Chromium-catalyzed production of diols from olefins

Patent metadata

Field	Value
Publication number	US-11142491-B2
Application number	US-202017019449-A
Country	US
Kind code	B2
Filing date	Sep 14, 2020
Priority date	Sep 16, 2019
Publication date	Oct 12, 2021
Grant date	Oct 12, 2021

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 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 olefin reactant from the reaction product, wherein the at least a portion of the olefin reactant is recycled and irradiated with the supported chromium catalyst again.

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

3. 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.

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 −100° C. to about 100° C.

8. 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.

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 olefin reactant is at least about 10 wt. %.

11. The process of claim 1 , 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.

12. The process of claim 1 , wherein:
the olefin reactant comprises ethylene and the diol compound comprises ethanediol;
the olefin reactant comprises propylene and the diol compound comprises propanediol;
the olefin reactant comprises 1-pentene and the diol compound comprises a pentanediol; or
the olefin reactant comprises 1-hexene and the diol compound comprises a hexanediol.

13. 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; and
(ii) hydrolyzing the reduced chromium catalyst to form a reaction product comprising the diol compound;
wherein a molar yield of the diol compound is from about 0.01 to about 2 moles of the diol compound per mole of chromium (VI) in the supported chromium catalyst.

14. The process of claim 13 , wherein the diol compound comprises a 1,2-diol compound.

15. The process of claim 13 , wherein:
the supported chromium catalyst contains from about 0.2 to about 10 wt. % of chromium, based on the weight of the supported chromium catalyst; and
the olefin reactant comprises ethylene, propylene, butene, pentene, hexene, heptene, octene, decene, dodecene, tetradecene, hexadecene, octadecene, or any combination thereof.

16. The process of claim 15 , wherein the 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.

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