Chromium-catalyzed production of alcohols from hydrocarbons

Patent metadata

Field	Value
Publication number	US-11440864-B2
Application number	US-202117372657-A
Country	US
Kind code	B2
Filing date	Jul 12, 2021
Priority date	Sep 16, 2019
Publication date	Sep 13, 2022
Grant date	Sep 13, 2022

Abstract

Processes for converting a hydrocarbon reactant into an alcohol compound and/or a carbonyl compound are disclosed, and these processes include the steps of irradiating the hydrocarbon reactant and a supported chromium catalyst comprising chromium in a hexavalent oxidation state with a light beam at a wavelength in the UV-visible spectrum to reduce at least a portion of the supported chromium catalyst to form a reduced chromium catalyst, and hydrolyzing the reduced chromium catalyst to form a reaction product comprising the alcohol compound and/or the carbonyl compound. In addition, these processes can further comprise a step of calcining all or a portion of the reduced chromium catalyst to regenerate the supported chromium catalyst.

First claim

We claim:

1. A process for converting a hydrocarbon reactant into an alcohol compound and/or a carbonyl compound, the process comprising:
(i) irradiating the hydrocarbon reactant and a supported chromium catalyst comprising chromium in a hexavalent oxidation state with at least about 10,000 lux of a light beam at a wavelength in the UV-visible spectrum to reduce at least a portion of the supported chromium catalyst to form a reduced chromium catalyst; and
(ii) hydrolyzing the reduced chromium catalyst to form a reaction product comprising the alcohol compound and/or the carbonyl compound.

2. The process of claim 1 , wherein:
the supported chromium catalyst contains from about 0.01 to about 50 wt. % of chromium, based on the weight of the supported chromium catalyst; and
the reduced chromium catalyst contains chromium having an average valence of less than or equal to about 5.25.

3. The process of claim 1 , wherein the process comprises:
contacting the hydrocarbon reactant with a fluidized bed of the supported chromium catalyst, and irradiating while contacting; or
contacting the hydrocarbon reactant with a fixed bed of the supported chromium catalyst, and irradiating while contacting.

4. The process of claim 1 , wherein:
hydrolyzing is conducted at a temperature from about 0° C. to about 100° C.; and
hydrolyzing comprises contacting the reduced chromium catalyst with a hydrolysis agent comprising water, steam, an alcohol agent, an acid agent, an alkaline agent, or any combination thereof.

5. The process of claim 1 , wherein the hydrocarbon reactant and the supported chromium catalyst are irradiated with from about 50,000 to about 500,000 lux.

6. The process of claim 5 , wherein the hydrocarbon reactant comprises a C 1 to C 6 alkane compound.

7. The process of claim 6 , wherein:
the light beam is from a blue light source or a UV light source; and
the irradiating step is conducted at a temperature from about 0° C. to about 100° C.

8. The process of claim 1 , wherein a molar yield of the alcohol compound and/or the carbonyl compound is from about 0.05 to about 1.8 moles of the alcohol compound and/or the carbonyl compound per mole of chromium (VI) in the supported chromium catalyst.

9. The process of claim 1 , further comprising:
a step of separating at least a portion of the alcohol compound and/or the carbonyl compound from the reaction product after step (ii); and/or
a step of separating at least a portion of the hydrocarbon reactant from the reaction product after step (ii), and wherein the at least a portion of the hydrocarbon reactant is recycled and irradiated with the supported chromium catalyst again.

10. The process of claim 1 , wherein the hydrocarbon reactant and the supported chromium catalyst are irradiated with from about 50,000 to about 200,000 lux.

11. The process of claim 1 , wherein the hydrocarbon reactant comprises methane and the alcohol compound comprises methanol.

12. A process for converting a hydrocarbon reactant into an alcohol compound and/or a carbonyl compound, the process comprising:
(i) irradiating the hydrocarbon reactant and a supported chromium catalyst comprising chromium in a hexavalent oxidation state with at least about 10,000 lux of a light beam at a wavelength in the UV-visible spectrum to reduce at least a portion of the supported chromium catalyst to form a reduced chromium catalyst;
(ii) hydrolyzing the reduced chromium catalyst to form a reaction product comprising the alcohol compound and/or the carbonyl compound;
(iii) separating at least a portion of the reduced chromium catalyst from the reaction product after step (ii); and
(iv) calcining the at least a portion of the reduced chromium catalyst to regenerate the supported chromium catalyst.

13. The process of claim 12 , wherein:
the supported chromium catalyst contains from about 0.01 to about 50 wt. % of chromium, based on the weight of the supported chromium catalyst; and
the reduced chromium catalyst contains chromium having an average valence of less than or equal to about 5.25.

14. The process of claim 13 , wherein:
hydrolyzing is conducted at a temperature from about 0° C. to about 100° C.; and
hydrolyzing comprises contacting the reduced chromium catalyst with a hydrolysis agent comprising water, steam, an alcohol agent, an acid agent, an alkaline agent, or any combination thereof.

15. The process of claim 12 , wherein the hydrocarbon reactant and the supported chromium catalyst are irradiated with from about 50,000 to about 500,000 lux.

16. The process of claim 15 , wherein the hydrocarbon reactant comprises a C 1 to C 6 alkane compound.

17. The process of claim 16 , wherein:
the light beam is from a blue light source or a UV light source; and
the irradiating step is conducted at a temperature from about 0° C. to about 100° C.

18. The process of claim 15 , wherein a molar yield of the alcohol compound and/or the carbonyl compound is from about 0.05 to about 1.8 moles of the alcohol compound and/or the carbonyl compound per mole of chromium (VI) in the supported chromium catalyst.

19. The process of claim 15 , wherein the hydrocarbon reactant comprises methane and the alcohol compound comprises methanol.

20. The process of claim 15 , further comprising:
a step of separating at least a portion of the alcohol compound and/or the carbonyl compound from the reaction product after step (ii); and/or
a step of separating at least a portion of the hydrocarbon reactant from the reaction product after step (ii), and wherein the at least a portion of the hydrocarbon reactant is recycled and irradiated with the supported chromium catalyst again.

21. The process of claim 12 , wherein the hydrocarbon reactant and the supported chromium catalyst are irradiated with from about 50,000 to about 200,000 lux.

Assignees

• Chevron Phillips Chemical Co Lp

Inventors

• Mcdaniel Max P
• Cruz Carlos A
• Monwar Masud M
• Barr Jared L
• Ellis William C

Classifications

• B01J35/40

  characterised by dimensions, e.g. grain size (in a colloidal state B01J35/23; crystallite size B01J35/77) · CPC title

• C07C29/50

  with molecular oxygen only · CPC title

• C07C31/202

  Ethylene glycol · CPC title

• C07C45/33

  of CHx-moieties · CPC title

• C07C49/04

  Saturated compounds containing keto groups bound to acyclic carbon atoms · CPC title