Chromium-catalyzed production of alcohols from hydrocarbons

Patent metadata

Field	Value
Publication number	US-11440865-B2
Application number	US-202117501020-A
Country	US
Kind code	B2
Filing date	Oct 14, 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 forming a supported chromium catalyst comprising chromium in a hexavalent oxidation state, irradiating the hydrocarbon reactant and the supported chromium catalyst 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. The supported chromium catalyst can be formed by heat treating a supported chromium precursor, contacting a chromium precursor with a solid support while heat treating, or heat treating a solid support and then contacting a chromium precursor with the solid support.

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) contacting a solid support with an inorganic chromate compound to form a supported chromium precursor;
(ii) heat treating the supported chromium precursor at a peak temperature from about 50° C. to about 1000° C. to form a supported chromium catalyst comprising chromium in a hexavalent oxidation state;
(iii) irradiating the hydrocarbon reactant and the supported chromium catalyst 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
(iv) 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 inorganic chromate compound comprises potassium chromate, sodium chromate, ammonium chromate, potassium dichromate, sodium dichromate, ammonium dichromate, or any combination thereof.

3. The process of claim 1 , wherein step (ii) is conducted in an oxidizing atmosphere.

4. The process of claim 1 , wherein step (ii) is conducted in an inert atmosphere.

5. The process of claim 1 , wherein the peak temperature is in a range from about 100° C. to about 500° C.

6. The process of claim 1 , wherein the peak temperature is in a range from about 50° C. to about 200° C.

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

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

9. The process of claim 1 , wherein the hydrocarbon reactant comprises a C 2 to C 36 olefin compound, a C 6 to C 36 aromatic compound, or any combination thereof.

10. 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.

11. 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.

12. 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 of the light beam; and
the light beam comprises wavelengths above 350 nm and below 500 nm.

13. The process of claim 1 , wherein the solid support comprises a solid oxide, a chemically-treated solid oxide, a zeolite, or a combination thereof.

14. The process of claim 1 , wherein:
the light beam is from a blue light source or a UV light source;
the reduced chromium catalyst contains chromium having an average valence of less than or equal to about 4.5; and
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.

15. A process for converting a hydrocarbon reactant into an alcohol compound and/or a carbonyl compound, the process comprising:
(i) contacting a solid support with an inorganic chromate compound to form a supported chromium precursor, the inorganic chromate compound comprising potassium chromate, sodium chromate, potassium dichromate, sodium dichromate, or any combination thereof;
(ii) heat treating the supported chromium precursor at a peak temperature from about 50° C. to about 1000° C. to form a supported chromium catalyst comprising chromium in a hexavalent oxidation state;
(iii) irradiating the hydrocarbon reactant and the supported chromium catalyst 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
(iv) hydrolyzing the reduced chromium catalyst to form a reaction product comprising the alcohol compound and/or the carbonyl compound.

16. The process of claim 15 , wherein step (ii) is conducted in an oxidizing atmosphere.

17. The process of claim 15 , wherein step (ii) is conducted in an inert atmosphere.

18. The process of claim 15 , wherein the hydrocarbon reactant comprises a C 1 to C 36 linear, branched, or cyclic alkane compound.

19. The process of claim 18 , wherein:
the hydrocarbon reactant and the supported chromium catalyst are irradiated with from about 50,000 to about 500,000 lux of the light beam; and
the light beam comprises wavelengths above 350 nm and below 500 nm.

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

Assignees

• Chevron Phillips Chemical Co Lp

Inventors

• Cruz Carlos A
• Monwar Masud M
• Mcdaniel Max P
• Barr Jared L
• Clear Kathy S
• 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

• C07C45/292

  with chromium derivatives · CPC title

• B01J37/16

  Reducing · CPC title

• B01J23/26

  Chromium · CPC title

• C07C29/50

  with molecular oxygen only · CPC title