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

Patent metadata

Field	Value
Publication number	US-10112878-B2
Application number	US-201615391795-A
Country	US
Kind code	B2
Filing date	Dec 27, 2016
Priority date	Dec 24, 2015
Publication date	Oct 30, 2018
Grant date	Oct 30, 2018

Abstract

Described herein are compositions having an eight-membered monocyclic unsaturated hydrocarbon, methods and system to separate the eight-membered monocyclic unsaturated hydrocarbon from a hydrocarbon mixture including additional nonlinear unsaturated C 8 H 2 m 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 NH 4 + , Li + , Na + , K + and Ca ++ .

First claim

What is claimed is:

1. A method to separate an eight-membered monocyclic unsaturated hydrocarbon at an initial concentration C i , from a hydrocarbon mixture further comprising additional nonlinear unsaturated C 8 H 2m hydrocarbons with 4≤m≤8, the method comprising
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 .

2. The method of claim 1 , wherein the eight-membered monocyclic unsaturated hydrocarbon is an eight-membered monocyclic olefin.

3. The method of claim 1 , wherein the eight-membered monocyclic unsaturated hydrocarbon is one or more of compounds 1 to 10

4. The method of claim 1 , wherein the eight-membered monocyclic unsaturated hydrocarbon is compound 1

5. The method of claim 1 , wherein the additional nonlinear unsaturated C 8 H 2m hydrocarbons with 4≤m≤8, comprise at least one compound having structure of Formula (I)

wherein
represents a single bond, or a double bond;
r1 represents 1 to 4;
R10, R11 and R12 are independently selected from H, C1 to C5 linear, branched or cyclic alkyl, alkenyl, or an alkynyl groups, wherein the R11 and R12 are on a same carbon or a different carbon of a ring, and wherein R10, R11 and R12 together contain (6-r1) carbon atoms;

at least one compound having structure of Formula (II)

wherein
represents a single bond, or a double bond;
r2, r3 and r4 each represents 0 to 4, wherein r2, r3 and r4 together is 2 to 6, and r2+r3, r3+r4 and r2+r4 are 0 to 4;
R20, R21 are independently selected from H, C1 to C4 linear, branched or cyclic alkyl, alkenyl, alkynyl, groups, wherein the R20 and R21 are on a same or a different carbon of a ring and wherein R20 and R21 together contain (6-r2-r3-r4) carbon atoms,

and/or at least one compound having structure of Formula (III)

wherein R30 to R35 are independently selected from H, C1 to C6 linear, branched alkyl, alkenyl, alkynyl, groups, wherein R30 to R35 represent separate groups or any two of R30 to R32 or R33 to R35 include at least one tertiary or quaternary carbon, wherein R30 to R35 together contains 6 carbons.

6. The method of claim 1 , wherein the additional nonlinear unsaturated C 8 H 2m hydrocarbons with 4≤m≤8, comprise 4-vinyl-1-cyclohexene.

7. The method 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 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 between 1.1 and 1.25.

8. The method 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 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.

9. The method 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.

10. The method 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.

11. The method of claim 1 , wherein in the 10-ring pore molecular sieve, T1 is Si and T2 is Al.

12. The method of claim 1 , wherein in the 10-ring pore molecular sieve, T1 is Si and T2 is Al and the ratio of Si to Al is between 50:1 and 80:1.

13. The method of claim 1 , wherein in the 10-ring pore molecular sieve has a framework type selected from MEL, or MFI.

14. The method of claim 1 , wherein in the 10-ring pore molecular sieve is selected from ZSM-5 and ZSM-11.

15. The method of claim 1 , wherein the eight-membered monocyclic unsaturated hydrocarbon is compound 1, and

wherein the additional nonlinear unsaturated C 8 H 2m hydrocarbons with 4≤m≤8 comprise 4-vinyl-1-cyclohexene.

16. 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, with the method of claim 1 , the sieved hydrocarbon mixture comprising the eight-membered monocyclic unsaturated hydrocarbon at a separation concentration Cs≥99.3% wt.

17. The sieved hydrocarbon mixture of claim 16 , wherein the eight-membered monocyclic unsaturated hydrocarbon is

18. 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 99.3% wt, at least 99.5% wt, at least 99.7% wt, at least 99.8% wt, at least 99.9% wt, or at least 99.99% wt.

19. The sieved hydrocarbon mixture of claim 16 , wherein the eight-membered monocyclic unsaturated hydrocarbon is

20. A method to provide a hydrocarbon polymer starting from a hydrocarbon mixture comprising an eight-membered monocyclic unsaturated hydrocarbon and additional nonlinear unsaturated C 8 H 2m hydrocarbons with 4≤m≤8, the method comprising
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 or a combination thereof, and T2 is an element independently selected from Al, B and Ga or a combination thereof,
t

Assignees

• California Inst Of Techn

Inventors

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

Classifications

• C08G2261/122

  statistical · CPC title

• C08G2261/418

  Ring opening metathesis polymerisation [ROMP] · CPC title

• C08G2261/11

  Homopolymers · CPC title

• C08G2261/3323

  derived from other monocyclic systems · CPC title

• C07C7/13 Primary

  by molecular-sieve technique · CPC title