Method for conversion of diols to olefin products

Patent metadata

Field	Value
Publication number	US-11780787-B2
Application number	US-202318104545-A
Country	US
Kind code	B2
Filing date	Feb 1, 2023
Priority date	Feb 2, 2022
Publication date	Oct 10, 2023
Grant date	Oct 10, 2023

Abstract

A method for converting a diol in solution to an olefin fraction, the method comprising: (i) reacting a diol of the formula HO—R—OH in solution with a carbonyl-containing molecule of the formula:in the presence of an acid catalyst to result in a dioxolane molecule of the formula:wherein R is a hydrocarbon linker containing 1-12 carbon atoms, and R1 and R2 are independently selected from hydrogen atom and hydrocarbon groups containing 1-12 carbon atoms, wherein R1 and R2 optionally interconnect; (ii) removing the dioxolane molecule from the solution by phase separation; and (iii) contacting the dioxolane molecule with a metal-loaded zeolite at a temperature of 100-500° C. to convert the dioxolane molecule to an olefin fraction.

First claim

What is claimed is:

1. A method for converting a diol in solution to an olefin fraction, the method comprising:
(i) reacting a diol of the formula HO—R—OH in solution with a carbonyl-containing molecule of the formula:

in the presence of an acid catalyst to result in a dioxolane molecule of the formula:

wherein R is a hydrocarbon linker containing 1-12 carbon atoms, and R 1 and R 2 are independently selected from hydrogen atom and hydrocarbon groups containing 1-12 carbon atoms, wherein R 1 and R 2 optionally interconnect;
(ii) removing the dioxolane molecule from the solution by phase separation; and
(iii) contacting the dioxolane molecule with a metal-loaded zeolite at a temperature of 100-500° C. to convert the dioxolane molecule to an olefin fraction.

2. The method of claim 1 , wherein said solution contains water in an amount of at least 20 wt %.

3. The method of claim 1 , wherein said solution contains water in an amount of at least 50 wt %.

4. The method of claim 1 , wherein the diol comprises 2,3-butanediol.

5. The method of claim 4 , wherein the solution is an aqueous 2,3-butanediol fermentation mixture.

6. The method of claim 5 , wherein the aqueous 2,3-butanediol fermentation mixture further comprises acetoin and/or ethanol.

7. The method of claim 1 , wherein the carbonyl-containing molecule is an aldehyde.

8. The method of claim 1 , wherein the carbonyl-containing molecule is a ketone.

9. The method of claim 1 , wherein the carbonyl-containing molecule is formaldehyde or acetaldehyde.

10. The method of claim 1 , wherein the carbonyl-containing molecule is butyraldehyde or isobutyraldehyde.

11. The method of claim 1 , wherein the metal-loaded zeolite is a metal-loaded beta zeolite.

12. The method of claim 1 , wherein the metal-loaded zeolite is a metal-loaded pentasil zeolite.

13. The method of claim 12 , wherein the metal-loaded zeolite is a metal-loaded ZSM-5 type of zeolite.

14. The method of claim 1 , wherein the metal in the metal-loaded zeolite is selected from the group consisting of copper, silver, gold, nickel, palladium, platinum, rhodium, iridium, and ruthenium.

15. The method of claim 1 , wherein the metal is present in the metal-loaded zeolite in an amount of 1-30 wt % by weight of the zeolite.

16. The method of claim 1 , wherein the metal-loaded zeolite is Cu-loaded ZSM-5.

17. The method of claim 1 , wherein the metal-loaded zeolite is Cu-loaded beta zeolite.

18. The method of claim 1 , wherein step (iii) is performed in the presence of a carrier gas.

19. The method of claim 18 , wherein the carrier comprises an inert gas.

20. The method of claim 18 , wherein the carrier gas comprises hydrogen gas.

21. The method of claim 1 , wherein after step (ii) but before step (iii) the dioxolane molecule is washed with a saturated bicarbonate solution.

22. The method of claim 1 , wherein after step (ii) but before step (iii) the dioxolane molecule is substantially removed of water.

23. The method of claim 1 , wherein the process achieves at least 70% selectivity in butenes.

24. The method of claim 1 , wherein the process achieves less than 20% ethylene in the olefin fraction.

25. The method of claim 1 , wherein the process achieves less than 10% ethylene in the olefin fraction.

26. The method of claim 1 , wherein the process achieves less than 5% ethylene in the olefin fraction.

27. The method of claim 1 , further comprising: (iv) oligomerizing the olefin fraction to produce longer chain hydrocarbons.

Assignees

• Ut Battelle Llc
• Triad Nat Security Llc

Inventors

• Li Zhenglong
• Sutton Andrew
• Moore Cameron M
• Cordon Michael

Classifications

• C07C2/46 Primary

  Catalytic processes · CPC title

• B01J29/40

  of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively · CPC title

• C07C7/11

  by absorption, i.e. purification or separation of gaseous hydrocarbons with the aid of liquids · CPC title

• B01J29/46 Primary

  Iron group metals or copper · CPC title

• B01J29/42

  containing iron group metals, noble metals or copper · CPC title