Production of cyclopentadiene from furfural

Patent metadata

Field	Value
Publication number	US-11377397-B2
Application number	US-202017077327-A
Country	US
Kind code	B2
Filing date	Oct 22, 2020
Priority date	Dec 20, 2019
Publication date	Jul 5, 2022
Grant date	Jul 5, 2022

Abstract

The application relates to processes and systems that use a furfural compound for producing five-membered carbocyclic rings that are unsaturated, such as cyclopentene and cyclopentadiene. Examples methods for conversion of furfural compounds may include converting a furfural compound to at least a five-membered, saturated carbocyclic ring, and converting the five-membered, saturated carbocyclic ring in a presence of a catalyst to at least a five-membered, unsaturated carbocyclic ring.

First claim

The invention claimed is:

1. A method for conversion of furfural compounds, comprising:
converting a furfural compound to at least a five-membered, saturated carbocyclic rings wherein the five-membered, saturated carbocyclic ring is selected from the group consisting of a cyclopentanol product, a cyclopentanone product, a cyclopentanediol product, and combinations thereof; and
converting the five-membered, saturated carbocyclic ring to at least a five-membered, unsaturated carbocyclic ring, wherein the five-membered, unsaturated carbocyclic ring is selected from the group consisting of a cyclopentene product, a cyclopentadiene product, and combinations thereof;
wherein the cyclopentanol product comprises cyclopentanol, a substituted cyclopentanol, or a combination thereof;
wherein the cyclopentanone product comprises cyclopentanone, a substituted cyclopentanone, or a combination thereof;
wherein the cyclopentanediol product comprises cyclopentanediol, a substituted cyclopentanediol, or a combination thereof;
wherein the cyclopentene product comprises cyclopentene, a substituted cyclopentene, or a combination thereof;
wherein the cyclopentadiene product comprises cyclopentadiene, a substituted cyclopentadiene, or a combination thereof; and
wherein the converting the furfural compound and the converting the five-membered, saturated carbocyclic ring occur in a single step over a bifunctional catalyst comprising a hydrogenation/dehydrogenation metal and a heterogenous acid component.

2. The method of claim 1 , wherein the converting the furfural compound and the converting the five-membered, saturated carbocyclic ring occur in at least one reactor selected from the group consisting of a fixed bed reactor, a batch reactor, a slurry reactor, a semi-batch reactor, and a fluidized-bed reactor.

3. The method of claim 1 , wherein the furfural compound is represented by the following structure:

wherein R1, R2, and R3 are individually selected from hydrogen or a hydrocarbyl group containing 1 carbon atom to 10 carbon atoms, and wherein the hydrocarbyl group is linear, branched, an aromatic cyclic hydrocarbyl, or a non-aromatic cyclic hydrocarbyl;
wherein the cyclopentene product is represented by at least one of the following structures:

wherein the cyclopentadiene product is represented at least one of the following structures:

wherein R1, R2, and R3 are individually selected from hydrogen or a hydrocarbyl group containing 1 carbon atom to 10 carbon atoms, and wherein the hydrocarbyl group is linear, branched, an aromatic cyclic hydrocarbyl, or a non-aromatic cyclic hydrocarbyl.

4. The method of claim 1 , wherein the converting the furfural compound is at a temperature of about 20° C. to about 400° C. and at a pressure of about 15 psig to about 1000 psig, and wherein the five-membered, saturated carbocyclic ring is selected from the group consisting of cyclopentanol, cyclopentanone, cyclopentanediol, and combinations thereof.

5. The method of claim 1 , wherein the converting the five-membered, saturated carbocyclic ring comprises dehydrating the five-membered, saturated carbocyclic ring comprising the cyclopentanol product to produce at least water and the cyclopentene product.

6. The method of claim 5 , further comprising dehydrogenating the cyclopentene product to produce at least hydrogen and the cyclopentadiene product, wherein the dehydrating is at a temperature of about 25° C. to about 300° C. and at a pressure of about 15 psig to about 1000 psig.

7. The method of claim 1 , wherein the converting the five-membered, saturated carbocyclic ring comprises dehydrating the five-membered, saturated carbocyclic ring comprising the cyclopentanone product to produce at least water and the cyclopentadiene product, wherein the dehydrating is at a temperature of about 25° C. to about 500° C. and at a pressure of about 15 psig to about 1000 psig.

8. The method of claim 1 , wherein the furfural compound comprises furfural, and wherein the five-membered, unsaturated carbocyclic ring comprises a combination of cyclopentene and cyclopentadiene, and wherein the five-membered, saturated carbocyclic ring comprises a combination of cyclopentanol and cyclopentanone.

9. The method of claim 1 , wherein the five-membered, saturated carbocyclic ring comprises cyclopentane-1,3-diol, and wherein the cyclopentane-1,3-diol is converted to the cyclopentadiene.

10. The method of claim 9 , wherein the hydrogenation/dehydrogenation metal comprises at least one metal selected from the group consisting of Pd, Pt, Ni, Rh, Ru, Ni, Co, and combinations thereof, and wherein the heterogenous acid component comprises at least one component selected from the group consisting of a zeolite, a mixed metal oxide, a resin, and combinations thereof, where the heterogenous acid component has an alpha value of less than 100.

11. The method of claim 1 , wherein products of the converting the furfural compound comprising the five-membered, saturated carbocyclic ring are not purified prior to the step of converting the five-membered, saturated carbocyclic ring.

12. A method for conversion of furfural compounds, comprising:
contacting furfural and hydrogen with a catalyst to produce at least a five-membered, saturated carbocyclic ring, wherein the five-membered, saturated carbocyclic ring is selected from the group consisting of cyclopentanol, cyclopentanone, cyclopentanediol, and combinations thereof; and
contacting the five-membered, saturated carbocyclic ring with a catalyst to produce at least water and a five-membered, unsaturated carbocyclic ring, wherein the five-membered, unsaturated carbocyclic ring comprises.

13. The method of claim 12 , wherein the contacting the five-membered, saturated carbocyclic ring comprises dehydrating and dehydrogenating the five-membered, saturated carbocyclic ring comprising the cyclopentanol to produce the five-membered, unsaturated carbocyclic ring comprising the cyclopentadiene.

14. The method of claim 12 , wherein the contacting the five-membered, saturated carbocyclic ring comprises dehydrating the five-membered, saturated carbocyclic ring comprising the cyclopentanone to produce the five-membered, unsaturated carbocyclic ring comprising the cyclopentadiene.

15. The method of claim 12 , wherein the five-membered, saturated carbocyclic ring comprises cyclopentane-1,3-diol, and wherein the cyclopentane-1,3-diol is converted to cyclopentadiene.

16. A method for conversion of furfural compounds, comprising:
hydrogenating furfural by catalytically reacting the furfural and hydrogen to produce a five-membered, saturated carbocyclic ring, wherein the five-membered, saturated carbocyclic ring is selected from the group consisting of cyclopentanol, cyclopentanone, cyclopentanediol and combinations thereof; and
converting the five-membered, saturated carbocyclic ring to cyclopentadiene;
wherein the hydrogenating furfural and the converting the five-membered, saturated carbocyclic ring occur in a single step over a bifunctional catalyst comprising a hydrogenation/dehydrogenation metal and a heterogenous acid component.

Assignees

• Exxonmobil Technology & Engineering Company

Inventors

• Wang Kun
• Sattler Aaron
• Dakka Jihad M

Classifications

• C07C1/247

  by splitting of cyclic ethers · CPC title

• B01J2208/06

  Details of tube reactors containing solid particles · CPC title

• B01J8/008 Primary

  Details of the reactor or of the particulate material; Processes to increase or to retard the rate of reaction (B01J8/0285, B01J8/067, B01J8/087, B01J8/1836 take precedence) · CPC title

• C07C2529/068

  Noble metals · CPC title

• C07C1/24 Primary

  by elimination of water · CPC title