Oligomerization of isobutanol in the presence of MWW zeolite solid acid catalysts

Patent metadata

Field	Value
Publication number	US-11452997-B2
Application number	US-202017136553-A
Country	US
Kind code	B2
Filing date	Dec 29, 2020
Priority date	Jan 29, 2020
Publication date	Sep 27, 2022
Grant date	Sep 27, 2022

Abstract

Isobutanol may be converted into predominantly C 12+ olefin oligomers under specified conditions. Such methods may comprise: contacting a feed comprising isobutanol with a zeolite solid acid catalyst having a MWW framework under conditions effective to convert the isobutanol into a product comprising C 4n olefin oligomers, wherein n is an integer having a value of two or greater and about 80 wt. % or greater of the C 4n olefin oligomers are larger than C 8 .

First claim

What is claimed is:

1. A method comprising:
contacting a feed comprising isobutanol with a zeolite solid acid catalyst having an MWW framework under conditions effective to convert the isobutanol into a product comprising C 4n olefin oligomers, wherein n is an integer having a value of two or greater and about 80 wt. % or greater of the C 4n olefin oligomers are larger than C 8 .

2. The method of claim 1 , wherein about 90 wt. of the C 4n olefin oligomers are larger than C 8 .

3. The method of claim 1 , wherein the zeolite solid acid catalyst is selected from the group consisting of MCM-22, PSH-3, SSZ-25, ERB-1, ITQ-1, ITQ-2, MCM-36, MCM-49, MCM-56, EMM-10, EMM-12, EMM-13, UZM-8, UZM-8HS, UZM-37, MIT-1, and any combination thereof.

4. The method of claim 1 , wherein the zeolite solid acid catalyst is MCM-49.

5. The method of claim 1 , wherein the isobutanol is biologically derived.

6. The method of claim 5 , wherein the isobutanol is formed as a byproduct of producing bioethanol.

7. The method of claim 1 , wherein the feed further comprises one or more fermentation byproducts.

8. The method of claim 7 , wherein the one or more fermentation byproducts comprise at least one member selected from the group consisting of ethanol, xylose, furfural, lactic acid, 5-hydroxymethylfurfural, and any combination thereof.

9. The method of claim 1 , wherein the contacting is performed in an absence of co-fed water.

10. The method of claim 9 , wherein the product comprises at least about 45 wt. % C 12 olefin oligomers.

11. The method of claim 9 , wherein the product comprises at least about 30 wt. % C 16 olefin oligomers.

12. The method of claim 1 , wherein the product comprises C 8 olefin oligomers and at least about 80 wt. % of the C 8 olefin oligomers are di branched.

13. The method of claim 1 , wherein less than about 0.1 wt. % of the isobutanol is converted into C 3− hydrocarbons.

14. The method of claim 1 , further comprising:
hydrogenating the C 4n olefin oligomers to form C 4n isoparaffins.

15. The method of claim 14 , wherein formation of the Can olefin oligomers and hydrogenation of the C 4n olefin oligomers take place in a single reactor, the feed being contacted with the zeolite solid acid catalyst in an upstream portion of the single reactor and the C 4n olefin oligomers being contacted with a hydrogenation catalyst in a downstream portion of the single reactor.

16. The method of claim 14 , wherein the formation of the C 4n olefin oligomers and hydrogenation of the C 4n olefin oligomers take place in separate reactors.

17. The method of claim 1 , further comprising:
recycling unconverted isobutanol to the feed.

18. The method of claim 1 , wherein the conditions effective to convert the isobutanol comprise one or more of a temperature of about 100° C. to about 300° C., a pressure ranging from atmospheric pressure up to about 1000 psig, and a liquid hourly space velocity (LHSV) of about 0.25 hour-1 to about 6 hour-1.

19. The method of claim 1 , wherein contacting takes place in a fixed catalyst bed reactor, a batch reactor, a slurry reactor, or a fluidized bed reactor.

20. The method of claim 1 , further comprising:
processing the C 4n olefin oligomers into a jet fuel.

Assignees

• Exxonmobil Technology & Engineering Company

Inventors

• Dakka Jihad M
• Hanks Patrick L
• Carcuffe Brandon M
• Omilian Cynthia F
• Dehaas Ralph C
• Behkish Arsam

Classifications

• C07C2529/70

  of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65 · CPC title

• C10G2300/4018

  Spatial velocity, e.g. LHSV, WHSV · CPC title

• C07C9/15

  Straight-chain hydrocarbons · CPC title

• B01J29/7038 Primary

  MWW-type, e.g. MCM-22, ERB-1, ITQ-1, PSH-3 or SSZ-25 · CPC title

• C07C1/24

  by elimination of water · CPC title