Chromium-catalyzed reactions of carbon monoxide with hydrocarbons in the presence of UV light

Patent metadata

Field	Value
Publication number	US-12528073-B2
Application number	US-202318295302-A
Country	US
Kind code	B2
Filing date	Apr 4, 2023
Priority date	Apr 6, 2022
Publication date	Jan 20, 2026
Grant date	Jan 20, 2026

Abstract

A hydrocarbon compound and carbon monoxide are reacted in the presence of either a supported chromium (VI) catalyst or a supported chromium (II) catalyst, optionally with UV-visible light irradiation and/or exposure to an oxidizing atmosphere, followed by removing a reaction product containing an alcohol compound and/or a carbonyl compound from the respective chromium catalyst. Often, the reaction product contains one or more ketone and/or aldehyde compounds.

First claim

We claim:

1 . A process comprising:
(a) contacting a hydrocarbon reactant, carbon monoxide, and a supported chromium (II) catalyst to form a treated chromium catalyst; and (b) removing from the treated chromium catalyst a reaction product comprising an alcohol compound and/or a carbonyl compound.

2 . The process of claim 1 , wherein step (a) comprises contacting the hydrocarbon reactant, the carbon monoxide, and the supported chromium catalyst (II) catalyst while irradiating with a light beam at a wavelength in the UV-visible spectrum to form the treated chromium catalyst.

3 . The process of claim 1 , wherein the process further comprises a step of subjecting the treated chromium catalyst to an oxidizing atmosphere after step (a) and before step (b).

4 . The process of claim 3 , wherein step (a) comprises contacting the hydrocarbon reactant, the carbon monoxide, and the supported chromium catalyst (II) catalyst while irradiating with a light beam at a wavelength in the UV-visible spectrum to form the treated chromium catalyst.

5 . The process of claim 3 , wherein:
the oxidizing atmosphere comprises air; and a molar ratio of elemental oxygen in the oxidizing atmosphere to chromium of the supported chromium (II) catalyst is at least 10:1.

6 . The process of claim 1 , wherein the hydrocarbon reactant comprises a C 1 to C 8 alkane compound, a C 2 to C 12 olefin compound, a C 6 to C 12 aromatic compound, or any combination thereof.

7 . The process of claim 1 , wherein the hydrocarbon reactant comprises ethylene, and the carbonyl compound comprises cyclopentanone.

8 . The process of claim 1 , wherein:
the supported chromium (II) catalyst comprises a solid oxide, a chemically-treated solid oxide, a zeolite, or a combination thereof; and the supported chromium (II) catalyst has a pore volume from 0.1 to 5 mL/g and a BET surface area from 50 to 2000 m 2 /g.

9 . The process of claim 8 , wherein the supported chromium (II) catalyst contains from 0.01 to 50 wt. % chromium, based on the weight of the supported chromium (II) catalyst.

10 . The process of claim 1 , wherein a molar ratio of the hydrocarbon reactant to the carbon monoxide is from 0.1:1 to 10:1.

11 . The process of claim 1 , wherein a molar yield of the alcohol compound and/or the carbonyl compound is from 0.1 to 10 moles of the alcohol compound and/or the carbonyl compound per mole of chromium (II) of the supported chromium (II) catalyst.

12 . A process comprising:
performing the process of claim 1 , wherein the hydrocarbon reactant comprises ethylene, and the carbonyl compound comprises cyclopentanone; oxidizing the cyclopentanone to form valerolactone; and polymerizing valerolactone to form a polyester.

13 . A process comprising:
(i) irradiating a hydrocarbon reactant, carbon monoxide, 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) subjecting the reduced chromium catalyst to an oxidizing atmosphere, wherein:
the oxidizing atmosphere comprises air; and
a molar ratio of elemental oxygen in the oxidizing atmosphere to chromium of the reduced chromium catalyst is at least 10:1; and
(iii) removing from the reduced chromium catalyst a reaction product comprising an alcohol compound and/or a carbonyl compound.

14 . The process of claim 13 , wherein;
the light beam is from a blue light source or a UV light source; the light beam comprises wavelengths above 350 nm and below 500 nm; the hydrocarbon reactant, the carbon monoxide, and the supported chromium catalyst are irradiated with an illuminance of at least 10,000 lux; or any combination thereof.

15 . The process of claim 14 , wherein a molar yield of the alcohol compound and/or the carbonyl compound is from 0.1 to 10 moles of the alcohol compound and/or the carbonyl compound per mole of chromium (VI) of the supported chromium catalyst.

16 . The process of claim 13 , wherein the hydrocarbon reactant comprises a C 1 to C 8 alkane compound, a C 2 to C 12 olefin compound, a C 6 to C 12 aromatic compound, or any combination thereof.

17 . The process of claim 13 , wherein:
the supported chromium catalyst contains from 0.01 to 50 wt. % chromium, based on the weight of the supported chromium catalyst; and a molar ratio of the hydrocarbon reactant to the carbon monoxide is from 0.1:1 to 10:1.

18 . The process of claim 13 , wherein the hydrocarbon reactant comprises ethylene, and the carbonyl compound comprises cyclopentanone.

19 . A process comprising:
(a) contacting ethylene, carbon monoxide, and a supported chromium (II) catalyst to form a treated chromium catalyst; and (b) contacting the treated chromium catalyst and an optional co-catalyst with ethylene and an optional olefin comonomer in a polymerization reactor system under polymerization reaction conditions to produce an ethylene polymer.

20 . A process comprising:
(a) contacting ethylene, carbon monoxide, and a supported chromium (II) catalyst to form a treated chromium catalyst; and (b) contacting the treated chromium catalyst and an optional co-catalyst with ethylene in a polymerization reactor system under polymerization reaction conditions to produce an ethylene/carbon monoxide copolymer.

Assignees

• Chevron Phillips Chemical Co Lp

Inventors

• Mcdaniel Max P
• Refvik Mitchell D
• Praetorius Jeremy M
• Clear Kathy S
• Barr Jared L
• Cruz Carlos A
• Monwar Masud M

Classifications

• B01J35/40

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

• C08G63/08

  Lactones or lactides · CPC title

• C08F10/02

  Ethene · CPC title

• C07D307/33

  in position 2, the oxygen atom being in its keto or unsubstituted enol form · CPC title

• C07C45/28

  of CHx-moieties · CPC title