Methanol production from methane utilizing a supported chromium catalyst

Patent metadata

Field	Value
Publication number	US-12351545-B2
Application number	US-202418829583-A
Country	US
Kind code	B2
Filing date	Sep 10, 2024
Priority date	Oct 31, 2022
Publication date	Jul 8, 2025
Grant date	Jul 8, 2025

Abstract

Processes for converting methane into methanol are disclosed in which methane, water, and a supported chromium (VI) catalyst are contacted with a light beam at a wavelength in the UV-visible spectrum in an oxidizing atmosphere in a single reactor to form a reaction product comprising methanol, followed by discharging a reactor effluent containing the reaction product from the single reactor, and then separating methanol from the reaction product. Processes to produce methanol using additional reactors also are described, as well as related methanol production systems.

First claim

We claim:

1. A process for converting methane into methanol, the process comprising:
(a) contacting methane and a supported chromium catalyst comprising chromium in a hexavalent oxidation state with a light beam at a wavelength in the UV-visible spectrum, optionally in a first oxidizing atmosphere, in a first reactor to form a reduced chromium catalyst;
(b) contacting the reduced chromium catalyst with water, optionally in a second oxidizing atmosphere, in a second reactor to form a reaction product comprising methanol;
(c) discharging a reactor effluent containing the reaction product from the second reactor; and
(d) separating methanol from the reaction product;
wherein a molar ratio of water in step (b) to methane in step (a) is from 1:2 to 2:1.

2. The process of claim 1 , wherein:
chromium of the reduced chromium catalyst in step (a) has an average valence of less than or equal to 5;
the first reactor and the second reactor are fluidized bed reactors;
the first oxidizing atmosphere is present in step (a);
the second oxidizing atmosphere is present in step (b); and
the process further comprises a step of calcining the reduced chromium catalyst after step (b) to regenerate at least a portion of the supported chromium catalyst.

3. The process of claim 2 , 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 450 nm;
the methane and the supported chromium catalyst are irradiated with an illuminance of at least 10,000 lux; or
any combination thereof.

4. The process of claim 2 , wherein step (a) is conducted at:
a temperature from 20° C. to 250° C.;
a pressure from 10 to 200 psig; and
an average contact time of the supported chromium catalyst with methane from 3 sec to 150 sec.

5. The process of claim 1 , wherein:
a molar ratio of methane to chromium of the supported chromium catalyst in step (a) is at least 10:1; and
a molar ratio of water to chromium of the reduced chromium catalyst in step (b) is at least 5:1.

6. The process of claim 1 , wherein step (a) comprises contacting methane with a fluidized bed of the supported chromium catalyst while irradiating.

7. The process of claim 6 , wherein the supported chromium catalyst:
has a pore volume from 0.1 to 1 mL/g and a BET surface area from 750 to 2000 m 2 /g;
contains from 1 to 10 wt. % chromium, based on the weight of the supported chromium catalyst;
comprises a chromium/silica catalyst; or
any combination thereof.

8. The process of claim 1 , wherein a molar yield of methanol is from 0.25 to 100 moles of the methanol per mole of chromium (VI) of the supported chromium catalyst.

9. The process of claim 1 , further comprising;
a step of condensing to separate the reaction product from the reactor effluent, and wherein separating methanol from the reaction product comprises distillation;
a step of recycling unreacted methane from the reactor effluent to the first reactor;
a step of calcining the reduced chromium catalyst after step (b) to regenerate at least a portion of the supported chromium catalyst; or
any combination thereof.

10. The process of claim 1 , wherein the first reactor and the second reactor are fluidized bed reactors.

11. The process of claim 10 , wherein water is added in step (b) via steam injection into the second reactor.

12. The process of claim 1 , wherein the first reactor has one or more immersion lamps as a source of the light beam attached to a top, attached to a bottom, attached to a wall, or positioned in a wall of the first reactor, or any combination thereof.

13. The process of claim 1 , wherein the first reactor has one or more internal light sources of the light beam, the internal light sources entering through one or more ports positioned at a wall of the first reactor.

14. The process of claim 1 , wherein the reactor effluent comprises methanol, unreacted methane, and a reaction by-product comprising formic acid.

15. A process for converting methane into methanol, the process comprising:
(a) contacting methane and a supported chromium catalyst comprising chromium in a hexavalent oxidation state with a light beam at a wavelength in the UV-visible spectrum, in a first oxidizing atmosphere comprising air and in a first reactor to form a reduced chromium catalyst, wherein a molar ratio of molecular oxygen in the first oxidizing atmosphere to methane is from 0.1:1 to 1:1;
(b) contacting the reduced chromium catalyst with water, optionally in a second oxidizing atmosphere, in a second reactor to form a reaction product comprising methanol;
(c) discharging a reactor effluent containing the reaction product from the second reactor; and
(d) separating methanol from the reaction product.

16. The process of claim 15 , wherein:
chromium of the reduced chromium catalyst in step (a) has an average valence of less than or equal to 5;
the first reactor and the second reactor are fluidized bed reactors;
the second oxidizing atmosphere is present in step (b); and
the process further comprises a step of calcining the reduced chromium catalyst after step (b) to regenerate at least a portion of the supported chromium catalyst.

17. The process of claim 15 , 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 450 nm;
the methane and the supported chromium catalyst are irradiated with an illuminance of at least 10,000 lux; or
any combination thereof.

18. The process of claim 15 , wherein:
water is added in step (b) via steam injection into the second reactor;
step (a) comprises contacting methane with a fluidized bed of the supported chromium catalyst while irradiating; and
step (a) is conducted at:
a temperature from 20° C. to 250° C.;
a pressure from 10 to 200 psig; and
an average contact time of the supported chromium catalyst with methane from 3 sec to 150 sec.

19. The process of claim 15 , wherein the supported chromium catalyst:
has a pore volume from 0.1 to 1 mL/g and a BET surface area from 750 to 2000 m 2 /g;
contains from 1 to 10 wt. % chromium, based on the weight of the supported chromium catalyst; and
comprises a chromium/silica catalyst.

20. The process of claim 15 , wherein:
a molar ratio of methane to chromium of the supported chromium catalyst in step (a) is at least 10:1;
a molar ratio of water to chromium of the reduced chromium catalyst in step (b) is at least 5:1; and
a molar yield of methanol is from 0.25 to 100 moles of the methanol per mole of chromium (VI) of the supported chromium catalyst.

21. The process of claim 15 , further comprising:
a step of condensing to separate the reaction product from the reactor effluent, and wherein separating methanol from the reaction product comprises distillation;
a step of recycling unreacted methane from the reactor effluent to the first reactor;
a step of calcining the reduced chromium catalyst after step (b) to regenerate at least a portion of the supported chromium catalyst; or
any combination thereof.

22. The process of claim 15 , wherein the first reactor has:
one or more immersion lamps as a source of the light beam attached to a top, attached to a bottom, attached to a wall, or positioned in a wall of the first reactor, or any combination thereof;
one or more internal light sources of the light beam, the internal light sources entering through one or more ports positioned at a wall of the fi

Assignees

• Chevron Phillips Chemical Co Lp

Inventors

• Sutherland Jamie N
• Hillier James
• Hendrickson Gregory G
• Mcdaniel Max P

Classifications

• B01J19/123

  Ultraviolet light · CPC title

• B01J8/20

  with liquid as a fluidising medium · CPC title

• B01D53/00

  Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols, (recovery of volatile solvents by condensation B01D5/00; sublimation B01D7/00; cold traps, cold baffles B01D8/00; working-up undefined gaseous mixtures obtained by cracking hydrocarbon oils C10G70/00; cleaning coal gas C10K; working-up of natural gas, or synthetic natural gas, C10L3/10; separation of difficult-to-condense gases or air by liquefaction F25J; for investigating materials G01N30/00) · CPC title

• B01D3/14

  Fractional distillation {or use of a fractionation or rectification column} · CPC title

• C07C29/09

  by hydrolysis · CPC title