Chromium-catalyzed production of alcohols from hydrocarbons

Patent metadata

Field	Value
Publication number	US-11078143-B2
Application number	US-202017019413-A
Country	US
Kind code	B2
Filing date	Sep 14, 2020
Priority date	Sep 16, 2019
Publication date	Aug 3, 2021
Grant date	Aug 3, 2021

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 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; and
(iii) separating at least a portion of the hydrocarbon reactant from the reaction product, wherein the at least a portion of the hydrocarbon reactant is recycled and irradiated with the supported chromium catalyst again.

2. The process of claim 1 , wherein the hydrocarbon reactant comprises a C 1 to C 36 linear, branched, or cyclic alkane compound.

3. The process of claim 1 , wherein the hydrocarbon reactant comprises methane, ethane, propane, butane, or a combination thereof.

4. 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.

5. The process of claim 1 , wherein the reduced chromium catalyst contains chromium having an average valence of less than or equal to about 5.25.

6. The process of claim 1 , wherein the wavelength comprises a single wavelength or a range of wavelengths in a range from about 200 nm to about 750 nm.

7. The process of claim 1 , wherein the irradiating step is conducted at a temperature from about 0° C. to about 100° C.

8. 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.

9. 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.

10. The process of claim 1 , wherein a conversion of the hydrocarbon reactant is at least about 10 wt. %.

11. The process of claim 1 , wherein a molar yield of the alcohol compound and/or the carbonyl compound is from about 0.01 to about 2 moles of the alcohol compound and/or the carbonyl compound per mole of chromium (VI) in the supported chromium catalyst.

12. 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).

13. A process for converting a C 1 -C 6 alkane compound into a C 1 -C 6 alcohol compound, the process comprising:
(a) irradiating the C 1 -C 6 alkane compound 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;
(b) hydrolyzing the reduced chromium catalyst to form a reaction product comprising the C 1 -C 6 alcohol compound; and
(c) separating at least a portion of the C 1 -C 6 alkane compound from the reaction product, wherein the at least a portion of the C 1 -C 6 alkane compound is recycled and irradiated with the supported chromium catalyst again.

14. The process of claim 13 , 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.

15. The process of claim 13 , wherein the alkane compound comprises methane and the alcohol compound comprises methanol.

16. The process of claim 15 , wherein the reaction product further comprises formic acid.

17. 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 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; and
(iv) calcining the at least a portion of the reduced chromium catalyst to regenerate the supported chromium catalyst.

18. The process of claim 17 , 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 hydrocarbon reactant comprises methane, ethane, propane, butane, or a combination thereof.

19. The process of claim 17 , 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.

20. The process of claim 17 , wherein a conversion of the hydrocarbon reactant is at least about 10 wt. %.

21. The process of claim 17 , 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.

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

• C07C51/215

  of saturated hydrocarbyl groups · CPC title

• C07C49/04

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

• C07C47/02

  Saturated compounds having —CHO groups bound to acyclic carbon atoms or to hydrogen · CPC title

• C07C45/33

  of CHx-moieties · CPC title