Process for making cyclohexanone

Patent metadata

Field	Value
Publication number	US-10053408-B2
Application number	US-201515504217-A
Country	US
Kind code	B2
Filing date	Aug 3, 2015
Priority date	Sep 30, 2014
Publication date	Aug 21, 2018
Grant date	Aug 21, 2018

Abstract

Disclosed are processes for making cyclohexanone from a mixture comprising phenol, cyclohexanone, cyclohexylbenzene, and an S-containing component, comprising a step of removing at least a portion of the S-containing component to reduce poisoning of a hydrogenation catalyst used for hydrogenating phenol to cyclohexanone.

First claim

The invention claimed is:

1. A process for making cyclohexanone, the process comprising:
(Ia) providing a crude mixture comprising cyclohexanone, phenol, cyclohexylbenzene, and an S-containing component;
(Ib) contacting the crude mixture with an anterior sorbent capable of removing at least a portion of the S-containing component to obtain a first mixture comprising cyclohexanone, phenol, and cyclohexylbenzene;
(Ic) feeding the first mixture into a first distillation column;
(II) obtaining from the first distillation column:
a first upper effluent comprising cyclohexanone at a concentration higher than the first mixture;
a first middle effluent comprising phenol at a concentration higher than the first mixture, cyclohexanone, cyclohexylbenzene, and bicyclohexane; and
a first lower effluent comprising cyclohexylbenzene at a concentration higher than the first mixture;
(III) providing hydrogen and at least a portion of the first middle effluent as at least a portion of a hydrogenation feed to a hydrogenation reaction zone;
(IV) contacting the hydrogenation feed with hydrogen in the hydrogenation reaction zone where phenol reacts with hydrogen in the presence of a hydrogenation catalyst under hydrogenation reaction conditions to obtain a hydrogenation reaction product comprising cyclohexanone at a concentration higher than the hydrogenation feed, phenol at a concentration lower than the hydrogenation feed, cyclohexylbenzene, and bicyclohexane; and
(V) feeding at least a portion of the hydrogenation reaction product into the first distillation column.

2. The process of claim 1 , wherein the anterior sorbent in step (Ib) comprises a solid-phase basic material selected from: (i) oxides of alkali metals, alkaline earth metals, and zinc; (ii) hydroxides of alkali metals, alkaline earth metals, and zinc; (iii) carbonates of alkali metals, alkaline earth metals, and zinc; (iv) bicarbonates of alkali metals, alkaline earth metals, and zinc; (v) complexes of two or more of (i), (ii), (iii), and (iv); (vi) solid amines; (vii) ion-exchange resins; and (viii) mixtures and combinations of two or more thereof.

3. The process of claim 1 , wherein the S-containing component comprises SO 3 , HSO 4 − , R—HSO 4 and/or sulfuric acid.

4. The process of claim 1 , wherein the concentration of the S-containing component in the crude mixture is in a range from 10 ppm to 10,000 ppm by weight based on the total weight of the crude mixture.

5. The process of claim 1 , wherein the concentration of the S-containing component in the first middle effluent is in a range from 1 ppm to 1,000 ppm by weight based on the total weight of the first middle effluent.

6. The process of claim 1 , wherein the concentration of the S-containing component in the hydrogenation feed is at most 100 ppm by weight based on the total weight of the hydrogenation feed.

7. The process of claim 1 , wherein the concentration of the S-containing component in the hydrogenation feed based on the total weight of the hydrogenation feed is at most 10% of the concentration of the S-containing component in the crude mixture based on the total weight of the crude mixture.

8. The process of claim 1 , wherein the first upper effluent comprises the sulfur-containing component at a concentration of no greater than 50 ppm by weight, based on the total weight of the first upper effluent.

9. The process of claim 1 , wherein step (III) comprises:
(IIIa) contacting at least a portion of the first middle effluent with a posterior sorbent capable of removing at least a portion of the S-containing component to obtain the hydrogenation feed.

10. The process of claim 9 , wherein the posterior sorbent comprises a solid-phase basic material selected from: (i) oxides of alkali metals, alkaline earth metals, and zinc; (ii) hydroxides of alkali metals, alkaline earth metals, and zinc; (iii) carbonates of alkali metals, alkaline earth metals, and zinc; (iv) bicarbonates of alkali metals, alkaline earth metals, and zinc; (v) complexes of two or more of (i), (ii), (iii), and (iv); (vi) solid amines; (vii) ion-exchange resins; and (viii) mixtures and combinations of two or more thereof.

11. The process of claim 1 , wherein the first distillation column operates at a temperature of at least 120° C.

12. The process of claim 1 , wherein the first distillation column operates at a temperature higher than the disassociation temperature of at least one of the following: (i) 1,5-pentane diamine sulfuric acid complex; (ii) 1-methyl-1,5-pentane diamine sulfuric acid complex; and (iii) 1,6-hexane diamine sulfuric acid complex.

13. The process of claim 9 , wherein the concentration of the S-containing component in the hydrogenation feed based on the total weight of the hydrogenation feed is at most 10% of the concentration of the S-containing component in the first middle effluent based on the total weight of the first middle effluent.

14. A process for making cyclohexanone, the process comprising:
(I) feeding a first mixture comprising cyclohexanone, phenol, cyclohexylbenzene, and an S-containing component into a first distillation column;
(II) obtaining from the first distillation column:
a first upper effluent comprising cyclohexanone at a concentration higher than the first mixture;
a first middle effluent comprising phenol at a concentration higher than the first mixture, cyclohexanone, cyclohexylbenzene, bicyclohexane, and a portion of the S-containing component; and
a first lower effluent comprising cyclohexylbenzene at a concentration higher than the first mixture;
(III) removing at least a portion of the S-containing component from the first middle effluent to obtain a hydrogenation feed;
(IV) feeding at least a portion of the hydrogenation feed and hydrogen into a hydrogenation reaction zone where phenol reacts with hydrogen in the presence of a hydrogenation catalyst under hydrogenation reaction conditions to obtain a hydrogenation reaction product comprising cyclohexanone at a concentration higher than the hydrogenation feed, phenol at a concentration lower than the hydrogenation feed, cyclohexylbenzene, and bicyclohexane; and
(V) feeding at least a portion of the hydrogenation reaction product into the first distillation column.

15. The process of claim 14 , wherein the S-containing component comprises SO 3 , HSO 4 − , R—HSO 4 and/or sulfuric acid.

16. The process of claim 14 , wherein step (III) comprises:
(IIIa) contacting at least a portion of the first middle effluent with a posterior sorbent capable of removing at least a portion of the S-containing component to obtain the hydrogenation feed.

17. The process of claim 16 , wherein the posterior sorbent comprises a solid-phase basic material selected from: (i) oxides of alkali metals, alkaline earth metals, and zinc; (ii) hydroxides of alkali metals, alkaline earth metals, and zinc; (iii) carbonates of alkali metals, alkaline earth metals, and zinc; (iv) bicarbonates of alkali metals, alkaline earth metals, and zinc; (v) complexes of two or more of (i), (ii), (iii), and (iv); (vi) solid amines; (vii) ion-exchange resins; and (viii) mixtures and combinations of two or more thereof.

18. The process of claim 14 , wherein the concentration of the S-containing component in the first middle effluent is in a range from 1 ppm to 1,000 ppm by weight based on the total weight of the first middle effluent.

19. The process of claim 14 , wherein step (I) comprises:
(Ia) providing a crude mixture comprising cyclohexanone, phenol, cyclohexylbenzene, and the S-contain

Assignees

• Exxonmobil Chemical Patents Inc

Inventors

• Kuechler Keith H
• Weber Jörg F W
• Poucher Ashley J
• Davis Jason D
• Becker Christopher L
• Dakka Jihad M

Classifications

• C07C45/82

  by distillation · CPC title

• C07C45/006 Primary

  by hydrogenation of aromatic hydroxy compounds · CPC title

• C07C2601/14

  The ring being saturated · CPC title

• C07C45/79

  by solid-liquid treatment; by chemisorption · CPC title

• C07C37/82

  by solid-liquid treatment; by chemisorption · CPC title