Chromium-catalyzed production of diols from olefins

Patent metadata

Field	Value
Publication number	US-11345649-B2
Application number	US-202117406208-A
Country	US
Kind code	B2
Filing date	Aug 19, 2021
Priority date	Sep 16, 2019
Publication date	May 31, 2022
Grant date	May 31, 2022

Abstract

Processes for converting an olefin reactant into a diol compound are disclosed, and these processes include the steps of contacting the olefin reactant and a supported chromium catalyst comprising chromium in a hexavalent oxidation state 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 diol compound. While being contacted, the olefin reactant and the supported chromium catalyst can be irradiated with a light beam at a wavelength in the UV-visible spectrum. Optionally, these processes can further comprise a step of calcining at least a portion of the reduced chromium catalyst to regenerate the supported chromium catalyst.

First claim

We claim:

1. A process for converting an olefin reactant into a diol compound, the process comprising:
(i) irradiating the olefin reactant and a supported chromium catalyst comprising chromium in a hexavalent oxidation state with at least 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 diol compound.

2. The process of claim 1 , wherein the olefin reactant comprises ethylene, propylene, butene, pentene, hexene, heptene, octene, decene, dodecene, tetradecene, hexadecene, octadecene, or any combination thereof.

3. 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.

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

5. 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.

6. The process of claim 1 , wherein the lux of the light beam is in a range from about 50,000 to about 500,000 lux.

7. The process of claim 6 , wherein a molar yield of the diol compound is from about 0.05 to about 1.8 moles of the diol compound per mole of chromium (VI) in the supported chromium catalyst.

8. The process of claim 6 , wherein the light beam is from a blue light source or a UV light source.

9. A process for converting an olefin reactant into a diol compound, the process comprising:
(i) irradiating the olefin reactant and a supported chromium catalyst comprising chromium in a hexavalent oxidation state with from about 50,000 to about 500,000 lux of a light beam comprising wavelengths above 350 nm and below 500 nm 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 diol compound.

10. The process of claim 9 , wherein the olefin reactant comprises ethylene, propylene, 1-butene, 1-pentene, 1-hexene, or any combination thereof.

11. The process of claim 10 , wherein the reduced chromium catalyst contains chromium having an average valence of less than or equal to about 4.5.

12. The process of claim 11 , wherein the light beam comprises wavelengths above 350 nm and below 450 nm.

13. The process of claim 9 , wherein the light beam is from a blue light source or a UV light source.

14. A process for converting an olefin reactant into a diol compound, the process comprising:
(i) irradiating the olefin 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 diol compound; and
(iii) separating at least a portion of the diol compound from the reaction product;
wherein a molar yield of the diol compound is from about 0.05 to about 1.8 moles of the diol compound per mole of chromium (VI) in the supported chromium catalyst.

15. The process of claim 14 , wherein the olefin reactant comprises ethylene, propylene, 1-butene, 1-pentene, 1-hexene, or any combination thereof.

16. The process of claim 14 , further comprising a step of separating at least a portion of the olefin reactant from the reaction product after step (ii), and wherein the at least a portion of the olefin reactant is recycled and irradiated with the supported chromium catalyst again.

17. The process of claim 14 , further comprising:
separating at least a portion of the reduced chromium catalyst from the reaction product after step (ii); and
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 reduced chromium catalyst contains chromium having an average valence of less than or equal to about 4.5.

19. A process for converting an olefin reactant into a diol compound, the process comprising:
(i) irradiating the olefin 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 diol compound;
(iii) separating at least a portion of the diol compound and 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.

20. The process of claim 19 , wherein the olefin reactant comprises ethylene, propylene, 1-butene, 1-pentene, 1-hexene, or any combination thereof.

21. The process of claim 20 , wherein the reduced chromium catalyst contains chromium having an average valence of less than or equal to about 4.5.

Assignees

• Chevron Phillips Chemical Co Lp

Inventors

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

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