U.S. patent application number 16/997756 was filed with the patent office on 2020-12-03 for molecular sieves mediated unsaturated hydrocarbon separation and related compositions, materials, methods and systems.
The applicant listed for this patent is CALIFORNIA INSTITUTE OF TECHNOLOGY. Invention is credited to Mark E. DAVIS, Simon C. JONES, Julia A. KORNFIELD, Ming-Hsin WEI.
Application Number | 20200377432 16/997756 |
Document ID | / |
Family ID | 1000005030727 |
Filed Date | 2020-12-03 |
View All Diagrams
United States Patent
Application |
20200377432 |
Kind Code |
A1 |
KORNFIELD; Julia A. ; et
al. |
December 3, 2020 |
MOLECULAR SIEVES MEDIATED UNSATURATED HYDROCARBON SEPARATION AND
RELATED COMPOSITIONS, MATERIALS, METHODS AND SYSTEMS
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
C.sub.8H.sub.2m hydrocarbons with 4.ltoreq.m.ltoreq.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 .ANG. 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 .gtoreq.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.sub.4.sup.+, Li.sup.+, Na.sup.+, K.sup.+ and Ca.sup.++.
Inventors: |
KORNFIELD; Julia A.;
(PASADENA, CA) ; DAVIS; Mark E.; (PASADENA,
CA) ; WEI; Ming-Hsin; (PASADENA, CA) ; JONES;
Simon C.; (WHITTIER, CA) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
CALIFORNIA INSTITUTE OF TECHNOLOGY |
Pasadena |
CA |
US |
|
|
Family ID: |
1000005030727 |
Appl. No.: |
16/997756 |
Filed: |
August 19, 2020 |
Related U.S. Patent Documents
|
|
|
|
|
|
Application
Number |
Filing Date |
Patent Number |
|
|
16542238 |
Aug 15, 2019 |
10781150 |
|
|
16997756 |
|
|
|
|
16146019 |
Sep 28, 2018 |
10427995 |
|
|
16542238 |
|
|
|
|
15391795 |
Dec 27, 2016 |
10112878 |
|
|
16146019 |
|
|
|
|
62387373 |
Dec 24, 2015 |
|
|
|
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C08G 2261/3322 20130101;
C07C 7/13 20130101; C08G 61/08 20130101; C08G 2261/122 20130101;
C08G 2261/11 20130101; C08G 2261/418 20130101; C08G 2261/3323
20130101 |
International
Class: |
C07C 7/13 20060101
C07C007/13; C08G 61/08 20060101 C08G061/08 |
Claims
1. A method to separate an eight-membered monocyclic unsaturated
hydrocarbon at an initial concentration C.sub.i, from a hydrocarbon
mixture further comprising additional nonlinear unsaturated
C.sub.8H.sub.2m hydrocarbons with 4.ltoreq.m.ltoreq.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 .ANG. 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 .gtoreq.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.sub.4.sup.+, Li.sup.+,
Na.sup.+, K.sup.+ and Ca.sup.++ or a combination thereof, and
contacting the hydrocarbon mixture with the 10-ring pore molecular
sieve at a temperature of -20.degree. C. to 60.degree. 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.sub.s>C.sub.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
##STR00020##
3. The method of claim 1, wherein the eight-membered monocyclic
unsaturated hydrocarbon is compound 1 ##STR00021##
4. The method of claim 1, wherein the additional nonlinear
unsaturated C.sub.8H.sub.2m hydrocarbons with 4.ltoreq.m.ltoreq.8,
comprise at least one compound having structure of Formula (I)
##STR00022## wherein represents a single bond, or a double bond; r1
represents 1 to 4; R10, R11 and R12 are independently selected from
H, C.sub.1 to C.sub.5 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-r) carbon atoms; at least one compound having structure
of Formula (II) ##STR00023## 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, C.sub.1 to C.sub.4
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)
##STR00024## wherein R30 to R35 are independently selected from H,
C.sub.1 to C.sub.6 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.
5. The method of claim 1, wherein the additional nonlinear
unsaturated C.sub.8H.sub.2m hydrocarbons with 4.ltoreq.m.ltoreq.8,
comprise 4-vinyl-1-cyclohexene.
6. 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
.ANG. to less than 5 .ANG. and the ratio of the maximum
crystallographic free diameter to the minimum crystallographic free
diameter between 1.1 and 1.25.
7. 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 .ANG.
to less than 6 .ANG. and the ratio of the maximum crystallographic
free diameter to the minimum crystallographic free diameter is
between 1.0 and 1.1.
8. 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.
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 3D channels network.
10. The method of claim 1, wherein in the 10-ring pore molecular
sieve, T1 is Si and T2 is Al.
11. 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.
12. The method of claim 1, wherein in the 10-ring pore molecular
sieve has a framework type selected from MEL, or MFI.
13. The method of claim 1, wherein in the 10-ring pore molecular
sieve is selected from ZSM-5 and ZSM-11.
14. The method of claim 1, wherein the eight-membered monocyclic
unsaturated hydrocarbon is compound 1, and ##STR00025## wherein the
additional nonlinear unsaturated C.sub.8H.sub.2m hydrocarbons with
4.ltoreq.m.ltoreq.8 comprise 4-vinyl-1-cyclohexene.
15. A sieved hydrocarbon mixture obtainable by separating an
eight-membered monocyclic unsaturated hydrocarbon from a
hydrocarbon mixture further comprising additional nonlinear
unsaturated C.sub.8H.sub.2m hydrocarbons with 4.ltoreq.m.ltoreq.8,
with the method of claim 1.
16. The sieved hydrocarbon mixture of claim 15, wherein the
eight-membered monocyclic unsaturated hydrocarbon is
##STR00026##
17. A hydrocarbon mixture comprising an eight-membered monocyclic
unsaturated hydrocarbon and additional nonlinear unsaturated
C.sub.8H.sub.2m hydrocarbons with 4.ltoreq.m.ltoreq.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.
18. The sieved hydrocarbon mixture of claim 15, wherein the
eight-membered monocyclic unsaturated hydrocarbon is
##STR00027##
19. A method to provide a hydrocarbon polymer starting from a
hydrocarbon mixture comprising an eight-membered monocyclic
unsaturated hydrocarbon and additional nonlinear unsaturated
C.sub.8H.sub.2m hydrocarbons with 4.ltoreq.m.ltoreq.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 .ANG. 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 .gtoreq.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.sub.4.sup.+, Li.sup.+,
Na.sup.+, K.sup.+ and Ca.sup.++ or a combination thereof, and the
contacting performed at a temperature of -20.degree. C. to
60.degree. C. for a time and under conditions to provide a sieved
hydrocarbon mixture comprising the eight-membered monocyclic
unsaturated hydrocarbon at a separation concentration
C.sub.s.gtoreq.99.3% wt, and contacting the sieved hydrocarbon
mixture with a polymerization catalyst for a time and under
condition to allow the eight-membered monocyclic unsaturated
hydrocarbon to polymerize thus forming the hydrocarbon polymer.
20. The method of claim 19, wherein the eight-membered monocyclic
unsaturated hydrocarbon is an eight-membered monocyclic olefin.
21. The method of claim 19, wherein the eight-membered monocyclic
unsaturated hydrocarbon is compound 1 and/or 2 ##STR00028##
22. The method of claim 19, wherein the eight-membered monocyclic
unsaturated hydrocarbon is compound 1 ##STR00029##
23. The method of claim 19, wherein the additional nonlinear
unsaturated C.sub.8H.sub.2m hydrocarbons with 4.ltoreq.m.ltoreq.8,
comprise at least one compound having structure of Formula (I)
##STR00030## wherein represents a single bond, or a double bond; r1
represents 1 to 4; R10, R11 and R12 are independently selected from
H, C.sub.1 to C.sub.5 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.
24. The method of claim 19, wherein the additional nonlinear
unsaturated C.sub.8H.sub.2m hydrocarbons with 4.ltoreq.m.ltoreq.8,
comprise 4-vinyl-1-cyclohexene.
25. The method of claim 19, 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 .ANG. to less than 5 .ANG. and the ratio of the maximum
crystallographic free diameter to the minimum crystallographic free
diameter is between 1.1 and 1.25.
26. The method of claim 19, 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
.ANG. to less than 6 .ANG. and the ratio of the maximum
crystallographic free diameter to the minimum crystallographic free
diameter is between 1.0 and 1.1.
27. The method of claim 19, 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.
28. The method of claim 19, 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.
29. The method of claim 19, wherein in the 10-ring pore molecular
sieve has a framework type selected from MEL, or MFI.
30. The method of claim 19, wherein in the 10-ring pore molecular
sieve is selected from ZSM-5 and ZSM-11.
31. The method of claim 19, wherein the eight-membered monocyclic
unsaturated hydrocarbon is compound 1 ##STR00031## and the
additional nonlinear unsaturated C.sub.8H.sub.2m hydrocarbons with
4.ltoreq.m.ltoreq.8, comprise 4-vinyl-1-cyclohexene.
32. The method of claim 19, wherein the eight-membered monocyclic
unsaturated hydrocarbon is compound 1 and/or 2 ##STR00032## and the
contacting is performed to provide a co-copolymer of compounds (1)
and (2).
33. A system is described to provide a polymer starting from a
hydrocarbon mixture comprising an eight-membered monocyclic
unsaturated hydrocarbon and additional nonlinear unsaturated
C.sub.8H.sub.2m hydrocarbons with 4.ltoreq.m.ltoreq.8, the system
comprising 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 .ANG. 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 .gtoreq.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.sub.4.sup.+, Li.sup.+, Na.sup.+,
K.sup.+ and Ca.sup.++ or a combination thereof, and a
polymerization catalyst, for sequential use in the method to
provide a polymer comprising at least one eight-membered cyclic
hydrocarbon ring monomer starting from hydrocarbon mixture of claim
19.
Description
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] The present application claims priority to U.S. Provisional
Application No. 62/387,373, entitled "Purification of Cyclic
Olefins" filed on Dec. 24, 2015 with docket number CIT-7400-P, the
content of which is incorporated herein by reference in its
entirety.
FIELD
[0002] The present disclosure relates to molecular sieves mediated
unsaturated hydrocarbon separation and related compositions,
materials, methods and systems.
BACKGROUND
[0003] Separations of chemical mixtures, inclusive of separation of
a substance into its components as well as removal of impurities in
a mixture comprising one or more components of interest, have been
developed and are currently used in a large number of applications
in fields such as medicine and manufacturing.
[0004] Separations differentiate among constituents in a mixture
based on differences in chemical properties or physical properties
such as size, shape, mass, density, or chemical affinity, between
the constituents of a mixture. Separation processes are often
classified according to the particular differences they use to
achieve separation. If no single difference can be used to
accomplish a desired separation, multiple operations will often be
performed in combination to achieve a desired end.
[0005] Despite development of various methods, separation of
mixtures of structurally similar components can still be
challenging.
SUMMARY
[0006] Provided herein are molecular sieves mediated unsaturated
hydrocarbon separation and related materials, compositions, methods
and systems that in several embodiments allow separation of
mixtures of unsaturated hydrocarbons having a similar molecular
weight, molecular structure and/or polarity.
[0007] In particular, methods and systems and related materials and
compositions that are based on the use of a 10-ring pore molecular
sieve to separate an eight-membered monocyclic unsaturated
hydrocarbon from a hydrocarbon mixture further comprising
additional nonlinear unsaturated C.sub.8H.sub.2m hydrocarbons with
4.ltoreq.m.ltoreq.8, The 10-ring pore molecular sieve herein
described has a sieving channel with a 10-ring sieving aperture
with a minimum crystallographic free diameter greater than 3 .ANG.
and a maximum crystallographic free diameter to minimum
crystallographic free diameter ratio between 1 and 2. The 10-ring
pore molecular sieve herein described has a T1/T2 ratio
.gtoreq.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 herein described has a counterion
selected from NH.sub.4.sup.+, Li.sup.+, Na.sup.+, K.sup.+ and
Ca.sup.++ or a combination thereof.
[0008] According to a first aspect, a method to separate an
eight-membered monocyclic unsaturated hydrocarbon at an initial
concentration C.sub.i, from a hydrocarbon mixture further
comprising additional nonlinear unsaturated C.sub.8H.sub.2m
hydrocarbons with 4.ltoreq.m.ltoreq.8, the method comprising
providing a 10-ring pore molecular sieve herein described having a
sieving channel with a 10-ring sieving aperture with a minimum
crystallographic free diameter greater than 3 .ANG. and a ratio of
the maximum crystallographic free diameter to the minimum
crystallographic free diameter between 1 and 2. In the method the
molecular sieve has a T1/T2 ratio .gtoreq.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. In the method the 10-ring pore
molecular sieve further having a counterion selected from
NH.sub.4.sup.+, Li.sup.+, Na.sup.+, K.sup.+ and Ca.sup.++ or a
combination thereof. The method further comprises contacting the
hydrocarbon mixture with the 10-ring pore molecular sieve at a
temperature of -20.degree. C. to 60.degree. 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.sub.s>C.sub.i.
[0009] According to a second aspect, a sieved hydrocarbon mixture
is described that is obtainable by separating an eight-membered
monocyclic unsaturated hydrocarbon from a hydrocarbon mixture
further comprising additional nonlinear unsaturated C.sub.8H.sub.2m
hydrocarbons with 4.ltoreq.m.ltoreq.8, with methods herein
described.
[0010] According to a third aspect, a method is described to
provide an eight-membered monocyclic unsaturated hydrocarbon
starting from precursors of the an eight-membered monocyclic
unsaturated hydrocarbon, the method comprising reacting the
precursors to provide the eight-membered simple-ring cyclic
olefinic hydrocarbon in a hydrocarbon mixture comprising
C.sub.8H.sub.2m nonlinear olefinic hydrocarbons with
4.ltoreq.m.ltoreq.8. The method further comprises contacting the
hydrocarbon mixture with a 10-ring pore molecular sieve herein the
described. In the method, the 10-ring pore molecular sieve has a
sieving channel with a 10-ring sieving aperture with a minimum
crystallographic free diameter greater than 3 .ANG. and a ratio of
the maximum crystallographic free diameter to the minimum
crystallographic free diameter between 1 and 2 In the method, the
10-ring pore molecular sieve has a T1/T2 ratio .gtoreq.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. In the method, the
10-ring pore molecular sieve has the 10-ring pore molecular sieve
further having a counterion selected from NH.sub.4.sup.+, Li.sup.+,
Na.sup.+, K.sup.+ and Ca.sup.++ or a combination thereof. In the
method, the contacting performed at a temperature of -20.degree. C.
to 60.degree. C. for a time and under conditions to provide a
sieved hydrocarbon mixture comprising the eight-membered monocyclic
unsaturated hydrocarbon at a separation concentration
C.sub.s.gtoreq.99.3% wt.
[0011] According to a fourth aspect, a system is described to
provide an eight-membered monocyclic unsaturated hydrocarbon
starting from precursors the eight-membered monocyclic unsaturated
hydrocarbon, the system comprising one or more precursor of the
eight-membered monocyclic unsaturated hydrocarbon; and a 10-ring
pore molecular sieve herein the described. In the system, the
10-ring pore molecular sieve has a sieving channel with a 10-ring
sieving aperture with a minimum crystallographic free diameter
greater than 3 .ANG. and a ratio of the maximum crystallographic
free diameter to the minimum crystallographic free diameter between
1 and 2. In the system, the 10-ring pore molecular sieve has a
T1/T2 ratio .gtoreq.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. In the system, the 10-ring pore molecular sieve has a
counterion selected from NH.sub.4.sup.+, Li.sup.+, Na.sup.+,
K.sup.+ and Ca.sup.++ or a combination thereof. In the system, the
one or more precursors and the 10-ring pore molecular sieve are
comprised for sequential use in the method to provide an
eight-membered monocyclic unsaturated hydrocarbon herein
described.
[0012] According to a fifth aspect, a hydrocarbon mixture
comprising an eight-membered monocyclic unsaturated hydrocarbon and
additional nonlinear unsaturated C.sub.8H.sub.2m hydrocarbons with
4.ltoreq.m.ltoreq.8, the eight-membered monocyclic unsaturated
hydrocarbon comprised in the hydrocarbon mixture at a concentration
of at least 99.3% wt, or 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%.
[0013] According to a sixth aspect, a method is described to
provide a hydrocarbon polymer starting from a hydrocarbon mixture
comprising an eight-membered monocyclic unsaturated hydrocarbon and
additional nonlinear unsaturated C.sub.8H.sub.2m hydrocarbons with
4.ltoreq.m.ltoreq.8, the method comprising contacting the
hydrocarbon mixture with a 10-ring pore molecular sieve herein
described. In the method, the 10-ring pore molecular sieve has a
sieving channel with a 10-ring sieving aperture with a minimum
crystallographic free diameter greater than 3 .ANG. and a ratio of
the maximum crystallographic free diameter to the minimum
crystallographic free diameter between 1 and 2. In the method, the
10-ring pore molecular sieve has a T1/T2 ratio .gtoreq.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. In the method, the
10-ring pore molecular sieve has a counterion selected from
NH.sub.4.sup.+, Li.sup.+, Na.sup.+, K.sup.+ and Ca.sup.++ or a
combination thereof. In the method contacting the hydrocarbon
mixture with a 10-ring pore molecular sieve is performed at a
temperature of -20.degree. C. to 60.degree. C. for a time and under
conditions to provide a sieved hydrocarbon mixture comprising the
eight-membered monocyclic unsaturated hydrocarbon at a separation
concentration C.sub.s.gtoreq.99.3% wt. The method further comprises
contacting the sieved hydrocarbon mixture with a polymerization
catalyst for a time and under condition to allow the eight-membered
monocyclic unsaturated hydrocarbon to polymerize thus forming the
hydrocarbon polymer.
[0014] According to a seventh aspect, a system is described to
provide a polymer starting from a hydrocarbon mixture comprising an
eight-membered monocyclic unsaturated hydrocarbon and additional
nonlinear unsaturated C.sub.8H.sub.2m hydrocarbons with
4.ltoreq.m.ltoreq.8, the system comprising a 10-ring pore molecular
sieve and a polymerization catalyst. In the system the 10-ring pore
molecular sieve has a sieving channel with a 10-ring sieving
aperture with a minimum crystallographic free diameter greater than
3 .ANG. and a ratio of the maximum crystallographic free diameter
to the minimum crystallographic free diameter between 1 and 2. In
the system the 10-ring pore molecular sieve has a T1/T2 ratio
.gtoreq.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.
In the system the 10-ring pore molecular sieve has a counterion
selected from NH.sub.4.sup.+, Li.sup.+, Na.sup.+, K.sup.+ and
Ca.sup.++ or a combination thereof. In the system the 10-ring pore
molecular sieve and the polymerization catalyst are comprised for
sequential use in the method to provide a polymer comprising at
least one eight-membered cyclic hydrocarbon ring monomer starting
from hydrocarbon mixture herein described.
[0015] According to an eighth aspect, a method is described to
provide a hydrocarbon polymer starting from precursors of an
eight-membered monocyclic unsaturated hydrocarbon, the method
comprising reacting the precursors to provide the an eight-membered
monocyclic unsaturated hydrocarbon in a hydrocarbon mixture further
comprising additional nonlinear unsaturated C.sub.8H.sub.2m
hydrocarbons with 4.ltoreq.m.ltoreq.8. The method further comprises
contacting the hydrocarbon mixture with a 10-ring pore molecular
sieve herein described. In the method, the 10-ring pore molecular
sieve has a sieving channel with a 10-ring sieving aperture with a
minimum crystallographic free diameter greater than 3 .ANG. and a
maximum crystallographic free diameter to minimum crystallographic
free diameter ratio between 1 and 2. In the method, the 10-ring
pore molecular sieve has a T1/T2 ratio .gtoreq.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. In the method, the 10-ring pore
molecular sieve has a counterion selected from NH.sub.4.sup.+,
Li.sup.+, Na.sup.+, K.sup.+ and Ca.sup.++ or a combination thereof.
In the method, contacting the hydrocarbon mixture with a 10-ring
pore molecular sieve is performed at a temperature of -20.degree.
C. to 60.degree. C. for a time and under conditions to provide a
sieved hydrocarbon mixture comprising the an eight-membered
monocyclic unsaturated hydrocarbon at a separation concentration
C.sub.s.gtoreq.99.3% wt. The method further comprises contacting
the sieved hydrocarbon mixture with a polymerization catalyst for a
time and under condition to allow the eight-membered monocyclic
unsaturated hydrocarbon to polymerize thus forming the hydrocarbon
polymer.
[0016] According to a ninth aspect, a system is described to
provide a polymer starting from precursors of an eight-membered
monocyclic unsaturated hydrocarbon, the system comprising one or
more precursors of an eight-membered monocyclic unsaturated
hydrocarbon, a 10-ring pore molecular sieve and a polymerization
catalyst. In the system, the 10-ring pore molecular sieve has a
sieving channel with a 10-ring sieving aperture with a minimum
crystallographic free diameter greater than 3 .ANG. and a ratio of
the maximum crystallographic free diameter to the minimum
crystallographic free diameter between 1 and. In the system, the
10-ring pore molecular sieve has a T1/T2 ratio .gtoreq.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. In the system, the
10-ring pore molecular sieve has a counterion selected from
NH.sub.4.sup.+, Li.sup.+, Na.sup.+, K.sup.+ and Ca.sup.++ or a
combination thereof. In the system, the one or more precursors of
an eight-membered monocyclic unsaturated hydrocarbon, the 10-ring
pore molecular sieve and the polymerization catalyst for sequential
use in the method to provide a polymer starting from precursors of
an eight-membered cyclic hydrocarbon ring monomer herein
described.
[0017] The molecular sieves mediated olefin separation method and
related materials, compositions and systems allow in some
embodiments to separate cyclic olefins such as cyclooctene,
cyclooctadiene, cyclooctatriene, cyclooctatetraene and
cyclododecatriene with a higher purity and/or yield compared to
purity and yields achievable with separation performed with
conventional methods.
[0018] The molecular sieves mediated olefin separation herein
described and related materials, compositions, methods and systems,
allow in some embodiments to obtain highly-pure reagents or
monomers that undergo useful reactions with high fidelity.
[0019] In particular, the molecular sieves mediated olefin
separation herein described and related materials, compositions,
methods and systems allow in some embodiments to obtain prepare
highly-pure monomers that polymerize at extremely-low catalyst
loadings to give controlled, high-molecular weight functionalized
polymers with high fidelity.
[0020] The molecular sieves mediated olefin separation herein
described and related materials, compositions, methods and systems
allow in some embodiments to provide simple, cost-effective
purification methods to remove impurities from cyclic olefin
monomers such as cyclooctene, cyclooctadiene and
cyclododecatriene.
[0021] The molecular sieves mediated olefin separation, herein
described and related compositions, materials, methods, and systems
can be used in several embodiments in connection with applications
wherein separation of cyclic olefins with high purity is desirable,
including but not limited to manufacturing of polymers, catalysts
and other fine chemicals suitable to be used in applications such
as fuels and more particularly crude oils and refined fuels, inks,
paints, cutting fluids, drugs, lubricants, pesticides and
herbicides as well adhesive processing aids, personal care products
(e.g. massage oils or other non-aqueous compositions) and
additional applications which are identifiable by a skilled person.
Additional applications comprise industrial processes in which
reduction of flow resistance, mist control, lubrication, and/or
control of viscoelastic properties (for example, to improve the
viscosity index of a non-polar composition) of a non-polar
composition and in particular a liquid non-polar composition is
desired.
[0022] The details of one or more embodiments of the disclosure are
set forth in the accompanying drawings and the detailed description
and examples below. Other features, objects, and advantages will be
apparent from the detailed description, examples and drawings, and
from the appended claims
BRIEF DESCRIPTION OF THE DRAWINGS
[0023] The accompanying drawings, which are incorporated into and
constitute a part of this specification, illustrate one or more
embodiments of the present disclosure and, together with the
detailed description and the examples, serve to explain the
principles and implementations of the disclosure.
[0024] FIG. 1 shows a schematic summary of the features of the
exemplary molecular sieve ZSM-5 from Atlas of Zeolites Framework
Types by Ch. Baerlocher W. M. Meier and D. H Olson, Sixth Edition
Elsevier.
[0025] FIG. 2 shows a schematic summary of the features of the
exemplary molecular sieve Apo-11 from Atlas of Zeolites Framework
Types by Ch. Baerlocher W. M. Meier and D. H Olson, Sixth Edition
Elsevier.
[0026] FIG. 3 shows a schematic summary of the features of
molecular sieve Ferrierite from Atlas of Zeolites Framework Types
by Ch. Baerlocher W. M. Meier and D. H Olson, Sixth Edition
Elsevier.
[0027] FIG. 4 shows proton NMR spectra of a mixture of COD and VCH
before and after borane-tetrahydrofuran (BH.sub.3THF) treatment
using conventional procedure.
[0028] FIG. 5 shows a schematic illustration of an exemplary
implementation of methods herein described wherein the
schematically that VCH passes through pore opening of a zeolite and
was trapped retained inside the pores, in contrast COD is not
absorbed into the pores of the same zeolite, causing removal and
separation of VCH from a mixture containing COD and VCH.
[0029] FIG. 6 shows proton NMR spectra of a mixture of COD and VCH
before and after zeolite ZSM-5 treatment according to some
embodiments of the present disclosure.
[0030] FIG. 7 shows a schematic illustration of a synthesis of
di-TE PCOD via two-stage ROMP of COD as the benchmark reaction for
the influence of the purity of VCH-free COD.
[0031] FIG. 8 shows a synthesis of a CTA with only one tert-butyl
ester on each side (compound 10), with the conditions being: (a)
2.2 eq. of 2 or 2', K.sub.2CO.sub.3, N,N-dimethylformamide (DMF),
80.degree. C., 5 h; (b) 4 eq. of LiAlH.sub.4, THF, R.T., overnight;
(c) 6 eq. of 2 or 2', 6 eq. of PPh.sub.3, 6 eq. of DIAD, THF,
0.degree. C. then 40.degree. C., overnight; (d) 8 eq. of
LiAlH.sub.4, THF, R.T., overnight; (c) 12 eq. of 3, 12 eq. of
PPh.sub.3, 12 eq. of DIAD, THF, 0.degree. C. then 40.degree. C.,
overnight.
[0032] FIG. 9 shows a list of molecular sieves with related
features from Atlas of Zeolites Framework Types by Ch. Baerlocher
W. M. Meier and D. H Olson, Sixth Edition Elsevier.
[0033] FIG. 10 shows TGA results of ZSM-5 23:1, ZSM-5 28:1, ZSM-5
50:1, ZSM-5 80:1, and zeolite ferrierite.
[0034] FIG. 11 shows a schematic diagram of an exemplary process to
convert a precursor to a desired sieved hydrocarbon mixture.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
[0035] Provided herein is a molecular sieve mediated olefin
separation and related materials, compositions, methods and systems
that in several embodiments allow separation of mixtures of cyclic
olefins having a similar molecular weight and molecular
structure.
[0036] The term "molecular sieves" as used herein refers to a
crystalline porous solid having interconnected channels of same or
different sizes defined by rings of tetrahedra forming the
crystalline structure of the solid. A tetrahedron is the basic
building unit of a molecular sieve and each tetrahedron is formed
by a central atom with relatively low electronegativity, e.g.,
Si(IV), Ge(IV) Al(III), B(III), Ga(III), P(V), and Zn(II) (also
identified as T-atom) and oxygen anions occupying the corners of
the tetrahedron. These combinations can be depicted as [Si.sub.4],
[AlO.sub.4], [PO.sub.4], etc.
[0037] In a molecular sieve, the tetrahedra formed by various
combinations of T-atoms according to the material of the sieve, are
linked via the apical oxygen (T-O-T) to form rings of tetrahedra of
different sizes. In general, a ring containing n tetrahedral
T-atoms is called an "n-ring." The most common n-rings contain 4,
5, 6, 8, 10, or 12 tetrahedra, but materials with rings formed of
14, 18, up to 20 tetrahedra have been prepared. Materials with 3-,
7- or 9-rings, are rare as will be understood by a skilled
person.
[0038] In a molecular sieve, the n-rings form part of the
crystalline structure of the molecular sieve also indicated as
crystalline framework of the molecular sieves. Crystalline
frameworks can be grouped according to "framework types" as would
be understood by a skilled person. The term "framework type", as
used herein with reference to of a molecular sieve having a
framework formed by one or more T-atoms indicates the idealized
structure of the framework provided by replacing the T-atoms of the
framework with Si T-atoms only. Accordingly, an unlimited number
molecular sieves with different T-atoms and different compositions
can and do have a same framework type as will be understood by a
skilled person. The structure commission of the International
Zeolite Association (IZA) periodically reviews publications
containing new tetrahedral frameworks and assigns a "three-letter
code" to each distinct new framework type (see e.g. SZR, MTT, TON,
MWW, MFI, ETL, FER, MEL, EUO, LAU and others identifiable by a
skilled person). At the filing date of the present disclosure,
there are at least 176 different framework types with assigned
three-letter codes. Description of a specific molecular sieve
typically includes the framework type and the selection of T-atoms
as will be understood by a skilled person.
[0039] In a molecular sieve, the n-rings forming part of the
crystalline framework) define cavities, channels and other
structures such as chains and cages, as will be understood by a
skilled person.
[0040] The term "cavity" as used herein refers to a polyhedral
enclosure formed by n-rings with the largest of the n-rings forming
the enclosure defining an opening (herein also "aperture`) which
allows the passage of molecules larger than water to move in and
out of the polyhedral enclosure. Accordingly, an "aperture" as used
herein indicate an opening of a cavity which allows the passage of
molecules larger than water to move in and out of the cavity. In a
molecular sieve, cavities can be connected one to another to form
"channels".
[0041] The term "channel" as used herein refers to a plurality of
connected cavities infinitely extended in at least one dimension.
The "minimum aperture" of a channel refers to the smallest aperture
of the channel. The "pore" of a channel refers to the
crystallographic cross section through which a molecule can pass at
the minimum aperture of a channel.
[0042] In a molecular sieve, the minimum aperture of a channel
limits the size of molecules that can diffuse along the channel. In
a sieve, the channel having the largest minimum aperture compared
to the other channels of the sieve, is herein also called "sieving
channel". A sieving channel of a particular molecular sieve has a
minimum aperture herein also indicated as "sieving aperture" which
defines the minimum dimension of the compounds that can be sieved
with that particular molecular sieve. Additional channels can be
comprised in the molecular sieves that interconnect with one or
more sieving channels. Those additional channels can be sieving
channels and/or "venting channels" which are channels other than a
sieving channel that intersects with the sieving channel. Venting
channels provide a path for small adsorbates to leave the sieving
channel. In a molecular sieve, sieving channels and/or venting
channels can be interconnected to form a 3D, or a 2D channel
network. The existence, number and orientation of channels,
including sieving channels, in a particular molecular sieve is
determined by its framework type. The framework type specifies the
number of T-atoms in the n-ring that encloses the minimum aperture
of a channel in any molecular sieve having that framework type.
[0043] In a molecular sieve, channels and in particular sieving
channels can be characterized by their crystallographic diameter.
The "crystallographic diameter" of a channel as used herein
indicates the crystallographic distance between centers of oxygen
atoms at opposite sides of the n-ring that forms the minimum
aperture of a channel. The "crystallographic free diameter" of a
channel as used herein is 2.7 .ANG. less than the crystallographic
diameter of the channel. This value is chosen based on the ionic
radius of oxygen, which is approximately 1.35 .ANG.. In general,
the minimum aperture of a channel is not circular. Therefore, a
channel is usually characterized by two crystallographic free
diameters, and in particular by the diameter defined by the
smallest crystallographic distance between centers of oxygen atoms
at opposite sides of the n-ring that forms the minimum aperture of
a channel (minimum crystallographic free diameter) and the diameter
defined by the largest crystallographic distance between centers of
oxygen atoms at opposite sides of the n-ring that forms the minimum
aperture of a channel (maximum crystallographic free diameter). The
values of minimum and maximum crystallographic diameters are
identifiable by a skilled person. In particular, the minimum and
maximum crystallographic free diameters of the sieving channel for
each specific framework type is tabulated by the Structure
Commission of the International Zeolite Association and described
for example in the periodical publication Atlas of Zeolites
Framework Types, Published regularly by Elsevier. The Sixth Edition
of Atlas of Zeolites Framework Types by Ch. Baerlocher W. M. Meier
and D. H Olson in particular is incorporated herein by reference in
its entirety.
[0044] Molecular sieves can be categorized based on the minimum
aperture of their respective sieving channel. Accordingly, a
molecular sieve in which the sieving channel has minimum aperture
defined by a 8-ring is identified as an "8-ring molecular sieve" or
a "small-pore molecular sieve," and a molecular sieve in which the
sieving channel has a minimum aperture defined by a 10-ring is
identified as a "10-ring molecular sieves" or a "medium-pore
molecular sieve," and a molecular sieve in which the sieving
channel has a minimum aperture defined by a 12-ring is identified
as a "12-ring molecular sieve" or "large-pore molecular sieve." The
precise size and shape of the pore of a specific channel in a
specific molecular sieve depends on the framework type, selection
of T-atoms, counter ion and temperature. Nevertheless, the typical
values of the free diameters show an increasing trend with
increasing numbers of tetrahedra encircling the largest pore of a
channel with "small-pore," "medium-pore" and "large-pore" zeolites
having free diameters of approximately 4.0 .ANG., 5.6 .ANG. and 7.6
.ANG., respectively.
[0045] A schematic of exemplary 10-ring molecular sieves from Atlas
of Zeolites Framework Types by Ch. Baerlocher W. M. Meier and D. H
Olson sixth edition inclusive of information concerning their
respective minimum and maximum crystallographic free diameters are
reported with the respective framework type in FIGS. 1 to 3.
[0046] Molecular sieves in the sense of the disclosure can also be
categorized based on the ratios of the elements which form the
T-atoms of the tetrahedra in view of the actual material forming
the molecular sieve. Several molecular sieves comprise two T-atoms
selected among trivalent, tetravalent or pentavalent elements and
the related structure can be characterized by the related ratio as
will be understood by a skilled person. For example, molecular
sieves in the sense of the disclosure comprise crystalline metal
aluminosilicates having a three-dimensional interconnecting network
of silica and alumina tetrahedrals presenting oxygens on their
apices, also indicated as zeolites as well as additional sieves
such as borosilicates, gallogermanates, and many other materials
that have an open three-dimensional network of 4-connected
tetrahedra. Zeolites, borosilicates, and gallogermanates can be
characterized by the respective Si/Al, Si/B and Ge/Ga ratios as
will be understood by a skilled person.
[0047] Molecular sieves in the sense of the disclosure can comprise
one or more cations also indicated as "counterions" to neutralize
negative charges introduced by having tetrahedrals formed by
trivalent rather than tetravalent T-atoms. Common counterions
include sodium ion (Na.sup.+), potassium ion (K.sup.+), ammonium
ion (NH.sub.4+), calcium ion (Ca.sup.++), and proton (H). Selection
of a proper counterion in a zeolite framework can be achieved, as
understood by a skilled person in the art, by using an aqueous
mineralizing medium with the desired cation in the hydrothermal
synthesis of a zeolite or by subsequent ion exchange (see Cundy and
Cox, Microporous and Mesoporous Materials, 2005, 82(1-2), 1-78).
Typically molecular sieves are synthesized by combining
non-molecular building blocks such as alumina and silica with a
chosen alkali metal hydroxide and water, then incubating the
mixture in the presence of organic chemicals called Structure
Directing Agents (SDAs) in an enclosed environment at an
appropriate temperature in the range 50-200.degree. C. for an
appropriate period of time. The SDA is selected such that it
influences the self-assembly of the molecular sieve toward a
desired framework type. The final structure is a product of
synthetic conditions and post-synthetic treatment, including the
conditions used to decompose and remove the SDA and subsequent ion
exchange to introduce a desired counterion.
[0048] Molecular sieves in the sense of the disclosure can also
comprise water and the molecular sieves can also have a water
content referred to as the weight fraction of water bound to the
interior of a zeolite (such as cavities and channels) by
interactions of physical nature in a zeolite (see Esposito et al.,
Microporous and Mesoporous Materials, 2015, 202, 36-43). The water
content of a zeolite can be experimentally determined by measuring
the weight loss of a zeolite sample due to heating to elevated
temperature (such as 600.degree. C.) under inert atmosphere using
thermal gravimetric analysis (TGA) and additional methods as will
be understood by a skilled person. The ratio of trivalent T-atoms
to tetravalent T-atoms correlates with the number of negatively
charged sites on the inorganic crystal framework. Increasing the
number of charges sites on the framework tends to increase the
amount of water absorbed by a molecular sieve and tends to increase
the difficulty of driving water out of the pores to make them
available for sieving the hydrocarbon molecules of the present
invention.
[0049] Molecular sieves in the sense of the disclosure can be used
in methods and systems herein described to perform separation of an
eight-membered monocyclic ring unsaturated hydrocarbon from a
mixture of unsaturated hydrocarbons as will be understood by a
skilled person.
[0050] The word "separation" as used herein indicates a process
directed to convert a mixture of chemical substances into two or
more distinct product mixtures, at least one of which is enriched
in one or more of the mixture's constituents. In particular, the
word separation as used herein indicates a process that removes,
isolates, separates, enriches or depletes one or more substances
from a mixture by methods that involve differences in the chemical
or physical properties of the substances involved, such as
extraction, distillation, selective sieving, and selective chemical
consumption of undesired components. The goals of performing a
separation process include increasing concentrations of desired
components in a mixture and reducing concentrations of undesired
components that can interfere with an intended application of the
desired component or components in a mixture. While distillation is
the most commonly used method to separate hydrocarbons with
different boiling points, selective adsorption by ordered porous
materials such as a molecular sieve is known to a skilled person in
the art as an effective method to separate hydrocarbon molecules
that have similar molecular weights and boiling points yet
different size or shape. A skilled person in the art can understand
that selective reaction can also be used to separate hydrocarbon
isomers with same molecular weight and difference in boiling points
.ltoreq.30.degree. C. (which is too low to allow efficient
separation using distillation). Approaches to overcome this
difficulty by preferentially consuming the undesired component or
components using a chemical reaction are exemplified in Ji et al.,
Macromolecules 2004, 37, 5485-5489: the fact that terminal double
bonds (also known as vinyl groups) react faster with
borane-tetrahydrofuran (BH.sub.3THF) than non-terminal double bonds
by a factor of 14 was used to remove 4-vinyl-1-cyclohexene (VCH),
which is an isomer of cis,cis-1,5-cyclooctadiene (COD) present in
the commercially available COD at 0.2-0.5 wt % and has a boiling
point 20.degree. C. lower than that of COD, from COD with a 40%
loss of COD in the process.
[0051] The wording unsaturated hydrocarbons as used herein
indicates hydrocarbons that have double or triple covalent bonds
between adjacent carbon atoms. In particular unsaturated
hydrocarbons with at least one carbon-to-carbon double bond are
called alkenes or olefins and those with at least one
carbon-to-carbon triple bond are called alkynes. The word "olefin"
as used herein indicates a compound also called alkene, formed by
hydrogen and carbon and containing one or more pairs of carbon
atoms linked by a double bond. Unsaturated hydrocarbons are more
reactive than alkanes due to the reactivity of the carbon-carbon
double bond or carbon-carbon triple bond and the presence of
allylic C-H centers. Unsaturated hydrocarbons can be classified
based on the number of double bonds or triple bonds in the
compounds (see e.g. monoolefins or monoalkyne, diolefins or
dialkynes, triolefins trialkynes, etc., in which the number of
double bonds or triple bonds per molecule is, respectively, one,
two, three, or some other number). Olefins can also be classified
based on cys-trans-isomerism of H or C atoms with respect to at
least one non-terminal double bond given that fact that a double
bond cannot rotate: if the two hydrogen atoms attached to a
carbon-carbon double bond are on the same side of the said double
bond, the isomer is a cis olefin; if the two hydrogen atoms lie on
opposite side of the double bond, the isomer is a trans olefin.
[0052] Unsaturated hydrocarbons can also be classified as cyclic or
acyclic unsaturated hydrocarbons, in which the double bond is
located between carbon atoms forming part of a cyclic (closed-ring)
or of an acyclic (open-chain) grouping, respectively. In
particular, the wording "cyclic unsaturated hydrocarbons" as used
herein indicates a type of alkene or alkyne hydrocarbon which is
both aliphatic and cyclic, having at least one closed unsaturated
ring of carbon atoms but do not have aromatic character. The term
"monocyclic unsaturated hydrocarbon" or "monocyclic unsaturated
hydrocarbon" as used herein refers to cyclic unsaturated
hydrocarbons where the carbon atoms forming part of a cyclic
grouping are within a single closed ring which has one or more
pairs of carbon atoms linked by a double bond or triple bond.
Examples of monocyclic cycloalkenes are cyclopropene, cyclobutene,
cyclopentene, cyclopentadiene, cyclohexene, cyclohexadiene,
cycloheptene, cycloheptadiene, cyclooctene, cyclooctadiene. Some
cycloalkenes, such as cyclobutene, cyclopentene and cyclooctadiene
can be used as monomers to produce polymer chains. Due to
geometrical considerations, smaller cycloalkenes are typically cis
isomers, even if the term cis tends to be omitted from the names.
In larger rings (from around 8 atoms), cis-trans isomerism of the
double bond can occur.
[0053] The term "bicyclic unsaturated hydrocarbon" as used herein
refers to hydrocarbon compounds in which the carbon atoms forming
part of a cyclic grouping are contained in two rings having at
least one common carbon atom, and at least one pair of carbon atoms
in at least one of the two rings is linked by a double bond or a
triple bond. Structures that have two rings that share one or more
carbon atoms may be designated by specialized names: "spiro" if the
two rings share one carbon atom, "fused" if the two rings share two
adjacent carbon atoms, and "bicycle" if the two rings share
non-adjacent carbon atoms. Examples of C.sub.8H.sub.12 bicyclic
olefins are bicyclo[3.3.0]oct-2-ene and
bicyclo[3.2.1]oct-2-ene.
[0054] Cyclic unsaturated hydrocarbon can be categorized based on
the total number of carbon atoms in the compound which is
indicated. In particular, cyclic or acylic unsaturated carbons have
C.sub.nH.sub.2(n-k-j+1) wherein n is the total number of C atoms in
the unsaturated carbon atoms, k is the degree of unsaturation (1
for a double bond, 2 for a triple bond) in the olefins and j is the
number of rings in the unsaturated hydrocarbon. Cyclic unsaturated
hydrocarbons can be categorized based on the number of carbon atoms
in each of the one or more closed rings of carbon atoms. For
example, unsaturated monocyclic hydrocarbons can be can be
categorized in 10-membered monocyclic unsaturated hydrocarbons,
9-membered monocyclic unsaturated hydrocarbons 8-membered
monocyclic unsaturated hydrocarbons, 6-membered monocyclic
unsaturated hydrocarbons and so on, based on the number of carbon
atoms forming the single ring of the monocyclic unsaturated
hydrocarbon.
[0055] Unsaturated hydrocarbons, and in particular cyclic olefins,
that have a same total number of carbon atoms and a same number of
rings have structure, molecular weight and polarity that are very
similar (within a 5% range) which makes the related separation
particularly challenging. In particular eight-membered monocyclic
unsaturated hydrocarbon can be challenging to separate from
mixtures further including other unsaturated monocyclic
hydrocarbons having the same total number carbon atoms.
[0056] In embodiments herein described, a method is described to
separate eight-membered monocyclic unsaturated hydrocarbon from a
hydrocarbon mixture comprising further comprising additional
nonlinear unsaturated C.sub.8H.sub.2m hydrocarbons with
4.ltoreq.m.ltoreq.8.
[0057] A "hydrocarbon mixture" in the sense of the disclosure
indicates a composition comprising hydrocarbons with various number
of carbon atoms and degree of saturation. Hydrocarbons that can be
part of a hydrocarbon mixture comprise linear branched or cyclic,
alkane, alkene, alkyne as well as aromatic hydrocarbon as will be
understood by a skilled person. A hydrocarbon mixture can be solid,
liquid or gaseous depending on the composition of the mixture.
[0058] In embodiments herein describe a hydrocarbon mixture
comprises C.sub.8H.sub.2m hydrocarbons with 4.ltoreq.m.ltoreq.8,
wherein m=n-k-j+1, which comprises non-linear unsaturated
hydrocarbons having a total of C atoms n=8. Non-linear unsaturated
hydrocarbons of the C.sub.8H.sub.2m hydrocarbons comprise in
particular, cyclic unsaturated hydrocarbons and unsaturated
hydrocarbons with at least one branch, and possibly two, or four
branches. In the hydrocarbon mixture, one of the C.sub.8H.sub.2m
hydrocarbons is an eight-membered monocyclic unsaturated
hydrocarbon and in particular an eight-membered monocyclic
olefin.
[0059] In particular, methods and systems herein embodiments herein
described are directed to separate the eight-membered monocyclic
unsaturated hydrocarbon from the hydrocarbon mixture further
comprising additional nonlinear unsaturated C.sub.8H.sub.2m
hydrocarbons with 4.ltoreq.m.ltoreq.8.
[0060] In particular, in some embodiments, the eight-membered
monocyclic unsaturated hydrocarbon can have one, two, three, or
four double bonds or one or two triple bonds. In particular, in
some embodiments, one or more of the 8-membered monocyclic
unsaturated hydrocarbons can be any one of compounds 1-10.
##STR00001##
[0061] In some embodiments, the hydrocarbon mixture comprises one
or more eight membered monocyclic unsaturated hydrocarbons in
various combinations. The total concentration of the one or more
eight membered monocyclic unsaturated hydrocarbons in a hydrocarbon
mixture to be subjected to separation is herein indicated as
C.sub.i which is the initial concentration of eight membered
monocyclic unsaturated hydrocarbons and can be typically expressed
in terms of weight percent or mole percent.
[0062] In methods herein described the method is directed to
separate eight-membered monocyclic unsaturated hydrocarbon from a
hydrocarbon mixture further comprising additional nonlinear
unsaturated C.sub.8H.sub.2m hydrocarbons with 4.ltoreq.m.ltoreq.8,
which can comprise three-membered, four-membered five-membered and
six-membered monocyclic or bicyclic unsaturated hydrocarbons and in
particular, three-membered, four-membered five-membered and
six-membered monocyclic or bicyclic olefins.
[0063] In some embodiments, the three-membered to six-membered
cyclic olefins can have formula (I)
##STR00002## [0064] wherein [0065] represents a single bond, or a
double bond; [0066] r1 represents 1 to 4; [0067] 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-r) carbon atoms.
[0068] In some embodiments, Formula (I) has a chemical formula of
C.sub.8H.sub.12, wherein r1 is 4, the Formula (I) includes the
Formula (I)(6a) to Formulas (I)(6a) to (I)(6k)
##STR00003## ##STR00004##
[0069] In some embodiments, Formula (I) has a chemical formula of
C.sub.8H.sub.12, and wherein r1 is 3, the Formula (I) includes the
Formula (I)(5a) to Formulas (I)(a) to (I)(5f)
##STR00005##
[0070] In some embodiments, Formula (I) has a chemical formula of
C.sub.8H.sub.12, and wherein r1 is 2, the Formula (I) includes the
Formula (I)(4a) to Formulas (I)(a) to (I)(4g)
##STR00006##
[0071] In some embodiments, Formula (I) has a chemical formula of
C8H10, and wherein r1 is 4, the Formula (I) includes the Formula
(I)(61) to Formulas (I)(6t)
##STR00007##
[0072] In some embodiments, Formula (I) has a chemical formula of
C8H10, and wherein r1 is 3, the Formula (I) includes the Formula
(I)(5g) to Formulas (I)(5j)
##STR00008##
[0073] In some embodiments, Formula (I) has a chemical formula of
C8H10, and wherein r1 is 1, the Formula (I) includes the Formula
(I)(3a) to Formulas (I)(3b)
##STR00009##
[0074] In some embodiments, the three-membered to six-membered
cyclic olefins of a hydrocarbon mixture herein described have
formula (II)
##STR00010## [0075] wherein [0076] represents a single bond, or a
double bond; [0077] 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; [0078] 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.
[0079] In some embodiments, the three-membered to six-membered
cyclic olefins of Formula (II) can have chemical formula of
C.sub.8H12, and in some of these embodiments when r2 equals to 0,
the Formula (II) can include the Formula (II)(a) to Formulas
(II)(d)
##STR00011##
[0080] In some embodiments, the three-membered to six-membered
cyclic olefins of Formula (II) can have chemical formula of
C.sub.8H.sub.12, and Formula (II) and in some of these embodiments
when r2 is 1, the Formula (II) can include the Formula (II)(e) to
Formulas (II)(g)
##STR00012##
[0081] In some embodiments, the three-membered to six-membered
cyclic olefins of Formula (II) can have chemical formula of
C.sub.8H12, and in some of these embodiments when r2 is 2, the
Formula (II) include Formula (II)(j)
##STR00013##
[0082] In some embodiments, the three-membered to six-membered
cyclic olefins of Formula (II) can have chemical formula of
C.sub.8H.sub.10, and in some of these embodiments when r2 is 0,
Formula (II) can include the Formula (II)(k) to Formulas
(II)(p)
##STR00014##
[0083] In some embodiments, the three-membered to six-membered
cyclic olefins of Formula (II) can have chemical formula of
C.sub.8H.sub.10, and in some of these embodiments when r2 is 1, the
Formula (II) includes Formula (II)(s)
##STR00015##
[0084] In some embodiments, C8 acyclic olefins have formula
(III)
##STR00016## [0085] 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.
[0086] In some embodiments, the three-membered to six-membered
cyclic olefins of Formula (III) can have chemical formula of
C.sub.8H.sub.10, and can include compounds of Formula (III)(a) to
Formulas (III)(f)
##STR00017##
[0087] In some embodiments, the three-membered to six-membered
cyclic olefins of Formula (III) C.sub.8H.sub.12, and can include
compounds of Formula (III)(r) to Formulas (III)(v)
##STR00018##
[0088] In methods to separate nonlinear unsaturated hydrocarbon
compounds are separated from the hydrocarbon, the hydrocarbon
mixture is contacted 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 .ANG. and a maximum
crystallographic free diameter to minimum crystallographic free
diameter ratio between 1 and 2.
[0089] In some embodiments, the 10-ring pore molecular sieve can
have a minimum crystallographic free diameter of the sieving
aperture of the sieving channel, equal to or higher than 4.0 .ANG.,
or equal to or higher than 4.5 .ANG., equal to or higher than 5
.ANG., or less than 6 .ANG..
[0090] In some embodiments, the 10-ring pore molecular sieve can
have a maximum crystallographic free diameter to minimum
crystallographic free diameter ratio of the sieving aperture
between 1.1 and 1.20, or between 1.21 to 1.40, or between 1.41 to
1.80.
[0091] In some embodiments, the 10-ring pore molecular sieve can
have a maximum crystallographic free diameter to minimum
crystallographic free diameter ratio of the sieving aperture of
1.1, or 1.25, or 1.5.
[0092] In some embodiments, the 10-ring pore molecular sieve can
have a minimum crystallographic free diameter of the sieving
aperture is equal to or greater than 4.0 .ANG. to less than 4.5
.ANG. and a maximum crystallographic free diameter to minimum
crystallographic free diameter ratio of the sieving aperture of
1.25 to 1.5 (herein 10-ring pore narrow molecular sieve).
[0093] In some embodiments, the 10-ring pore molecular sieve can
have a minimum crystallographic free diameter of the sieving
aperture equal to or greater than 4.5 .ANG. to less than 5 .ANG.
and a maximum crystallographic free diameter to minimum
crystallographic free diameter ratio of the sieving aperture from
1.1 to 1.25 (herein 10-ring pore intermediate molecular sieve).
[0094] In some embodiments, the 10-ring pore molecular sieve can
have a minimum crystallographic free diameter of the of the sieving
aperture equal to or greater than 5.0 .ANG. to less than 6 .ANG.
and a maximum crystallographic free diameter to minimum
crystallographic free diameter ratio of the sieving aperture of 1.0
to 1.1 (herein 10-ring pore wide molecular sieve).
[0095] In some embodiments, in the 10-ring pore molecular sieve the
sieving channel is interconnected with one or more sieving and/or
venting channels. In particular in some embodiments, the
interconnected venting channels can be one or more 10-ring pore
channels or one or more 8-ring pore channels. In some embodiments,
one or more venting channels can be a 10-ring wide channel. In some
embodiments, one or more venting channels can be 10-ring
intermediate channel. In some embodiments, one or more venting
channels can be 8-ring intermediate channel. In some embodiments,
one or more venting channels can be a combination of one or more
10-ring wide channels, 10-ring intermediate channels, and 8-ring
wide channels.
[0096] In preferred embodiments, the one or more sieving and/or
venting channels can be interconnected to form a 2D network and/or
more preferably a 3D network.
[0097] In some embodiments, the 10-ring pore molecular sieve can
have a framework type selected from MEL, TUN, IMF, MFI, OBW, MFS
and TER. In particular, molecular, 10-ring pore molecular sieve can
be MEL or MFI.
[0098] In some embodiments, the 10-ring pore molecular sieve has a
MFI framework having a sieving channel and a venting 10-ring
channel. In some embodiments, the 10-ring pore molecular sieve has
an OBW framework with a sieving channel and one or more venting
channels that are 8-ring channels.
[0099] In some embodiments, the 10-ring pore molecular sieve has a
MEL framework, having equally wide-10-ring sieving channels
interconnected in all three crystallographic directions (the
crystallographic free diameters are 5.3 .ANG..times.5.4 .ANG. for
all of the channels). In some embodiments, the 10-ring pore
molecular sieve has a TUN framework with a wide-10-ring sieving
channel (5.5 .ANG..times.5.6 .ANG.) and a wide-10-ring venting
channel (5.4 .ANG..times.5.5 .ANG.), interconnected to create a
three dimensional interconnected system. In some embodiments, the
10-ring pore molecular sieve has a IMF framework with a 5.5
.ANG..times.5.6 .ANG. sieving channel and a number of venting
channels that are all wide-10-ring channels (ranging from 5.3
.ANG..times.5.9 .ANG. to 4.8 .ANG..times.5.4 .ANG.) that provide a
highly accessible three dimensional network. In some embodiments,
the 10-ring pore molecular sieve has a MFI framework with, which
has a wide-10-ring sieving channel (5.3 .ANG..times.5.6 .ANG.) and
a wide-10-ring venting channel (5.1 .ANG..times.5.5 .ANG.), which
create a three dimensional interconnected system. In some
embodiments, the 10-ring pore molecular sieve has a OBW framework
with a 5.0 .ANG..times.5.0 .ANG. sieving channel that is
interconnected with 8-ring venting channels (the most open of which
is 3.4 .ANG..times.3.4 .ANG.). In some embodiments, In some
embodiments, the 10-ring pore molecular sieve can therefore
preferably have a MEL, TUN, IMF, MFI or OBW frameworks in relation
to maintaining the accessibility of the sieving channels.
[0100] In some embodiments, the 10-ring pore molecular sieve has a
TER framework with a wide-10-ring sieving channel (5.0
.ANG..times.5.0 .ANG.) and intermediate-10-ring venting channel
(4.8 .ANG..times.7.0 .ANG.). In some embodiments, the 10-ring pore
molecular sieve has a MFS framework with a wide-10-ring sieving
channel (5.1 .ANG..times.5.4 .ANG.) with the ability of obstructing
molecules to move out of the sieving channel being limited by the
size of the opening to the 8-ring venting channel (3.3
.ANG..times.4.8 .ANG.).
[0101] In methods herein described, the 10-ring pore molecular
sieve having a T1/T2 ratio .gtoreq.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.
[0102] In some embodiments, the 10-ring pore molecular sieve can
have a T1/T2 ratio between 20:1 and 50:1, between 50:1 and 80:1 or
between 80:1 and 100:1, or between 100:1 and 400:1. In some
embodiments, in the 10-ring pore molecular sieve T1 can be Si. In
some embodiments the 10-ring pore molecular sieve is a zeolite and
T1 is Si and T2 is Al.
[0103] In methods and systems herein described, the 10-ring pore
molecular sieve can further have a counterion selected from
NH.sub.4.sup.+, Li.sup.+, Na.sup.+, K.sup.+ and Ca.sup.++. In
particular in some embodiments, the counterions can be Na.sup.+ and
K.sup.+.
[0104] In some embodiments, the 10-ring pore molecular sieve can be
ZSM-5, ZSM-11 or SUZ-4.
[0105] In some embodiments the molecular sieve can have a water
content. In particular in some embodiments, the 10-ring pore
molecular sieve can further have a water content up to 8% wt. In
some embodiments the molecular sieve can have a water content from
0.1% to 5%. In some embodiments the molecular sieve can have a
water content from 0.1% wt to 2% wt. In some embodiments the
molecular sieve can have a water content from 0.1% wt to 1% wt.
[0106] In methods herein described, contacting the hydrocarbon
mixture with the 10-ring pore molecular sieve herein described is
performed a temperature of -20.degree. C. to 60.degree. C. In
particular, in some embodiments, the contacting can be performed
between -20.degree. C. to 0.degree. C. in some embodiments, the
contacting can be performed between -20.degree. C. to 25.degree. C.
In some embodiments, the contacting can be performed between
25.degree. C. to 60.degree. C. In some embodiments, the contacting
can be performed at room temperature (between 20.degree. C. to
25.degree. C.).
[0107] In methods herein described, contacting the hydrocarbon
mixture with the 10-ring pore molecular sieve herein described is
performed for a time and under conditions to obtain a sieved
hydrocarbon mixture comprising the eight-membered monocyclic
unsaturated hydrocarbon component at a sieved concentration
C.sub.s>C.sub.i. For example, in some embodiments, an
eight-membered monocyclic unsaturated hydrocarbon at an initial
concentration C.sub.i=70% with methods herein described can be
included in a sieved hydrocarbon mixture at a C.sub.s=85.2%. In
some embodiments, an eight-membered monocyclic unsaturated
hydrocarbon at an initial concentration C.sub.i=80% with methods
herein described can be included in a sieved hydrocarbon mixture at
a C.sub.s=99.2%. In some embodiments, an eight-membered monocyclic
unsaturated hydrocarbon at an initial concentration C.sub.i=99.2%
with methods herein described can be included in a sieved
hydrocarbon mixture at a C.sub.s=99.9%. An exemplary eight-membered
monocyclic unsaturated hydrocarbon is provided by
cis,cis,1,5-cyclooctadiene which can have a C.sub.i of 80% to 99.25
and can have a C.sub.s of 99.3% to 99.9%, or a C.sub.s of 99.91 to
99.99% wt.
[0108] In particular, in some embodiments, contacting the
hydrocarbon mixture with the 10-ring pore molecular sieve can be
performed under an inert atmosphere and in particular under
nitrogen or argon. In particular, in some embodiments, contacting
the hydrocarbon mixture with the 10-ring pore molecular sieve can
be performed under oxygen-free conditions.
[0109] In some embodiments, methods and systems herein provided
comprise reacting precursors of the eight-membered monocyclic
unsaturated hydrocarbon to provide to provide the eight-membered
simple-ring cyclic olefinic hydrocarbon component in the
hydrocarbon mixture herein described which is a hydrocarbon mixture
comprising C.sub.8H.sub.2m nonlinear olefinic hydrocarbons with
4.ltoreq.m.ltoreq.8.
[0110] Precursors of an eight-membered monocyclic unsaturated
hydrocarbons herein described comprise 1,3-butadiene, acetylene
(also known as ethyne), 1,5-hexadiene, barrelene,
cis,1,2-divinylcyclobutane, and 1,9-decadiene.
[0111] Reactions that can result in an eight-membered monocyclic
unsaturated hydrocarbon herein described comprise nickel catalyst
mediated dimerization, nickel cyanide/calcium carbide mediated
tetramerization, photolysis of barrelene, catalyzed Cope
rearrangement, uncatalyzed Cope rearrangement, partial
hydrogenation of an eight-membered monocyclic unsaturated
hydrocarbon, and ring-closing metathesis.
[0112] For example, in some embodiments, performing nickel catalyst
mediated dimerization of 1,3-butadiene provides an first
hydrocarbon mixture of cis,cis,1,5-cyclooctadiene, 4
vinyl-1-cyclohexene and cis-1,2-divynil-cyclo butane. Hydrogenation
of the first hydrocarbon mixture results in a second mixture
cis,cyclooctene ethyl-cyclohexane, cyclooctane and 1,2 diethyl
cyclobutane. The first mixture or the second mixture can then be
contacted with a 10-ring pore molecular sieve herein described to
obtain a sieved mixture wherein either the
cis,cis,1,5-cyclooctadiene (sieved first mixture) or a
eight-membered monocyclic unsaturated hydrocarbon component
comprising cis, cyclooctene and cyclooctane (sieved second
mixture).
[0113] In embodiments herein described the methods of the
disclosure, result in a hydrocarbon mixture wherein the
eight-membered monocyclic unsaturated hydrocarbon is comprised at a
separation concentration of at least 99.3% wt and possibly at least
99.5% wt, at least 99.7% wt, at least 99.8% wt or at least 99.9%
wt. Concentration of an eight-membered monocyclic unsaturated
hydrocarbon can be measured by proton NMR or gas chromatography
(GC) or additional techniques identifiable by a skilled person.
[0114] In some embodiments, methods and systems herein described
allow production of a hydrocarbon mixture comprising
cis,cis,1,5-cyclooctadiene at least 99.3% wt and possibly at least
99.5% wt, at least 99.7% wt, at least 99.8% wt or at least 99.9%
wt. In some embodiments, methods and systems herein described allow
production of a hydrocarbon mixture comprising
cis,cis,1,5-cyclooctadiene 99.9%.
[0115] In some embodiments, the sieved hydrocarbon mixture can be
further reacted with other reagents to remove one or more undesired
compounds from the mixture. For example, in some embodiments the
sieved hydrocarbon mixture can be further contacted with a
synthetic magnesium silicate (such as commercially available
Magnesol.RTM.) at room temperature to selectively remove peroxides
and hydroperoxides present in the sieved mixture (see Nickel et
al., Topics in Catalysis, 2012, 55(7-10), 518-523). When exposed to
air, eight-membered monocyclic unsaturated hydrocarbon react with
oxygen and thus form peroxides and/or hydroperoxides at trace
levels. Therefore, in some embodiments, synthetic magnesium
silicates can be used in combination with a molecular sieve to
further purify an eight-membered monocyclic unsaturated hydrocarbon
and in particular an eight-membered monocyclic cycloolefin.
[0116] In some embodiments, the sieved hydrocarbon mixture herein
described can be used in various reactions and chemical processes
starting from eight-membered monocyclic unsaturated hydrocarbons,
such as ring-opening metathesis polymerizations to synthesize
functional polymers and complexation with transition metals (such
as nickel, ruthenium, iridium) to form metathesis catalysts,
hydrogenation catalysts for unsaturated compounds and polymers,
carbon-carbon bond forming catalysts, and carbon-hydrogen bonding
activating catalyst. In some embodiments, sieved hydrocarbon
mixture can be subjected to oxidation reaction using ozone,
followed by further chemical transformations to intermediates such
as cycloketones, cyclic oximes, cyclic lactams, and linear
functional eight-carboned compounds that can be further used to
synthesize intermediates and products for agricultural,
pharmaceutical, and textile industries. In particular, in some
embodiments sieved eight-membered monocyclic unsaturated
hydrocarbons can be used to synthesize caprolactam, which can be
polymerized and form Nylon 8 polymers or be used to synthesize
polyurethane polymers. For example in embodiments where the sieved
hydrocarbon mixture includes eight membered monocyclic olefins,
additional reactions comprise ring-opening polymerizations to
synthesize functional polymers and complexation with transition
metals to prepare catalysts or intermediates for such
catalysts.
[0117] In particular, in exemplary embodiments, wherein the
eight-membered monocyclic olefin is 1,3,5,7-Cyclooctatetraene
(compound 7 or COT), the 1,3,5,7-Cyclooctatetraene can react with
potassium metal to form the corresponding salt K2COT in which the
COT exists as an aromatic dianion. In additional exemplary
embodiments, 1,3,5,7-Cyclooctatetraene reacts with suitable
transition metals to form corresponding organometallic complexes
sandwich compounds such as U(COT)2 (uranocene), and Fe(COT)2.
[0118] Additional reactions that can be performed with sieved
hydrocarbon mixture including eight membered monocyclic olefins,
comprise ring-opening polymerizations to synthesize functional
polymers and complexation with transition metals to prepare
catalysts or intermediates for such catalysts.
[0119] In some embodiments, the sieved hydrocarbon mixture herein
described can be used in polymerization processes. In particular in
some embodiments a sieved hydrocarbon mixture and in particular a
hydrocarbon mixture comprising a suitable eight-membered monocyclic
unsaturated hydrocarbon at least 99.3% wt and possibly at least
99.5% wt, at least 99.7% wt, at least 99.8% wt or at least 99.9% wt
can be contacted with a polymerization catalyst for a time and
under condition to allow the eight-membered monocyclic unsaturated
hydrocarbon to polymerize thus forming the hydrocarbon polymer.
[0120] In some embodiments, the sieved hydrocarbon mixture can be
treated with a synthetic magnesium silicate to eliminate undesired
interference with the catalyst by peroxides and hydroperoxides
before contacting the sieved hydrocarbon mixture with the
polymerization catalyst. In some of those embodiments pretreating
with a synthetic magnesium silicate can results in a polymerization
reaction with a lower required catalyst loading and a better
conversion of the sieved hydrocarbon mixture.
[0121] In several embodiments, a hydrocarbon polymer can be
provided starting from a hydrocarbon mixture of C.sub.8H.sub.2m
hydrocarbons with 4.ltoreq.m.ltoreq.8, the hydrocarbon mixture
comprising an eight-membered monocyclic unsaturated hydrocarbon at
an initial concentration C.sub.i together with at least one
additional nonlinear unsaturated C.sub.8H.sub.2m hydrocarbons with
4.ltoreq.m.ltoreq.8 compound.
[0122] In the method, the hydrocarbon mixture is contacted with a
10-ring pore molecular sieve herein described at a temperature of
-20.degree. C. to 60.degree. C. for a time and under conditions to
provide a sieved hydrocarbon mixture comprising the eight-membered
monocyclic unsaturated hydrocarbon at a separation concentration Cs
higher than the initial concentration Ci. In particular in some
embodiments, the separation concentration Cs can be
C.sub.s.gtoreq.99.3% wt.
[0123] In some embodiments, the contacting of the hydrocarbon
mixture with a 10-ring pore molecular sieve herein described can be
performed by a selective sieving process carried out in a
continuous manner. In particular in some embodiments, a stream of
hydrocarbon mixture can be continuous fed into a fluidized bed
packed with a 10-ring pore molecular sieve herein described or a
column packed with a desired 10-ring pore molecular sieve herein
described to remove the undesired components and the exit
hydrocarbon mixture stream can be fed into a subsequent
polymerization reactor along with streams of other components
required in the polymerization reaction, such as a solvent, one or
more catalysts, one or more chain-transfer agents (CTAs). In some
embodiments, the exit hydrocarbon mixture stream can be also split
and fed into more than one continuous polymerization reactors to
perform multi-stage polymerization reactions of sieved unsaturated
hydrocarbons and in particular sieved cycloolefins. The resulting
sieved hydrocarbon mixture contacted with a polymerization catalyst
for a time and under condition to allow the eight-membered
monocyclic unsaturated hydrocarbon to polymerize thus forming the
hydrocarbon polymer.
[0124] In some embodiments, the resulting sieved eight-membered
monocyclic unsaturated hydrocarbon's stream is met with a stream of
a polymerization catalyst solution in a solvent suitable for the
polymerization reaction at the entrance of a plug-flow type reactor
(or a cylindrical-shaped reactor packed with static mixers) which
allows sufficient mixing of the streams and the eight-membered
monocyclic unsaturated hydrocarbon to polymerize thus forming the
hydrocarbon polymer. Optionally a stream of functional CTA solution
can be fed into the reactor if telechelic hydrocarbon polymers are
the desired products. The volume and temperature of the
polymerization can be determined using the kinetics data of the
polymerization reaction and the projected production rate. In the
case all interfering impurities in the eight-membered monocyclic
unsaturated hydrocarbon stream are completely sieved before the
stream enters the polymerization reactor, a lower catalyst loading
is needed and higher reaction rate can be observed, and as a result
the polymerization reactor can be more compact, as will be
understood by a skilled person.
[0125] In some embodiments, the polymerization reactor can provide
sufficient mixing of the eight-membered unsaturated hydrocarbon
stream with the catalyst solution and optionally the functional CTA
solution streams, and the combined stream exiting the
polymerization reactor enters collection vessels where the
polymerization reaction goes to completion. In some embodiments,
telechelic polymers of weight-average molecular weight .gtoreq.400
kg/mol are desired products, and the corresponding polymerization
is performed in a two-stage manner, which requires a two-stage
reactor as the polymerization reactor.
[0126] In some embodiments, the sieved eight-membered monocyclic
unsaturated hydrocarbon stream can be split and fed into both the
first and the second stages at desired flow rates. The
eight-membered monocyclic unsaturated hydrocarbon stream entering
the first stage is met with the catalyst solution stream and the
functional CTA solution stream at the entrance, and the catalyst
reacts with the eight-membered monocyclic unsaturated hydrocarbon
and the CTA in the first stage reactor to form a macro
chain-transfer agent (MCTA) stream. The volume of the first-stage
reactor is selected to provide sufficient retention time that
allows <5% of the functional CTA to remain unreacted in the exit
MCTA stream. The sieved eight-membered monocyclic unsaturated
hydrocarbon stream entering the second-stage reactor is met with
the MCTA stream, and optionally a solvent stream and catalyst
solution stream at the entrance of the second-stage reactor, and
the combined stream forms a chain-extension reactive mixture inside
the second-stage reactor. The volume of the second-stage reactor is
selected to provide complete mixing for the entering streams. The
combined stream exiting the second-stage reactor is collected
subsequently in vessels, where the polymerization reaction goes to
completion.
[0127] In some embodiments the hydrocarbon mixture is continuously
passed through a sieving unit packed with a 10-ring pore molecular
sieve, and the exiting sieved mixture is fed into a fluidized bed
packed with a synthetic magnesium silicate or a column packed with
a synthetic magnesium silicate to selectively remove peroxides and
hydroperoxides from the sieved olefin mixture stream. In some
embodiments, after peroxides and hydroperoxides are removed by a
synthetic magnesium silicate the sieved olefin mixture stream is
fed into a desiccating unit in order to remove moisture introduced
into the olefin mixture by treating the olefin mixture with a
synthetic magnesium silicate that is not desiccated prior to
use
[0128] In some embodiments of the methods and systems herein
described, use of a sieved hydrocarbon mixture comprising an
eight-membered monocyclic unsaturated hydrocarbon allows performing
polymerization while minimizing impurity-related interference with
catalyst in the polymerization of sieved eight-membered monocyclic
unsaturated hydrocarbon and leads to desired effects such as a
lower required catalyst loading, better control on the monomer
conversions and molecular weights of the resulting polymers, and
lower production cost of polymers from sieved cycloolefins. An
exemplary polymerization process starting from a hydrocarbon
mixture in the sense of the present disclosure is the ring-opening
metathesis polymerization of sieved cis,cis-1,5-cyclooctadiene
(COD) in the presence of a functional chain-transfer agent (CTA),
as will be understood by a skilled person in the art (Example 3 and
Example 6).
[0129] Methods and systems herein described allow in some
embodiments performing a separation which is useful for obtaining
various unsaturated eight-membered monocyclic unsaturated
hydrocarbons and in particular, eight-membered monocyclic olefins
with arbitrarily low concentrations of any of the hundreds of
isomers of identical molar mass, but with topology that includes
three to six membered rings and branched acyclic olefins. The
separation can be performed under conditions that preserve the
unsaturation of unsaturated hydrocarbon and in particular
cycloolefins for their use as chemical intermediates or ligands.
Use of molecular sieves that have low catalytic activity permits
recovery of the separated olefins in a form that is free of simple
ring olefins.
[0130] In some embodiment, hydrocarbon mixtures, 10-ring pore
molecular sieves, precursor of eight-membered monocyclic
unsaturated hydrocarbon, additional reagents to perform the
reaction resulting in eight-membered monocyclic unsaturated
hydrocarbon, one or more polymerization catalysts and/or synthetic
magnesium silicate can be included in one or more systems to
perform methods herein described. In some embodiments, the systems
can be provided in the form of combination or kit of parts.
[0131] Additional materials and related methods and systems,
comprising for example kit of parts or related material herein
described, comprising suitable reagents, vehicles or compositions,
are identifiable by a skilled person upon reading of the present
disclosure.
[0132] In particular, further details concerning the hydrocarbon
mixtures, catalysts and molecular sieves and generally
manufacturing and packaging of the compositions and/or the kit, can
be identified by the person skilled in the art upon reading of the
present disclosure.
EXAMPLES
[0133] The hydrocarbon molecules, molecular sieves and related
hydrocarbon mixtures, materials compositions, methods and systems
herein described are further illustrated in the following examples,
which are provided by way of illustration and are not intended to
be limiting.
[0134] The following experimental procedures and characterization
data (.sup.1H and, GPC) were used for all compounds and their
precursors exemplified herein.
[0135] General Information. Chemical shifts for both .sup.1H and
.sup.13C spectra are reported in per million (ppm) relative to
Si(CH3)4 (.delta.=0) and referenced internally to the proteo
solvent resonance.
[0136] Materials and Methods. All chemical reagents were obtained
at 99% purity from Sigma-Aldrich, Alfa Aesar, or Mallinckrodt
Chemicals. Magnesol.RTM. XL was purchased from The Dallas Group of
America, Inc. .sup.1H-NMR spectra were obtained using a Varian
Inova 500 spectrometer (500 MHz); all spectra were recorded in
CDCl.sub.3. Chemical shifts were reported in parts per million
(ppm) and were referenced to residual proteo-solvent resonances.
Deuterated solvent used for .sup.1H-NMR experiments (CDCl.sub.3)
was purchased from Cambridge Isotope Laboratories.
Example 1: Removal of VCH from cis,cis-1,5-cyclooctadiene Using
Conventional Process
[0137] In an exemplary conventional purification procedure,
redistilled-grade cis,cis-1,5-cyclooctadiene (COD, 72.3 g, 0.67
mol) containing trace amount (.ltoreq.0.4 wt %) of
4-vinyl-1cyclohexene was syringe-transferred to a 250 ml Schlenk
flask in an ice bath at 0.degree. C. under argon atmosphere. Under
argon flow, 1-Molar borane-tetrahydrofuran complex in THF
(BH.sub.3THF, 108 mL, 0.11 mol) was slowly added into the flask
through an additional funnel over a period of 10 minutes. The flask
was taken out of the ice bath, and left to stir under argon
atmosphere at room temperature for 2 hrs. Remaining COD was
vacuum-distilled off the reaction mixture at 40.degree. C. and 100
mTorr.
[0138] Proton NMR spectrum of the resulting COD shows the
concentration of VCH is below the detection limit of NMR (.about.50
ppm) and some residual THF as shown in FIG. 4. The amount of
residual THF in COD was further reduced by subjecting the VCH-free
COD to reduced pressure (100 mTorr) at room temperature for 24 hrs,
and proton NMR analysis showed the concentration of THF was below
500 ppm. The yield of COD after evaporation of THF was 58%.
[0139] It was therefore concluded that the VCH passes through pore
opening of a zeolite and was trapped retained inside the pores, in
contrast COD is not absorbed into the pores of the same zeolite,
causing removal and separation of VCH from a the initial mixture
containing COD and VCH as schematically illustrated in FIG. 5.
Accordingly the sieving process resulted in a sieved mixture
enriched in COD as will be understood by a skilled person.
Example 3: Selective Adsorption of VCH from COD by a ZSM-5
Zeolite
[0140] Redistilled-grade cis,cis-1,5-cyclooctadiene (COD, 100 ml)
containing trace amount (.ltoreq.0.4 wt %) of 4-vinyl-1cyclohexene
(VCH) was syringe-transferred to a 250 ml Schlenk flask containing
10 grams of non-dried ZSM-5 (Si/Al=50, ammonium counterions) under
argon atmosphere. The mixture was stirred under argon atmosphere at
room temperature for 12 hrs.
[0141] The liquid was vacuum-distilled off from the mixture at
35.degree. C. and 100 mTorr, and the yield was 96%. Proton NMR
analysis of the distillate showed no detectable presence of VCH in
COD as illustrated in FIG. 6. The cost of treating the given amount
of COD with the selected zeolite is <50% of that of the same
amount of monomer.
Example 4: ROMP of COD Purified by ZSM-5 Treatment
[0142] Synthesis of di-TE PCOD (FIG. 7) was selected to test the
performance of ZSM-5 treated COD in two-stage ROMP in the presence
of a di-TE CTA (compound 8 in FIG. 8). VCH-free COD was prepared
according to the purification procedure described above in Example
3. A total COD-to-CTA ratio of 10,000:1 was used, and 100
equivalents of COD was used in the first-stage reaction, macro-CTA
synthesis, where a 30:1 CTA-to-Grubbs II ratio was used.
Specifically, 5.4 mg of the di-TE CTA (3.7 .mu.mol) was dissolved
in 1 mL of degassed dichloromethane (DCM) in a 100-mL Schlenk flask
under argon atmosphere, followed by the addition of 0.04 g of ZSM-5
treated COD (366 .mu.mol) and 0.1 mL of 1 mg/mL Grubbs II solution
in DCM. The mixture was stirred at 40.degree. C. for 1 hr. 3.96 g
of ZSM-5 treated COD (36.2 mmol) along with 8 mL of degassed DCM
were added to the Schlenk flask to start the chain extension
reaction. 5 minutes later, an aliquot was taken for NMR analysis,
and 50 mL of oxygenated DCM was added into the flask to terminate
the reaction. Proton NMR analysis showed the conversion of COD was
50%, and gel-permeation chromatography analysis in conjunction with
multi-angel laser light scattering (GPC-MALLS) showed the
weight-average molecular weight (M.sub.w) of the resulting di-TE
PCOD was 1,050 kg/mol (PDI=1.5). Under same conditions and
conversion of COD, BH.sub.3THF treated COD could only afford an
M.sub.w.ltoreq.500 kg/mol. A skilled person will understand that
purifying COD with ZSM-5 improves control of molecular weight in
the ROMP procedure, which cannot be achieved in ROMP of COD treated
with BH3 THF.
Example 5: Removal of Peroxides and Hydroperoxides from ZSM-5
Treated COD
[0143] 100 mL of ZSM-5 treated COD from Example 3 was stirred with
10 grams of oven-dried synthetic magnesium silicate,
Magnesol.RTM.-XL, under argon atmosphere at room temperature for 12
hours to remove peroxides and hydroperoxides from the olefin. The
liquid was separated from the adsorbent via vacuum distillation at
35.degree. C. with a yield.gtoreq.95%. The cost is <1% the cost
for the same amount of monomer. Magnesol.RTM.-XL treatment improves
activity of catalyst and thus conversion of COD in ring-opening
metathesis process.
Example 6: Comparative Study of ROMP of COD Treated with
BH.sub.3THF/5/Magnesol.RTM.-XL and ZSM-5/Magnesol.RTM.-XL
Procedures
[0144] To demonstrate the advantage of the invented method of
selective adsorption of undesired unsaturated hydrocarbons from a
desired eight-membered monocyclic unsaturated hydrocarbon, VCH-free
COD was prepared according to the purification procedure described
above in Examples 3 and 5, and the method of selective chemical
consumption of VCH by BH.sub.3THF described in Example 2 was used
to prepare VCH-free COD as the control. The synthesis of di-DE PCOD
via the two-stage ROMP of COD in the presence of a di-DE CTA, as
shown below, was selected to further benchmark the performance of
two different purification methods for COD:
##STR00019##
[0145] In the ROMP procedure, a total COD-to-CTA ratio of 2000:1, a
total CTA-to-catalyst (here 2.sup.nd generation Grubbs catalyst) of
30:1, and a total concentration of COD in DCM of 2.52 M were used.
50 equivalents of COD (treated with ZSM-5 and Magnesol.RTM.-xl)
were used in the first stage of ROMP to react with the CTA, and the
remaining 1950 equivalents of COD (treated with ZSM-5 and
Magnesol.RTM.-xl) were used in the second stage reaction.
Specifically, 11.7 mg of di-DE CTA was dissolved in 2 mL of
degassed DCM in a 100 mL Schlenk flask, followed by the addition of
0.1 g of VCH-free COD and 0.52 mL of 1 mg/mL Grubbs II solution in
degassed DCM. The mixture was stirred under argon atmosphere at
40.degree. C. for 1 hr. 3.9 g of VCH-free COD and 6 mL of degassed
DCM were subsequently added into the Schlenk flask to start the
second stage chain extension reaction. The reaction mixture was
left to stir at 40.degree. C. for 15 hrs, and aliquots were taken
for proton NMR and GPC-MALLS analysis. The same procedure was
repeated using COD treated with BH.sub.3THF and
Magnesol.RTM.-xl.
[0146] Results of the comparative study are shown in Table 1
below:
TABLE-US-00001 TABLE 1 Monomer Treatment Conv. Of COD (%) M.sub.w
(kg/mol) PDI BH.sub.3-THF 95 176 1.47 ZSM-5 + Magnesol 100 318
1.49
[0147] The ROMP procedure using COD treated with ZSM-5 and
Magnesol.RTM.-xl gave 100% conversion of COD, and the M.sub.n
(=M.sub.w/PDI) of the resulting polymer, 213 kg/mol, agreed very
well with the predicted value (i.e., molecular weight of
COD.times.2000). On the other hand, the reaction using COD treated
with BH.sub.3THF could achieve only 95% conversion of COD, and the
M.sub.w of the resulting polymer was 176 kg/mol, 55% of that from
the zeolite-purified COD. Besides, the M.sub.n of the resulting
polymer, 120 kg/mol, did not agree with the initial COD/CTA ratio,
indicating that undesired secondary metathesis reactions took place
along with the primary polymerization reaction. A skilled person
can understand that purifying COD with ZSM-5 and Magnesol.RTM.
enables control of molecular weight in the ROMP procedure by
adjusting the ratio of COD to CTA, which cannot be seen in ROMP of
COD treated with BH.sub.3THF and Magnesol.RTM.-xl.
Example 7: Comparative Study of ROMP of COD Purified by ZSM-5 Alone
and COD by ZSM-5/Magnesol.RTM.-xl
[0148] COD was purified according to the purification procedure
described above in Example 3. A portion of the zeolite-treated COD
was further purified using the procedure described in Example 5.
Synthesis of di-TE PCOD (FIG. 7) via two-stage ROMP in the presence
of a di-TE CTA (compound 8 in FIG. 8) was selected to benchmark the
performance of COD purified with ZSM-5 only and COD purified with
ZSM-5 and Magnesol.RTM.-xl. A total COD-to-CTA ratio of 4,000:1 was
used, and 50 equivalents of COD were used in the first-stage
reaction, macro-CTA synthesis, where a 30:1 CTA-to-Grubbs II ratio
was used. Specifically, 33.5 mg of the di-TE CTA (22.9 .mu.mol) was
dissolved in 3 mL of degassed dichloromethane (DCM) in a 250-mL
Schlenk flask under argon atmosphere, followed by the addition of
0.125 g of COD treated with ZSM-5 only (1.14 mmol) and 0.65 mL of 1
mg/mL Grubbs II solution in DCM. The mixture was stirred at
40.degree. C. for 30 min. 9.875 g of COD treated with ZSM-5 only
(36.2 mmol) along with 22 mL of degassed DCM were added to the
Schlenk flask to start the chain extension reaction. 16 hrs later,
aliquots were taken for proton NMR and GPC-MALLSs analysis, and 200
mL of oxygenated DCM was added into the flask to terminate the
reaction. The same polymerization procedure described here was
applied to the COD purified with ZSM-5 and Magnesol.RTM.-xl.
Results of the comparative study are shown in Table 2 below:
TABLE-US-00002 TABLE 2 Monomer Treatment Conv. Of COD (%) M.sub.w
(kg/mol) PDI ZSM-5 + Magnesol-XL 98 666 1.50 ZSM-5 Only 90 650
1.53
[0149] The results in Table 2 indicate that removal of peroxides
and hydroperoxides from COD using Magnesol.RTM.-xl can mitigate
catalyst interference and thus improve the conversion of COD in the
two-stage procedure. The benefit of and Magnesol.RTM.-xl for COD
purified using ZSM-5 is much greater than the benefit of and
Magnesol.RTM.-xl for COD purified using BH.sub.3THF.
Example 8: Regeneration ZSM-5
[0150] Zeolite adsorbent, ZSM-5, of example 3 is re-generated by
desorption of VCH using steam treatment. The ZSM-5 of example 2 was
steamed at 700.degree. C. to 1450.degree. F. (700.degree. C.) for
5-15 hours in 10-45% steam/90-55% air, at atmospheric pressure to
be regenerated for repeated use.
Example 9: GPC-MALLS for Characterization of Polymers
[0151] MALLS, i.e. Multi-angle Laser Light Scattering, was used in
conjunction with GPC to determine the molecular weights and
polydispersity of the polymers. The system used a Wyatt DAWN EOS
multi-angle laser light scattering detector (.lamda.=690 nm) with a
Waters 410 differential refractometer (RI) (.lamda.=930 nm)
connected in series. Chromatographic separation by the size
exclusion principle (largest comes out first) was achieved by using
four Agilent PLgel columns (pore sizes 10.sup.3, 10.sup.4,
10.sup.5, and 10.sup.6 .ANG.) connected in series. Degassed THF was
used as the mobile phase with a temperature of 35.degree. C. and a
flow rate of 0.9 ml/min. The time for complete elution through the
system was 50 min, and MALLS and RI data were recorded at 5 Hz.
[0152] Samples were prepared by dissolving 5 mg of polymer in 1 ml
of THF and filtering the solution through 0.45 m PTFE membrane
syringe filters immediately before injection. An injection volume
of 20 .mu.l was used. The data were analyzed by Wyatt Astra
Software (version 5.3.4) using the Zimm fitting formula with
dn/dc=0.125 for PCOD in THF to obtain weight-average molecular
weight (M.sub.w) for each polymer reported.
Example 10: Guidance on Molecular Sieve Selection
[0153] Given the following information on silicate and
aluminosilicate zeolites that possess at least one 10-ring channel
given in the 6.sup.th Edition of the Atlas of Zeolite Framework
Types the candidates for use in the present invention were
identified and are listed in FIG. 9.
[0154] Wenkite is eliminated because one of the crystallographic
diameters of its 10-ring channel that is less than 3 .ANG..
Heulandite is eliminated because the ratio of its larger
crystallographic diameter to its smaller crystallographic diameter
is greater than 2. The following approach was then followed to
select suitable molecular sieves.
[0155] A first step, Step 1) was that of identifying 10-ring,
wide-pore molecular sieve frameworks. The most promising candidates
were identified by selecting those that both have a minimum
crystallographic free diameter that is greater than 5 .ANG. and
have pore aspect ratio less than 1.1. Ten zeolite frameworks
satisfy both of these criteria: IMF, MEL, MFI, MFS, OBW, PON, SFF,
STF, TER and TUN.
[0156] A second step, Step 2) was that of identifying 10-ring,
wide-pore frameworks that permit diffusion in three dimensions.
Among this group of ten 10-ring, wide-pore molecular sieve
frameworks, four have channels that are connected in three
dimensions, two have channels that are connected in two dimensions,
and four only permit diffusion in one dimension. Therefore, the
four most promising candidates are identified (10-ring, wide-pore
molecular sieve frameworks that permit diffusion in three
dimensions): MEL, MFI, OBW and TUN.
[0157] An additional optional steps (since four strong candidates
have already been identified, further steps are optional) were that
of: identifying 10-ring, medium-pore molecular sieve frameworks
from the remaining zeolite frameworks by selecting those that both
have a minimum crystallographic free diameter that is greater than
4.5 .ANG. and have pore aspect ratio less than 1.25. Five of the
remaining zeolite frameworks satisfy both of these criteria: MTT,
NES, SFG, STI and TON. Among this group of five zeolite frameworks,
two have channels that are connected in two dimensions, none are
connected in three dimensions, and the majority only permit
diffusion in one dimension. Therefore, the most promising
candidates in this secondary group are NES and SFG.
[0158] A further additional optional step was that of identifying
10-ring, narrow-pore molecular sieve frameworks from the remaining
zeolite frameworks by selecting those that both have a minimum
crystallographic free diameter that is greater than 4 .ANG. and
have pore aspect ratio less than 1.5. Five of the remaining zeolite
frameworks satisfy both of these criteria: EUO, FER, LAU, MWW and
SZR.
[0159] Among this group of five zeolites, one has channels that are
connected in three dimensions and one is connected in two
dimensions (the majority only permit diffusion in one dimension).
Therefore, the most promising candidate in the third group is
SZR.
[0160] A survey of commercially available 10-ring zeolites
identified suppliers for five framework structures: MEL, MFI, MTT,
TON, FER and MWW. Two of these belong to the group of wide-10-ring
molecular sieves that are connected in three dimensions: MEL and
MFI.
[0161] The Atlas of Zeolite Framework Types indicates that zeolites
with MEL framework have the common name ZSM-11. Vendors offer
ZSM-11 with Si:Al ratios of 25, 30, 50, 80 and 280. Based on other
examples in this patent, the team chose to test ZSM-11 compositions
with the three highest Si:Al ratios (50, 80 and 280).
[0162] Similarly, MFI zeolites (common name ZSM-5) are available
commercially with a variety of Si:Al ratios, include 50, 80 and
>200. Therefore, the team ordered samples of ZSM-5 to include in
a trial study to identify the best zeolite for the desired
separation.
Example 11: Evaluation of Zeolite Efficacy in Selective Removal of
VCH from COD
[0163] A chemical process using cyclooctadiene (COD) was adversely
affected by the presence of vinylcyclohexene (VCH). Commercially
available redistilled-grade cyclooctadiene was found to contain
more than 1000 parts per million (ppm) VCH; the process required
that VCH content be less than 100 ppm.
[0164] A screening study was performed to evaluate the possibility
of using the separation method of the present invention. Molecular
sieves with framework MFI (ZSM-5) were chosen for testing and were
purchased with two different Si:Al ratios, 50 and 80, with ammonium
counterions.
[0165] For comparison, a small pore framework (LTA) and three large
pore frameworks (BEA, MOR and FAU) were included in the study. The
calcium Linde A zeolite (LTA), known as 5 .ANG., had Si:Al ratio
2:1. The Beta zeolite (BEA) with Si:Al 25:1 neutralized with
ammonium. Two MOR zeolites were studied: a sodium mordenite with
Si:Al of 13:1 and an ammonium mordenite with Si:Al of 20:1. The Y
zeolite (FAU) had Si:Al 5.2:1.
[0166] Trial samples consisting of 1 part vinylcylohexane to 99
parts cyclooctadiene were prepared to represent the mixtures that
require separation. In addition, samples with 1 part cyclooctadiene
to 99 parts of cyclododecatriene (CDDT) were used for
reference.
[0167] Vials were prepared with 0.5 g of zeolite and capped loosely
so that gas could escape. Then the vials and zeolites were dried in
a vacuum oven at 110.degree. C. at a reduced pressure (100 mtorr)
for 18 hours prior to use. Once cooled down to room temperature,
the oven was filled with argon, and the vials were immediately
capped tightly and taken out from the oven.
[0168] 2.5 g of the test sample, either 1% VCH in COD or 1% COD in
CDDT, was added to the vial. The content was magnetically stirred
for 2 hours at room temperature and ambient temperature.
[0169] After two hours, approximately 0.1 ml of each sample was
filtered to separate the sieved mixture from the zeolites using a
0.45 .mu.m syringe filter. Then 5 mg of filtrate was diluted in 0.9
ml of deuterated chloroform and .sup.1H NMR spectra were acquired
at 500 MHz.
[0170] The signal-to-noise ratio of the .sup.1H NMR spectra
permitted detection of as little at 50 ppm of either VCH in COD or
COD in CDDT. The outcomes of each experiment either showed
essentially no reduction of the minor component or reduction below
the detection limit. The .sup.1H NMR spectra of the constituents
that remained in the sieved mixture were unchanged relative to that
constituent in the trial sample. Therefore, the results are listed
in Table 3 below as "yes" the minor component was reduced below the
detection limit or "no" the minor component was not removed.
TABLE-US-00003 TABLE 3 removal of COD Classifi- Frame- Zeolite
Counter- VCH from enters cation work name Si:Al ion COD? pores?
8-ring LTA Linde A 2 Ca++ No No wide- MFI ZSM-5 50 NH4+ Yes No
10-ring 80 NH4+ Yes No 12-ring BEA Beta 25 NH4+ No Yes MOR
mordenite 13 Na+ No Yes 20 NH4+ No Yes FAU Y 5.2 NH4+ No Yes
[0171] The results summarized in Table 3 confirmed that: a) a
wide-10-ring zeolite with venting channels (MFI) can provide a
purity of better than 99.99% COD; b) a 0.5 g amount of zeolite is
sufficient to remove at least 0.025 g of VCH; c) separation can be
performed at ambient temperature; and d) separation is complete
within a time that is short compared to the rate of deleterious
reactions at the temperature used to perform the separation.
Example 12: Effect of Water Content on Separation Effectiveness
[0172] Two ZSM-5 zeolites with Si/Al of 28:1 and 80:1 respectively
were selected to demonstrate the importance of properly drying
molecular sieves before contacting a hydrocarbon mixture for
selective removal of undesired components. 0.5 g of each zeolite
was used as received and loaded into a 20 mL vial charged with a
stir bar, and 0.5 g of each zeolite was loaded in a 20 mL vial
charged with a stir bar, dried at 310.degree. C. and 100 mTorr for
20 min, cooled down to room temperature, and covered with argon
atmosphere prior to use. 2.5 g of 1 wt % VCH in COD described in
Example 11 was added to each of the four vials. The four mixtures
were stirred at room temperature and ambient pressure for 2
hrs.
[0173] After 2 hrs, approximately 0.1 ml of each sample was
filtered to separate the sieved mixture from the zeolites using a
0.45 m syringe filter. Then 5 mg of filtrate was diluted in 0.9 ml
of deuterated chloroform and .sup.1H NMR spectra were acquired at
500 MHz. The signal-to-noise ratio of the .sup.1H NMR spectra
permitted detection of as little at 50 ppm of either VCH in COD or
COD in CDDT. The results of the two zeolites dried at 310.degree.
C. and 100 mTorr prior to use show reduction of VCH concentration
below the detection limit, while the results of those used as
received show that the VCH concentration in the samples was reduced
to ca. 0.02 wt %. The comparisons exemplified here suggest a
skilled person should properly dry the molecular sieves to minimize
the amount of residual water in sieving channels before contacting
them with a hydrocarbon mixture, so that better separation
effectiveness can be achieved without increasing molecular sieve
loading.
Example 13: Determination of Water Content in a Zeolite Sample
Using Thermogravimetric Analysis (TGA)
[0174] Thermogravimetry, as will be understood by a skilled person,
is one of the effective ways to understand the water content in a
zeolite sample. The following five as-received zeolite samples were
analyzed on a PerkinElmer Simultaneous Thermal Analyzer (STA 6000)
equipped with an autosampler: ZSM-5 with Si/Al of 23:1 (ammonium
counterions), ZSM-5 with Si/Al of 28:1 (ammonium counterions),
ZSM-5 with Si/Al of 50:1 (ammonium counterions), ZSM-5 with Si/Al
of 80:1 (ammonium counterions), and zeolite ferrierite with Si/Al
of 20:1 (ammonium counterions). Approximately 6 mg of each sample
was analyzed under nitrogen flow at 20 mL/min, a heating rate of
5.degree. C./min, and a temperature range from 30 to 600.degree. C.
The results shown in FIG. 10 indicate that there is at least a
water content of 2 wt % in each zeolite sample, and that those with
a Si/Al ratio below 25:1 (i.e., ZSM-5 23:1 and zeolite ferrierite)
are more hydrophilic due to their relative high contents of
trivalent aluminum atoms and can contain up to 8 wt % water. The
comparisons demonstrated in this example provide a skilled person
guidance on how to select a molecular sieve according to its Si/Al
ratio, and that heating a molecular sieve at ambient pressure over
400.degree. C. can remove water molecules from the sieving
channels.
Example 14: Molecular Sieves Framework Categorization
[0175] Using data for all of the 10-ring molecular sieves
documented in the 6.sup.th edition of the Atlas of Zeolite
Frameworks, the 10-ring frameworks are categorized using the
criteria for: 1) dimensions of the minimum aperture of the sieving
channel (defined as the only 10-ring channel or the 10-ring channel
that has the largest minimum crystallographic free diameter among
the 10-ring channels in the framework); and B) connectivity of the
one or more sieving channels together with other channels.
[0176] The framework crystallographic free diameters of the sieving
pore can be accordingly categorized as: [0177] "wide" (minimum
crystallographic free diameter that is 5.0 .ANG. or greater and
less than 6 .ANG. and ratio of maximum/minimum crystallographic
free diameter is between 1.1 and 1.0), [0178] "intermediate"
(zeolites that only satisfy one of the two criteria for "wide" and
all zeolites that have a minimum crystallographic free diameter
that is 4.5 .ANG. or greater and less than 5.0 .ANG. and has a
ratio of maximum/minimum crystallographic free diameter between 1.1
and 1.25) [0179] "narrow" (zeolites that only satisfy one of the
two criteria for "intermediate" and all zeolites that have a
minimum crystallographic free diameter that is 4.0 .ANG. or greater
and less than 4.5 .ANG. and has a ratio of maximum/minimum
crystallographic free diameter between 1.25 and 1.5).
[0180] The framework crystallographic free diameters of the sieving
pore can also be categorized in view of the framework connectivity
as: [0181] "3D Sieving channel network" which indicates that the
framework offers a three-dimensional network in which all channels
are sieving channels. [0182] "3D Sieving channel+Venting channels
network" which indicates that the framework offers venting channels
that taken together with one or more sieving channels affords a
three dimensional network [0183] "2D Sieving channel+Venting
channel network" which indicates that the framework offers either
two sieving channels or a sieving channel with one venting channel
that together provide a two dimensional network; and [0184] "1D
Sieving channel" which indicates a framework in which the sieving
channels do not connect with an additional dimension.
[0185] The resulting assignments are given in Table 4 below.
TABLE-US-00004 TABLE 4 Classification subgroups of 10-ring
Frameworks Sieving Sieving channel + channel + 3D Venting Venting
sieving Sieving channels channel 1D channel channel provide a 3D
provide a 2D Sieving aperture network network network channel Wide-
MEL TUN, IMF, MFS, TER TON, SFF, 10-ring MFI, OBW STF Intermediate-
none none STI, SFG, NES MTT, TON 10-ring Narrow- none SZR FER, MWW
EUO, LAU 10-ring
[0186] This example shows how to organize a large list of possible
zeolites to plan an efficient set of experiments to evaluate them
for a separation of interest.
[0187] For example, the skilled person may choose to perform an
initial experiment with a zeolite having at least one
intermediate-width 10-ring sieving channel, the table above would
guide them to choose STI, SFG or NES first. The skilled person
chooses a zeolite having the NES framework in a form that has Si:Al
greater than or equal to 50 and neutralized with Ca.sup.++ (that
is, an example of the NES framework with pores that are kept open
by using Ca.sup.++ rather than Na.sup.+ or NH.sub.4.sup.+). If they
observe that the molecules to be retained in the sieve do not enter
this NES zeolite, they can rule out five frameworks: NES, STI and
SFG because they will behave similarly to one another, and MTT and
TON which will be inferior to NES, STI an SFG. If the molecules to
be retained in the sieve conform to one of the Markush groups in
the present invention, they will enter the pores of one of the
Wide-10-ring zeolites. Therefore, discouraging results on an Ca-NES
zeolite with high Si:Al indicates that the next tests should be
performed on one or more zeolites that have a framework selected
from of the Wide-10-ring category, preferrably frameworks with
venting channels. For efficiency, the skilled person might choose
one zeolite of framework MEL and one from the group of TUN, IMF,
MFI and OBW, initially choosing specific compositions that have
Si:Al greater than or equal to 50 and neutralized with Ca.sup.++.
In this way, a very small number of experiments can be used to
identify molecular sieves that perform the desired separation.
Example 15: Process to Produce Cyclooctadiene from Butadiene
[0188] In this example, 1,3-butadiene is fed to a dimerization
reactor that produces two products in the proportion 67.1% wt
cyclooctadiene (COD) and 23.6% wt cyclododecatriene (CDDT) per mass
of butadiene consumed. In addition, it produces 1.7% wt
4-vinyl-1-cyclohexene (VCH) per mass of butadiene consumed. The VCH
is difficult to separate from COD. Twice distilled COD continues to
have 0.2% wt to 0.5% wt VCH and approximately half of the COD is
lost to the stream that has the higher concentration of VCH. Borane
treated COD can reduce the VCH to less than 0.1%; however,
approximately half of the COD is lost and diverse impurities are
created that poisons the catalysts in important processes for which
COD is sold.
[0189] Therefore, separation using the present invention is
integrated into the process of converting butadiene to
products.
[0190] Reference is made in this connection to the schematics of
FIG. 11 showing an exemplary process that converts a "precursor" to
a desired "sieved mixture" and a stream of "displacement fluid" and
"adsorbate"; the precursor is introduced to a "reactor" in which
desired product molecules are formed (the stream from the reactor
may optionally be passed through a device that separates precursor
and recycles it to the reactor); the mixture from the reactor flows
into the "separation" in which at least one device with molecular
sieve is "on line" and at least one device with molecular sieve is
undergoing "regeneration"; the mixture that passes through the
device produces a "sieved mixture" that is on line is enriched in
one or more desired components and leaves adsorbate on the
molecular sieves; the device that is undergoing regeneration may
optionally be treated with a "displacement fluid" to recover the
adsorbate in a stream of "displacement fluid+adsorbate".
[0191] As applied to this example, the precursor of the schematics
of FIG. 11 is 1,3-butadiene. The 1,3-butadiene is easily recycled
because it has much higher vapor pressure than VCH, COD or CDDT.
The mixture is a liquid composed of VCH, COD and CDDT. When the
mixture passes through the inventive molecular sieve system that
can be dual bed (in which the two devices alternate between being
on line and being in regeneration), or multiple bed (in which the
scheduling can be designed using relationships that are known to
the skilled person) or fluidized bed (in which the zeolite moves
from the online device to the regeneration device). The mixture
flows through a device in which the molecular sieve adsorbs the VCH
at a flow rate that allows 99% of the VCH to adsorb to the
molecular sieve. The composition of the sieved mixture is 73.9% COD
and 26.0% CDDT and more than 99% of the COD that was present in the
mixture is still present in the sieved mixture. The stream of COD
and CDDT is fed to a vacuum distillation column that easily
separates the two in high yield by virtue of the large difference
in the boiling points of the two species (at ambient pressure, bp
151.degree. C. for COD and bp 231.degree. C. for CDDT). The
regeneration of the molecular sieve can be performed in two ways.
Regeneration without recovery of the adsorbate can be achieved
simply heating the molecular sieve to vaporize the VCH and then
burning off the organic vapor. Regeneration with recovery of the
adsorbate can be achieved by using benzene as the displacement
fluid and then using vacuum distillation to drive off benzene (at
ambient pressure, boiling point (i.e. bp) 80.degree. C. for benzene
and bp 129.degree. C. for VCH).
[0192] This example shows that the materials, methods and systems
of the present invention can be used in an integral manner with a
reactor the produces products that present separation challenges
downstream.
[0193] The example shows that products that are destroyed or lost
in prior art purifications such as sequential distillation or
reactive removal of contaminant can be obtained in high yield by
using the materials, methods and systems of the present
invention.
Example 16: Exemplary Desorption Systems for the Molecular
Sieves
[0194] Exemplary of adsorption systems for the molecular sieves of
the present invention include: [0195] Multiple-bed adsorption
[0196] Single-bed adsorption [0197] Static adsorption [0198]
Fluidized bed adsorption
[0199] Multiple-bed adsorption: Multiple bed adsorption is ideal
for most commercial, large-scale fluid purification operations.
Conventional fixed-bed adsorption equipment is used. For example, a
dual-bed installation places one bed on-stream to purify the fluid
while the other bed is being purged, either to discard or collect
the adsorbate. When the process design requires a shorter
adsorption time than the purge time, additional beds can be added
to permit continuous processing of the feed.
[0200] Single-bed adsorption: Single-bed adsorption can be used
when interrupted product flow is acceptable. When the adsorption
capacity of the bed is reached, it can be regenerated. The
regenerated bed can be used for another batch in the same process
or used for a batch of a different material or even moved to
another location where it is needed.
[0201] Static adsorption: When manufactured into various physical
forms, molecular sieves can be used as static adsorbents in closed
liquid systems.
[0202] Fluidized-bed adsorption: Fluidized bed-adsorption can be
used to provide continuous regeneration of zeolite that is
saturated with adsorbate by directing a stream of suspended zeolite
particles at the bottom of a fluidized adsorption column to the top
of a regeneration column and replenishing the zeolites in the
fluidized bed using a stream of zeolite suspension that has been
completely regenerated directed from the bottom of the regeneration
column to the top of the fluidized adsorption bed.
[0203] The examples set forth above are provided to give those of
ordinary skill in the art a complete disclosure and description of
how to make and use the embodiments of the hydrocarbon mixtures,
eight membered unsaturated hydrocarbons, nonlinear unsaturated
C.sub.8H.sub.2m hydrocarbons with 4.ltoreq.m.ltoreq.8, polymers,
compositions, systems and methods of the disclosure, and are not
intended to limit the scope of what the inventors regard as their
disclosure. Modifications of the above-described modes for carrying
out the disclosure that are obvious to persons of skill in the art
are intended to be within the scope of the following claims. All
patents and publications mentioned in the specification are
indicative of the levels of skill of those skilled in the art to
which the disclosure pertains.
[0204] The entire disclosure of each document cited (including
patents, patent applications, journal articles, abstracts,
laboratory manuals, books, or other disclosures) in the Background,
Summary, Detailed Description, and Examples is hereby incorporated
herein by reference. All references cited in this disclosure are
incorporated by reference to the same extent as if each reference
had been incorporated by reference in its entirety
individually.
[0205] It is to be understood that the disclosures are not limited
to particular compositions materials, or biological systems, which
can, of course, vary. It is also to be understood that the
terminology used herein is for the purpose of describing particular
embodiments only, and is not intended to be limiting. As used in
this specification and the appended claims, the singular forms "a,"
"an," and "the" include plural referents unless the content clearly
dictates otherwise. The term "plurality" includes two or more
referents unless the content clearly dictates otherwise. Unless
defined otherwise, all technical and scientific terms used herein
have the same meaning as commonly understood by one of ordinary
skill in the art to which the disclosure pertains.
[0206] Unless otherwise indicated, the disclosure is not limited to
specific reactants, substituents, catalysts, reaction conditions,
or the like, as such may vary. It is also to be understood that the
terminology used herein is for the purpose of describing particular
embodiments only and is not intended to be limiting.
[0207] As used in the specification and the appended claims, the
singular forms "a," "an," and "the" include plural referents unless
the context clearly dictates otherwise. Thus, for example,
reference to "a polymer" includes a single polymer as well as a
combination or mixture of two or more polymers, reference to "a
substituent" encompasses a single substituent as well as two or
more substituents, and the like.
[0208] As used in the specification and the appended claims, the
terms "for example," "for instance," "such as," or "including" are
meant to introduce examples that further clarify more general
subject matter. Unless otherwise specified, these examples are
provided only as an aid for understanding the applications
illustrated in the present disclosure, and are not meant to be
limiting in any fashion.
[0209] In this disclosure and in the claims that follow, reference
will be made to a number of terms, which shall be defined to have
the following meanings:
[0210] The term "alkyl" as used herein refers to a linear,
branched, or cyclic saturated hydrocarbon group typically although
not necessarily containing 1 to about 10 carbon atoms, preferably 1
to about 6 carbon atoms, such as methyl, ethyl, n-propyl,
isopropyl, n-butyl, isobutyl, t-butyl, octyl, decyl, and the like,
as well as cycloalkyl groups such as cyclopentyl, cyclohexyl and
the like. Generally, although again not necessarily, alkyl groups
herein contain 1 to about 6 carbon atoms. The term "cycloalkyl"
intends a cyclic alkyl group, typically having 4 to 12, preferably
5 to 8, carbon atoms. The term "substituted alkyl" refers to alkyl
substituted with one or more substituent groups of hydrocarbons, If
not otherwise indicated, the terms "alkyl" and "lower alkyl"
include linear, branched, cyclic, unsubstituted, substituted, alkyl
and lower alkyl, respectively.
[0211] The term "aryl" as used herein, and unless otherwise
specified, refers to an aromatic substituent containing a single
aromatic ring or multiple aromatic rings that are fused together,
directly linked, or indirectly linked (such that the different
aromatic rings are bound to a common group such as a methylene or
ethylene moiety). Exemplary aryl groups contain one aromatic ring
e.g., phenyl.
[0212] The terms "cyclic" and "ring" refer to alicyclic or aromatic
groups that may or may not be substituted and/or heteroatom
containing, and that may be monocyclic, bicyclic, or
polycyclic.
[0213] The term "alicyclic" is used in the conventional sense to
refer to an aliphatic cyclic moiety, as opposed to an aromatic
cyclic moiety, and may be monocyclic, bicyclic or polycyclic.
[0214] The term "olefins" as used herein indicates two carbons
covalently bound to one another that contain a double bond
(sp.sup.2-hybridized bond) between them.
[0215] By "substituted" as in "substituted alkyl," "substituted
aryl," and the like, as alluded to in some of the aforementioned
definitions, is meant that in the, alkyl, aryl, or other moiety, at
least one hydrogen atom bound to a carbon atom is replaced with one
or more hydrocarbon groups.
[0216] Examples of such substituents include, without limitation:
functional groups such as and the hydrocarbyl moieties
C.sub.1-C.sub.6 alkyl (preferably C.sub.1-C.sub.4 alkyl),
C.sub.2-C.sub.6 alkenyl (preferably C.sub.2-C.sub.4 alkenyl),
C.sub.2-C.sub.6 alkynyl (preferably C.sub.2-C.sub.4 alkynyl),
C.sub.6 aryl.
[0217] In addition, the aforementioned functional groups may, if a
particular group permits, be further substituted with one or more
additional functional groups or with one or more hydrocarbyl
moieties such as those specifically enumerated above. Analogously,
the above-mentioned hydrocarbyl moieties may be further substituted
with one or more functional groups or additional hydrocarbyl
moieties such as those specifically enumerated.
[0218] "Optional" or "optionally" means that the subsequently
described circumstance may or may not occur, so that the
description includes instances where the circumstance occurs and
instances where it does not. For example, the phrase "optionally
substituted" means that a non-hydrogen substituent may or may not
be present on a given atom, and, thus, the description includes
structures wherein a non-hydrogen substituent is present and
structures wherein a non-hydrogen substituent is not present.
[0219] In the molecular structures herein, the use of bold and
dashed lines to denote particular conformation of groups follows
the IUPAC convention. A bond indicated by a broken line indicates
that the group in question is below the general plane of the
molecule as drawn, and a bond indicated by a bold line indicates
that the group at the position in question is above the general
plane of the molecule as drawn.
[0220] The term "carbon chain" as used herein indicates a linear or
branched line of connected carbon atoms.
[0221] Although any methods and materials similar or equivalent to
those described herein can be used in the practice for testing of
the specific examples, additional appropriate materials and methods
are described herein.
[0222] A number of embodiments of the disclosure have been
described. Nevertheless, it will be understood that various
modifications may be made without departing from the spirit and
scope of the present disclosure. Accordingly, other embodiments are
within the scope of the following claims.
* * * * *