Production of cyclic C5 compounds

Patent metadata

Field	Value
Publication number	US-9994499-B2
Application number	US-201615288378-A
Country	US
Kind code	B2
Filing date	Oct 7, 2016
Priority date	Nov 4, 2015
Publication date	Jun 12, 2018
Grant date	Jun 12, 2018

Abstract

Disclosed is a process for the conversion of acyclic C 5 feedstock to a product comprising cyclic C 5 compounds, including cyclopentadiene, and catalyst compositions for use in such process. The process comprises contacting the feedstock and, optionally, hydrogen under acyclic C 5 conversion conditions in the presence of a catalyst composition to form said product. The catalyst composition comprises a microporous crystalline metallosilicate, a Group 10 metal or compound thereof, and a Group 11 metal or compound thereof.

First claim

What is claimed is:

1. A process for producing cyclic C 5 compounds including cyclopentadiene, the process comprising:
(a) contacting a feed containing acyclic C 5 hydrocarbons with a catalyst comprising (i) a microporous crystalline metallosilicate having a constraint index less than or equal to 12, (ii) a Group 10 metal or a compound thereof, and (iii) a Group 11 metal or a compound thereof under conditions effective to convert at least part of the acyclic C 5 hydrocarbons in the feed to produce an effluent comprising cyclopentadiene, wherein the microporous crystalline metallosilicate comprises a metallosilicate framework type selected from the group consisting of MWW, MFI, LTL, MOR, BEA, TON, MTW, MTT, FER, MRE, MFS, MEL, DDR, EUO, and FAU; and
(b) recovering cyclopentadiene from the effluent.

2. The process of claim 1 , wherein the microporous crystalline metallosilicate has a constraint index from 1 to 12.

3. The process of claim 1 , wherein the Group 10 metal is selected from the group consisting of Ni, Pd, Pt, and mixtures thereof.

4. The process of claim 1 , wherein the Group 10 metal is present in an amount in the range from about 0.005 wt % to about 10 wt % based on the weight of the catalyst composition.

5. The process of claim 1 , wherein the catalyst also contains a Group 1 alkali metal and/or a Group 2 alkaline earth metal.

6. The process of claim 1 , wherein the Group 11 metal is selected from the group consisting of silver, gold, copper, and mixtures thereof.

7. The process of claim 1 , wherein the Group 11 metal is present at a molar ratio of Group 11 metal to Group 10 metal of about 0.1 to about 5.

8. The process of claim 1 , wherein the effluent also includes cyclopentane and/or cyclopentene and the method further comprises:
(c) recovering at least part of the cyclopentane and/or cyclopentene and routing to a product disposition and/or recycling at least part of the cyclopentane and/or cyclopentene to the contacting (a).

9. The process of claim 1 , wherein the microporous crystalline metallosilicate has a silica to metal molar ratio in excess of 2.

10. The process of claim 1 , wherein the microporous crystalline metallosilicate is selected from the group consisting of Zeolite beta, mordenite, faujasite, Zeolite L, ZSM-5, ZSM-11, ZSM-22, ZSM-23, ZSM-35, ZSM-48, ZSM-50, ZSM-57, ZSM-58, MCM-22 family material, and mixtures of two or more thereof.

11. The process of claim 1 , wherein the microporous crystalline metallosilicate comprises ZSM-5.

12. The process of claim 1 , wherein the conditions employed in the contacting (a) comprise a temperature from 400° C. to 700° C. and a partial pressure of acyclic C 5 feedstock from 3 to 100 psia (21 kPa-a to 690 kPa-a) at the reactor inlet.

13. The process of claim 1 , wherein the acyclic C 5 feed comprises pentane, pentene, pentadiene, and mixtures thereof.

14. The process of claim 1 , wherein the acyclic C 5 feed comprises at least 75% by weight n-pentane.

15. The process of claim 1 , wherein the catalyst composition provides a conversion of at least about 70% of the acyclic C 5 feed under conversion conditions including an n-pentane feedstock with equimolar H 2 , a temperature in the range of about 550° C. to about 600° C., an n-pentane partial pressure from 3 to 30 psia at the reactor inlet (21 kPa-a to 207 kPa-a), and an n-pentane weight hourly space velocity from 5 to 20 hr −1 .

16. The process of claim 1 , wherein the catalyst composition provides a carbon selectivity to cyclic C 5 compounds of at least about 30% under conversion conditions including an n-pentane feedstock with equimolar H 2 , a temperature in the range of about 550° C. to about 600° C., an n-pentane partial pressure from 3 to 30 psia at the reactor inlet (21 kPa-a to 207 kPa-a), and an n-pentane weight hourly space velocity from 5 to 20 hr −1 .

17. A process for producing cyclic C 5 compounds including cyclopentadiene, the process comprising:
(a) contacting a feed containing acyclic C 5 hydrocarbons with a catalyst comprising (i) a microporous crystalline metallosilicate having a constraint index less than or equal to 12, (ii) platinum or a compound thereof, and (iii) silver or a compound thereof under conditions effective to convert at least part of the acyclic C 5 hydrocarbons in the feed to produce an effluent comprising cyclopentadiene, wherein the microporous crystalline metallosilicate comprises a metallosilicate framework type selected from the group consisting of MWW, MFI, LTL, MOR, BEA, TON, MTW, MTT, FER, MRE, MFS, MEL, DDR, EUO, and FAU; and
(b) recovering cyclopentadiene from the effluent.

18. A process for producing cyclic C 5 compounds including cyclopentadiene, the process comprising:
(a) contacting a feed containing acyclic C 5 hydrocarbons with a catalyst comprising (i) a microporous crystalline metallosilicate having a constraint index less than or equal to 12, (ii) platinum or a compound thereof, and (iii) copper or a compound thereof under conditions effective to convert at least part of the acyclic C 5 hydrocarbons in the feed to produce an effluent comprising cyclopentadiene, wherein the microporous crystalline metallosilicate comprises a metallosilicate framework type selected from the group consisting of MWW, MFI, LTL, MOR, BEA, TON, MTW, MTT, FER, MRE, MFS, MEL, DDR, EUO, and FAU; and
(b) recovering cyclopentadiene from the effluent.

Assignees

• Exxonmobil Chemical Patents Inc

Inventors

• Iaccino Larry L
• Bedard Jeremy W
• Lai Wenyih F

Classifications

• C07C2601/10

  the ring being unsaturated · CPC title

• C07C2601/06

  with a five-membered ring · CPC title

• C07C5/42

  by dehydrogenation with a hydrogen acceptor · CPC title

• B01J29/46 Primary

  Iron group metals or copper · CPC title

• B01J29/44

  Noble metals · CPC title