Molecular sieves mediated unsaturated hydrocarbon separation and related compositions, materials, methods and systems

Patent metadata

Field	Value
Publication number	US-10427995-B2
Application number	US-201816146019-A
Country	US
Kind code	B2
Filing date	Sep 28, 2018
Priority date	Dec 24, 2015
Publication date	Oct 1, 2019
Grant date	Oct 1, 2019

Abstract

Described herein are compositions having an eight-membered monocyclic unsaturated hydrocarbon, methods and system to separate the eight-membered monocyclic unsaturated hydrocarbon at from a hydrocarbon mixture including additional nonlinear unsaturated C8H2m hydrocarbons with 4≤m≤8, by contacting the hydrocarbon mixture with a 10-ring pore molecular sieve having a sieving channel with a 10-ring sieving aperture with a minimum crystallographic free diameter greater than 3 Å and a ratio of the maximum crystallographic free diameter to the minimum crystallographic free diameter between 1 and 2, the molecular sieve having a T1/T2 ratio≥20:1 wherein T1 is an element independently selected from Si and Ge, and T2 is an element independently selected from Al, B and Ga, the 10-ring pore molecular sieve further having a counterion selected from NH4+, Na+, K+ and Ca++.

First claim

What is claimed is:

1. A sieved hydrocarbon mixture obtained by separating an eight-membered monocyclic unsaturated hydrocarbon from a hydrocarbon mixture further comprising additional nonlinear unsaturated C 8 H 2m hydrocarbons with 4≤m≤8,
wherein separating the eight-membered monocyclic unsaturated hydrocarbon comprises
providing a 10-ring pore molecular sieve having a sieving channel with a 10-ring sieving aperture with a minimum crystallographic free diameter greater than 3 Å and a ratio of the maximum crystallographic free diameter to the minimum crystallographic free diameter between 1 and 2,
the 10-ring pore molecular sieve having a T1/T2 ratio≥20:1 wherein T1 is an element independently selected from Si and Ge or a combination thereof, and T2 is an element independently selected from Al, B and Ga or a combination thereof,
the 10-ring pore molecular sieve further having a counterion selected from NH 4 + , Li + , Na + , K + and Ca ++ or a combination thereof, and
contacting the hydrocarbon mixture with the 10-ring pore molecular sieve at a temperature of −20° C. to 60° C. for a time and under conditions to obtain a sieved hydrocarbon mixture comprising the eight-membered monocyclic unsaturated hydrocarbon at a separation concentration C s >C i ,

wherein the 10-ring pore molecular sieve has a framework type selected from group consisting of MEL, TUN, IMF, MFI, OBW, MFS and TER, and
wherein, the sieved hydrocarbon mixture comprises the eight-membered monocyclic unsaturated hydrocarbon at a separation concentration Cs≥99.3% wt.

2. The sieved hydrocarbon mixture of claim 1 , wherein the eight-membered monocyclic unsaturated hydrocarbon is selected from

or a combination thereof.

3. The sieved hydrocarbon mixture of claim 1 , wherein the eight-membered monocyclic unsaturated hydrocarbon is

4. The hydrocarbon mixture of claim 1 , wherein in the 10-ring pore molecular sieve is a 10-ring pore intermediate molecular sieve wherein the minimum crystallographic free diameter is equal to or greater than 4.5 Å to less than 5 Å and the ratio of the maximum crystallographic free diameter to the minimum crystallographic free diameter is between 1.1 and 1.25.

5. The hydrocarbon mixture of claim 1 , wherein in the 10-ring pore molecular sieve is a 10-ring pore wide molecular sieve wherein the minimum crystallographic free diameter is equal to or greater than 5.0 Å to less than 6 Å and the ratio of the maximum crystallographic free diameter to the minimum crystallographic free diameter is between 1.0 and 1.1.

6. The hydrocarbon mixture of claim 1 , wherein in the 10-ring pore molecular sieve, the sieving channel is interconnected to one or more sieving channels and/or venting channels to form a 2D channels network.

7. The hydrocarbon mixture of claim 1 , wherein in the 10-ring pore molecular sieve, the sieving channel is interconnected to one or more sieving channels and/or venting channels to form a 3D channels network.

8. The hydrocarbon mixture of claim 1 , wherein the 10-ring pore molecular sieve has a framework type selected from the group consisting of MEL, TUN, IMF, MFI, OBW, and TER.

9. The hydrocarbon mixture of claim 1 , wherein the 10-ring pore molecular sieve is selected from the group consisting of ZSM-5, ZSM-11, IM-5, ZSM-57, OSB-2, Terranovaite, and TNU-9.

10. A hydrocarbon mixture comprising an eight-membered monocyclic unsaturated hydrocarbon and additional nonlinear unsaturated C 8 H 2m hydrocarbons with 4≤m≤8, the eight-membered monocyclic unsaturated hydrocarbon comprised in the hydrocarbon mixture at a concentration of at least 99.5% wt.

11. The hydrocarbon mixture of claim 10 , wherein the eight-membered monocyclic unsaturated hydrocarbon comprised in the hydrocarbon mixture at a concentration of at least 99.7% wt.

12. The hydrocarbon mixture of claim 11 , wherein the eight-membered monocyclic unsaturated hydrocarbon is selected from the group consisting of

or a combination thereof.

13. The hydrocarbon mixture of claim 11 , wherein the eight-membered monocyclic unsaturated hydrocarbon is

14. The hydrocarbon mixture of claim 11 , wherein the eight-membered monocyclic unsaturated hydrocarbon is

15. The hydrocarbon mixture of claim 10 , wherein the eight-membered monocyclic unsaturated hydrocarbon comprised in the hydrocarbon mixture at a concentration of at least 99.8% wt.

16. The hydrocarbon mixture of claim 15 , wherein the eight-membered monocyclic unsaturated hydrocarbon is selected from the group consisting of

or a combination thereof.

17. The hydrocarbon mixture of claim 15 , wherein the eight-membered monocyclic unsaturated hydrocarbon is

18. The hydrocarbon mixture of claim 15 , wherein the eight-membered monocyclic unsaturated hydrocarbon is

19. The hydrocarbon mixture of claim 10 , wherein the eight-membered monocyclic unsaturated hydrocarbon comprised in the hydrocarbon mixture at a concentration of at least 99.9% wt.

20. The hydrocarbon mixture of claim 19 , wherein the eight-membered monocyclic unsaturated hydrocarbon is selected from the group consisting of

or a combination thereof.

21. The hydrocarbon mixture of claim 19 , wherein the eight-membered monocyclic unsaturated hydrocarbon is

22. The hydrocarbon mixture of claim 19 , wherein the eight-membered monocyclic unsaturated hydrocarbon is

23. The hydrocarbon mixture of claim 10 , wherein the eight-membered monocyclic unsaturated hydrocarbon comprised in the hydrocarbon mixture at a concentration of at least 99.99% wt.

24. The hydrocarbon mixture of claim 23 , wherein the eight-membered monocyclic unsaturated hydrocarbon is selected from the group consisting of

or a combination thereof.

25. The hydrocarbon mixture of claim 23 , wherein the eight-membered monocyclic unsaturated hydrocarbon is

26. The hydrocarbon mixture of claim 23 , wherein the eight-membered monocyclic unsaturated hydrocarbon is

27. The hydrocarbon mixture of cla

Assignees

• California Inst Of Techn

Inventors

• Kornfield Julia A
• Davis Mark E
• Wei Ming-Hsin
• Jones Simon C

Classifications

• C08G61/08 Primary

  of carbocyclic compounds containing one or more carbon-to-carbon double bonds in the ring · CPC title

• C08G2261/3323

  derived from other monocyclic systems · CPC title

• C08G2261/122

  statistical · CPC title

• C07C7/13 Primary

  by molecular-sieve technique · CPC title

• C08G2261/11

  Homopolymers · CPC title