effluent recycled to the first reaction zone is W1, the total weight of the final effluent is W2, and W1/W2 is in a range from 0.10 to 0.98.

16. The process of claim 1 , wherein:
in the final reaction zone, the residence time of the reaction medium is Tf;
in each reaction zone other than the final reaction zone, the residence time of the reaction medium is independently To; and
Tf/To is from 0.1 to 20.

17. The process of claim 1 , wherein the acid catalyst feed comprises at least one of sulfuric acid, sulfonic acid, p-toluene sulfonic acid, perchloric acid, hydrochloric acid, phosphoric acid, aluminum chloride, oleum, ferric chloride, boron trifluoride, sulfur dioxide, and sulfur trioxide.

18. The process of claim 1 , wherein the acid catalyst feed comprises sulfuric acid at a concentration of at least 90 wt %, based on the total weight of the acid catalyst feed.

19. The process of claim 1 , wherein the acid catalyst feed further comprises phenol at a concentration of 1 wt % to 40 wt %, the percentage based on the total weight of the acid catalyst feed.

20. The process of claim 1 , wherein the cyclohexylbenzene hydroperoxide is produced by a process comprising:
(i) contacting benzene and hydrogen with a catalyst under hydroalkylation conditions to produce a hydroalkylation effluent comprising cyclohexylbenzene; and
(ii) oxidizing at least a portion of the cyclohexylbenzene to produce an oxidation effluent comprising cyclohexylbenzene hydroperoxide.

21. A cleavage reactor having a plurality of reaction zones connected in series, the reaction zones comprising a first reaction zone, a final reaction, and optionally one or more intermediate reaction zone(s) between the first reaction zone and the final reaction zone, wherein:
each of the reaction zones comprises a processed feed port, a fresh feed port, a heat exchanger at least partly downstream of the processed feed port and the fresh feed port in the same reaction zone, and an effluent port;
the effluent port of any given reaction zone other than the final reaction zone is in fluid communication with the processed feed port of the immediately following reaction zone in the series;
the effluent port of the final reaction zone is in fluid communication with the processed feed port of the first reaction zone;
the final reaction zone comprises an outlet downstream of the effluent port thereof for withdrawing a portion of the final effluent exiting the final reaction zone;
the fresh feed port of each of the reaction zone(s) except the final reaction zone is in fluid communication with a source of cyclohexylbenzene hydroperoxide; and
the fresh feed port of the final reaction zone is in fluid communication with a source of an acid catalyst.

22. The cleavage reactor of claim 21 comprising from 3 to 50 reaction zones in total.

23. The cleavage reactor of claim 21 , wherein:
all of the reaction zones comprise a flui

Assignees

• Exxonmobil Chemical Patents Inc

Inventors

• Davis Jason D
• Becker Christopher L
• Patel Bryan A
• Coleman John S
• Nair Hari

Classifications

• C07C37/08 Primary

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

• C07C45/53

  of hydroperoxides · CPC title

• B01J2219/00103

  in a heat exchanger separate from the reactor · CPC title

• C07C407/00

  Preparation of peroxy compounds · CPC title

• C07C39/04

  Phenol · CPC title