U.S. patent application number 12/512577 was filed with the patent office on 2010-06-24 for liquid carbon dioxide absorbent and methods of using the same.
This patent application is currently assigned to GENERAL ELECTRIC COMPANY. Invention is credited to Dan Hancu, Sergei Kniajanski, Tunchiao Hubert Lam, Larry Neil Lewis, Michael Joseph O'Brien, Robert James Perry, Malgorzata Iwona Rubinsztajn, Grigorii Lev Soloveichik.
Application Number | 20100154639 12/512577 |
Document ID | / |
Family ID | 42289317 |
Filed Date | 2010-06-24 |
United States Patent
Application |
20100154639 |
Kind Code |
A1 |
Perry; Robert James ; et
al. |
June 24, 2010 |
LIQUID CARBON DIOXIDE ABSORBENT AND METHODS OF USING THE SAME
Abstract
A carbon dioxide absorbent comprising (i) a liquid, nonaqueous
silicon-based material, functionalized with one or more groups that
either reversibly react with CO.sub.2 or have a high-affinity for
CO.sub.2 is provided and (ii) a hydroxy-containing solvent. The
absorbent may be utilized in methods to reduce carbon dioxide in an
exhaust gas, and finds particular utility in power plants.
Inventors: |
Perry; Robert James;
(Niskayuna, NY) ; O'Brien; Michael Joseph;
(Clifton Park, NY) ; Lam; Tunchiao Hubert;
(Clifton Park, NY) ; Soloveichik; Grigorii Lev;
(Latham, NY) ; Kniajanski; Sergei; (Clifton Park,
NY) ; Lewis; Larry Neil; (Scotia, NY) ;
Rubinsztajn; Malgorzata Iwona; (Ballston Spa, NY) ;
Hancu; Dan; (Clifton Park, NY) |
Correspondence
Address: |
GENERAL ELECTRIC COMPANY;GLOBAL RESEARCH
ONE RESEARCH CIRCLE, PATENT DOCKET RM. BLDG. K1-4A59
NISKAYUNA
NY
12309
US
|
Assignee: |
GENERAL ELECTRIC COMPANY
Schenectady
NY
|
Family ID: |
42289317 |
Appl. No.: |
12/512577 |
Filed: |
July 30, 2009 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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12343905 |
Dec 24, 2008 |
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12512577 |
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Current U.S.
Class: |
95/236 ;
252/182.3 |
Current CPC
Class: |
F23J 2219/40 20130101;
Y02C 10/06 20130101; B01D 2252/2025 20130101; Y02A 50/2342
20180101; Y02C 20/40 20200801; B01D 2252/2056 20130101; B01D
2252/20421 20130101; B01D 2252/20415 20130101; B01D 2252/2026
20130101; B01D 2252/2028 20130101; B01D 2252/504 20130101; B01D
2252/202 20130101; B01D 53/1493 20130101; Y02A 50/20 20180101; Y02C
10/04 20130101; B01D 53/1475 20130101; F23J 2215/50 20130101; B01D
2252/2041 20130101 |
Class at
Publication: |
95/236 ;
252/182.3 |
International
Class: |
B01D 53/14 20060101
B01D053/14; C09K 3/00 20060101 C09K003/00 |
Goverment Interests
STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH &
DEVELOPMENT
[0002] This invention was made with Government support under grant
number DE-NT0005310 awarded by the Department of Energy-NETL. The
Government has certain rights in the invention.
Claims
1. A carbon dioxide absorbent comprising: (i) a liquid, nonaqueous
silicon-based material, functionalized with one or more groups that
reversibly react with CO.sub.2 and/or have a high-affinity for
CO.sub.2; and (ii) a hydroxy-containing solvent
2. The absorbent of claim 1, wherein the functionalized
silicon-based material comprises silanes, or compounds containing
one or more siloxy units, or combinations of these.
3. The absorbent of claim 1, wherein the silicon-based material is
functionalized with one or more nitrogen-containing groups.
4. The absorbent of claim 3, wherein the functional group(s)
comprise(s) one or more aliphatic amines, imines, amidines, amides,
heterocyclic amino compounds such as pyridine, aromatic amines such
as aniline, and combinations of these.
5. The absorbent of claim 4, wherein the functional group(s)
comprise(s) one or more amines.
6. The absorbent of claim 5, wherein the functional group(s)
comprise(s)one or more di-, tri- and polyamines or combinations of
these.
7. The absorbent of claim 6, wherein the functional group(s)
comprise(s) one or more aminomethyl, aminoethyl, aminopropyl,
aminoethylaminopropyl, piperazinopropyl, aminomethylaminoethyl,
2-aminopropylpryidyl, groups or combinations of these.
8. The absorbent of claim 7, wherein the functional group(s)
comprise(s) one or more amino hydroxy groups.
9. The absorbent of claim 1, wherein the said solvent has a vapor
pressure below 150 mm Hg at 100.degree. C.
10. The absorbent of claim 9, wherein the said solvent comprises
two or more hydroxyl groups.
11. The absorbent of claim 10, wherein the said solvent comprises a
glycol, a hydroxylated silicone, a phenol or combinations of
these.
12. The absorbent of claim 11, wherein the solvent comprises
trimethylolpropane, glycerol, triethylene glycol, tetraethylene
glycol, 1,3-bis(3-hydroxypropyl)tetramethyldisiloxane, a
hydrosilylation reaction product of 1,1,3,3-tetramethyldisiloxane
and trimethylolpropane allyl ether, eugenol, isoeugenol,
2-allyl-6-methylphenol or combinations of these.
13. The absorbent of claim 1, further comprising water.
14. The absorbent of claim 1, further comprising antioxidants,
stabilizers, accelerators, antifoaming agents or blends
thereof.
15. A method for reducing the amount of carbon dioxide in a process
stream comprising contacting the stream with a carbon dioxide
absorbent comprising (i) a liquid, nonaqueous silicon-based
material, functionalized with one or more groups that reversibly
react with CO.sub.2 and/or have a high-affinity for CO.sub.2; and
(ii) a hydroxy-containing solvent.
16. The method of claim 15, wherein the process stream comprises an
exhaust stream.
17. The method of claim 15, wherein the hydroxy-containing solvent
comprises trimethylolpropane, glycerol, ethylene glycol, diethylene
glycol, triethylene glycol, tetraethylene,
1,3-bis(3-hydroxypropyl)tetramethyldisiloxane, a hydrosilylation
reaction product of 1,1,3,3-tetramethyldisiloxane and
trimethylolpropane allylether, or combinations of these.
18. The method of claim 15, wherein the carbon dioxide solvent
further comprises water.
19. The method of claim 15, wherein the functionalized
silicon-based material comprises one or more aminosilicones.
20. The method of claim 15, wherein the functional group(s)
comprise(s) one or more amines.
21. The method of claim 20, wherein the functional group(s)
comprise(s) one or more di-, tri- and polyamines or combinations of
these.
22. A power plant comprising a carbon dioxide removal unit further
comprising a carbon dioxide absorbent comprising (i) a liquid,
nonaqueous silicon-based material, functionalized with one or more
groups that reversibly react with CO.sub.2 and/or have a
high-affinity for CO.sub.2; and (ii) a hydroxy-containing
solvent.
23. A method of generating electricity with reduced carbon dioxide
emissions comprising combusting a fuel to produce an exhaust gas
comprising carbon dioxide and directing the exhaust gas to a carbon
dioxide removal unit comprising a carbon dioxide absorbent
comprising (i) a liquid, nonaqueous silicon-based material,
functionalized with one or more groups that reversibly react with
CO.sub.2 and/or have a high-affinity for CO.sub.2; and (ii) a
hydroxy-containing solvent.
24. The method of claim 23, wherein the hydroxyl-containing solvent
comprises trimethylolpropane, glycerol, ethylene glycol, diethylene
glycol, triethylene glycol, tetraethylene,
1,3-bis(3-hydroxypropyl)tetramethyldisiloxane, a hydrosilylation
reaction product of 1,1,3,3-tetramethyldisiloxane and
trimethylolpropane allylether, or combinations of these.
25. The method of claim 23, wherein the absorbent further comprises
water.
26. The method of claim 23, wherein the functionalized
silicon-based material comprises one or more silicones.
27. The method of claim 26, wherein the functional group(s)
comprise(s) one or more amines.
Description
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] The present application is a continuation in part of U.S.
patent application Ser. No. 12/343,905, filed Dec. 24, 2008. The
present application is also related to co-pending United States
patent application having attorney docket number 237591-1 and filed
on even date herewith. Both of these applications are hereby
incoporated herein by reference to the extent they are consistent
with the definitions utilized herein.
BACKGROUND
[0003] Pulverized coal (PC) power plants currently produce over
half the electricity used in the United States. In 2007, these
plants emitted over 1900 million metric tons of carbon dioxide
(CO.sub.2), and as such, accounted for 83% of the total CO.sub.2
emissions from electric power generating plants and 33% of the
total US CO.sub.2 emissions. Eliminating, or even reducing, these
emissions will be essential in any plan to reduce greenhouse gas
emissions.
[0004] Separating CO.sub.2 from gas streams has been commercialized
for decades in food production, natural gas sweetening, and other
processes. Aqueous monoethanolamine (MEA) based solvent capture is
currently considered to be the best commercially available
technology to separate CO.sub.2 from exhaust gases, and is the
benchmark against which future developments in this area will be
evaluated. Unfortunately, such amine-based systems were not
designed for processing the large volumes of flue gas produced by a
PC plant. Scaling the MEA-based CO.sub.2 capture system to the size
required for PC plants would result in an 83% increase in the
overall cost of electricity for the PC plant. Applying this
technology to all existing PC plants in the US would cost $125
billion per year, making MEA-based CO.sub.2 capture an unlikely
choice for large-scale commercialization.
[0005] There are many properties that desirably would be exhibited,
or enhanced, in any CO.sub.2 capture technology contemplated to be
a feasible alternative to the currently utilized MEA-based systems.
For example, any such technology would desirably exhibit a high net
CO.sub.2 capacity, and could provide lower capital and operating
costs (less material volume required to heat and cool, therefore
less energy required). A lower heat of reaction would mean that
less energy would be required to release the CO.sub.2 from the
material. Desirably, the technology would not require a pre-capture
gas compression so that a high net CO.sub.2 capacity could be
achieved at low CO.sub.2 partial pressures, lowering the energy
required for capture. Technologies utilizing materials with lower
viscosities would provide improved mass transfer, reducing the size
of equipment needed, as well as a reduction in the cost of energy
to run it. Low volatility and high thermal, chemical and hydrolytic
stability of the material(s) employed could reduce the amount of
material needing to be replenished and emission of degradation
products. Of course, any such technology would also desirably have
low material costs so that material make-up costs for the system
would be minimized. Operability of CO.sub.2 release at high
pressures could reduce the energy required for CO.sub.2 compression
prior to sequestration. Finally, such technologies would also
desirably exhibit reduced corrosivity to help reduce capital and
maintenance costs, and further would not require significant
cooling to achieve the desired net CO.sub.2 loading, reducing
operating costs.
[0006] Unfortunately, many of the above delineated desired
properties interact and/or depend on one another, so that they
cannot be varied independently and trade-offs are required. For
example, in order to have low volatility, the materials used in any
such technology typically must have a fairly large molecular
weight, but to have low viscosity, the materials must have a low
molecular weight. To have a high CO.sub.2 capacity at low
pressures, the overall heat of reaction needs to be high, but to
have low regeneration energy, the overall heat of reaction needs to
be low.
[0007] Desirably, a CO.sub.2 capture technology would be provided
that optimizes as many of the above desired properties as possible,
yet without causing substantial detriment to other desired
properties. At a minimum, in order to be commercially viable, such
technology would desirably be low cost, and utilize materials(s)
having low volatility, high thermal stability and a high net
capacity for CO.sub.2.
BRIEF DESCRIPTION
[0008] In a first aspect, there is provided a carbon dioxide
absorbent comprising (i) a liquid, nonaqueous silicon-based
material, functionalized with one or more groups that reversibly
react with CO.sub.2 and/or have a high-affinity for CO.sub.2; and
(ii) a hydroxy-containing solvent.
[0009] Also, a second aspect provides a method for reducing the
amount of carbon dioxide in a process stream comprising contacting
the stream with a carbon dioxide absorbent comprising (i) a liquid,
nonaqueous, silicon-based material, functionalized with one or more
groups that reversibly react with CO.sub.2 and/or have a
high-affinity for CO.sub.2; and (ii) a hydroxy-containing
solvent.
[0010] In a third aspect, a power plant is provided, comprising a
carbon dioxide removal unit further comprising a carbon dioxide
absorbent comprising: (i) a liquid, nonaqueous silicon-based
material, functionalized with one or more groups that reversibly
react with CO.sub.2 and/or have a high-affinity for CO.sub.2; and
(ii) a hydroxy-containing solvent.
[0011] A method of generating electricity with reduced carbon
dioxide emissions is also provided. The method comprises combusting
a fuel (pulverized coal, liquid hydrocarbon, natural gas and the
like) and directing the flue gas comprising carbon dioxide to an
electricity generating equipment, e.g. steam or gas turbine and
then to a carbon dioxide removal unit comprising a carbon dioxide
absorbent comprising: (i) a liquid, nonaqueous silicon-based
material, functionalized with one or more groups that reversibly
react with CO.sub.2 and/or have a high-affinity for CO.sub.2; and
(ii) a hydroxy-containing solvent.
DETAILED DESCRIPTION
[0012] Unless defined otherwise, technical and scientific terms
used herein have the same meaning as is commonly understood by one
of skill in the art to which this invention belongs. The terms
"first", "second", and the like, as used herein do not denote any
order, quantity, or importance, but rather are used to distinguish
one element from another. Also, the terms "a" and "an" do not
denote a limitation of quantity, but rather denote the presence of
at least one of the referenced item, and the terms "front", "back",
"bottom", and/or "top", unless otherwise noted, are merely used for
convenience of description, and are not limited to any one position
or spatial orientation. If ranges are disclosed, the endpoints of
all ranges directed to the same component or property are inclusive
and independently combinable (e.g., ranges of "up to about 25 wt.
%, or, more specifically, about 5 wt. % to about 20 wt. %," is
inclusive of the endpoints and all intermediate values of the
ranges of "about 5 wt. % to about 25 wt. %," etc.). The modifier
"about" used in connection with a quantity is inclusive of the
stated value and has the meaning dictated by the context (e.g.,
includes the degree of error associated with measurement of the
particular quantity).
[0013] The subject matter disclosed herein relates generally to
carbon dioxide absorbents, power plants incorporating them, and
methods of using the absorbents to absorb carbon dioxide from
process streams, e.g., as may be produced by methods of generating
electricity. Conventional carbon dioxide absorbents lack one or
more of the properties considered important, if not critical, in
the commercial feasibility of their use in many technologies.
MEA-based aqueous absorbents, for example, were not designed for
use with large volumes of exhaust gas. As a result, use of these
absorbents in such processes is extremely energy intensive and
costly--too costly for implementation into power plants for post
combustion CO.sub.2 capture.
[0014] There are currently provided carbon dioxide absorbents
comprising liquid, nonaqueous silicon-based materials and a
hydroxy-containing solvent. Silicon-based materials are defined as
molecules having between one and twenty repeat units, and thus, may
include small molecules comprising silicon, i.e., molecules
comprising from one to five silicon atoms, or oligomeric materials
comprising between about 5 and 20 silicon atoms.
[0015] In one embodiment, the present absorbent comprises a
CO.sub.2-philic, silicon-containing oligomer, e.g., comprising less
than about 20 repeating, monomeric units, and desirably from about
5 to about 10 repeating monomeric units. As used herein, the term
"CO.sub.2-philic silicon containing oligomer" means an oligomer
that has an affinity for CO.sub.2, as may be evidenced by
solubility in liquid or supercritical CO.sub.2, or an ability to
physically absorb CO.sub.2. Liquid oligomers such as
poly(siloxanes), poly(ethylene glycols), poly(propylene glycols)
and perfluorinated polyethers, e.g., poly(fluoroethylene glycol),
are non-limiting examples of CO.sub.2-philic short chain oligomers
suitable for use in the present absorbent. These, as well as other
exemplary oligomers are shown below and may be derivatized on chain
or at the end of the oligomer or may be co- or ter-oligomers:
[0016] Of these, silicones are particularly well-suited for use in
the present absorbents. Also correctly referred to as polymerized
siloxanes or polysiloxanes, silicones are mixed inorganic-organic
polymers or oligomers with the chemical formula [R.sub.2SiO].sub.n,
wherein R comprises a linear, branched or aromatic organic group of
any number of carbons, e.g., methyl ethyl, phenyl, etc. These
materials thus comprise an inorganic silicon-oxygen backbone ( . .
. Si--O--Si--O--Si--O-- . . . ) with organic side groups attached
to the silicon atoms, which are four-coordinate. These silicones
may be linear with R and OR' end-capping groups or cyclic
containing only repeating units. An example of the latter is
octamethylcyclotetrasiloxane.
[0017] Silicones have low volatility even at short chain lengths
and liquid at room temperature. They are typically low cost, and
stable at high temperatures, e.g., up to about 150.degree. C.
Silicones are also readily functionalized, and so, could be
functionalized with groups that increase their affinity for
CO.sub.2.
[0018] Length of the silicone oligomer chain can be easily
controlled during synthesis that allows control of such physical
properties as viscosity and boiling point. In addition, siloxane
bonds are thermally stable and hydrolytically stable in the absence
of strong acids or bases. Many silicones precursors are
commercially available, and so advantageously, large scale
production capabilities would not have to be developed. Many of
these may be utilized in the present invention. One example of a
silicone suitable for functionalization in the present invention,
and available from a variety of sources, comprises
polyhydridomethylsiloxane.
[0019] In another embodiment, the present absorbent comprises a
CO.sub.2-philic, silicon-based small molecule, e.g., comprising
from about one to about five silicon atoms. As used herein, the
term "CO.sub.2-philic silicon-based small molecule " means a
material that reversibly reacts with or has an affinity for
CO.sub.2.
[0020] The silicon-based small molecules may comprise one silicon
atom as shown in Formula (I) wherein L=linking group of
C.sub.1-C.sub.18 and may be aliphatic, aromatic, heteroaliphatic,
heteroaromatic or mixtures thereof:
##STR00001##
where R.sub.1, R.sub.2, R.sub.3 may be the same or different and
may be C.sub.1-C.sub.18 aliphatic, aromatic, heteroaliphatic,
heteroaromatic or mixtures thereof and R.sub.4.dbd.NR.sub.5R.sub.6
where at least one of R.sub.5 or R.sub.6 is H. The other may be
C.sub.1-C.sub.18 aliphatic, aromatic, heteroaliphatic,
heteroaromatic or mixtures thereof.
[0021] Or, the silicon-based materials may be as shown in Formulas
II-VI, and, when x.ltoreq.5, y+z.ltoreq.5 and/or r.ltoreq.5 silicon
based materials represented by formulas II-VI would generally be
considered silicon based small molecules. Or, when x.gtoreq.5,
y+z.gtoreq.5 and/or r.gtoreq.5, silicon based materials represented
by formulas II-VI would generally be considered silicon-containing
oligomers. As depicted in structures II-VI, the core of the
silicon-based small molecule may be linear, cyclic or branched or
combinations.
##STR00002##
[0022] For Formula II, R.sub.7-R.sub.12 may be the same or
different. At least one of R.sub.7-R.sub.12 will desirably be
L-R.sub.4 while the remainder are desirably C.sub.1-C.sub.18
aliphatic, aromatic, heteroaliphatic, heteroaromatic or mixtures
thereof.
[0023] For formula III, R.sub.13-R.sub.16 may be the same or
different. At least one of R.sub.13--R.sub.16 will desirably be
L-R.sub.4 while the remainder are desirably C.sub.1-C.sub.18
aliphatic, aromatic, heteroaliphatic, heteroaromatic or mixtures
thereof, with the proviso that R.sub.16 is SiRR'R'', wherein R, R'
and R'' may be the same or different and may be C.sub.1-C.sub.18
aliphatic, aromatic, heteroaliphatic, heteroaromatic or mixtures
thereof and may be L-R.sub.4.
[0024] For formulas IV, V, and VI, R.sub.18-R.sub.23 and
R.sub.24-R.sub.25 and R.sub.26-R.sub.35 may be the same or
different and at least one of R.sub.18-R.sub.23=L-R.sub.4 and at
least one of R.sub.24-R.sub.25=L-R.sub.4 different and at least one
of R.sub.26-R.sub.35=L-R.sub.4 and the rest may be C.sub.1-C.sub.18
aliphatic, aromatic, heteroaliphatic, heteroaromatic or mixtures
with the proviso that R.sub.23 is SiRR'R'', wherein R, R' and R''
may be the same or different and may be C.sub.1-C.sub.18 aliphatic,
aromatic, heteroaliphatic, heteroaromatic or mixtures thereof and
may be L-R.sub.4.
[0025] The silicon-based material may desirably be functionalized
with groups that enhance its net capacity for CO.sub.2. Functional
groups that are expected to be CO.sub.2-philic, and react with
CO.sub.2 in a silicon-based material they functionalize, include
any of those including nitrogen, such as, for example aliphatic
amines, imines, amidines, amides, heterocyclic amino compounds such
as pyridine, aromatic amines such as aniline, and the like, as well
as combinations of any of these. The particular functional group
utilized will depend upon the silicon-based material chosen, and
for those embodiments wherein the silicon-based material comprises
a siloxane, amine functionality may be suitable, since many
aminosiloxanes are readily commercially available, and are readily
further functionalized if desired or required in order to increase
CO.sub.2 reactivity. Examples of amine functional groups that
exhibit CO.sub.2-reactivity include aminomethyl, aminoethyl,
aminopropyl, aminoethyl-aminopropyl, aminoethyl-aminoisobutyl,
aminoethylaminomethyl, 2-aminopyridyl, piperazine-propyl and
imidazoyl propyl.
[0026] Functional groups may be located in a side chain and also be
the end-capping groups. Aminoethyl-aminopropyl siloxane oligomers
with functional groups in the side chain, for example the molecule
shown below at Figure VII has a maximum theoretical CO.sub.2
capacity of about 20 wt %, compared to 10 wt % for 30 wt % aqueous
MEA.
##STR00003##
[0027] One other example of an aminosiloxane with end-capped
functional groups suitable for use in the present absorbent is
aminopropyl terminated polydimethyldisiloxane, shown below in
Figure VIII:
##STR00004##
One such aminosiloxane is used for hair conditioning and
commercially available from Gelest with a number average molecular
weight of from about 850 to about 900, and a calculated CO.sub.2
absorption capacity of from about 4.4 to about 5.2%. It is expected
that the addition of further amine functionality will result in an
increase in this absorption capacity.
[0028] Those of ordinary skill in the art of polymer chemistry are
well versed in methods of adding functional groups to the backbone
of an oligomer useful in the present absorbent. Numerous methods of
attachment of functional groups are known such as hydrosilylation
and displacement as shown in Michael A. Brook's book Silicon in
Organic, Organometallic, and Polymer Chemistry (Wiley VCH Press,
2000).
[0029] The absorbent also comprises one or more hydroxy-containing
solvents. As used herein, the phrase "hydroxy-containing solvent"
means a solvent that has one or more hydroxy groups. The
hydroxy-containing solvent also desirably has a low vapor pressure,
e.g., of from about 0.001 to about 30 mm Hg at 100.degree. C., so
that minimal loss of the hydroxy-containing solvent occurs via
evaporation. Suitable hydroxy-containing solvent are those that do
not substantially chemically react with CO.sub.2, but rather, serve
as a medium for CO.sub.2 transfer to the functionalized
silicon-based material. As a result, the hydroxy-containing
solvents are expected to be capable of increasing the reaction
rate, e.g., by increasing the mass transfer rate, of CO.sub.2 and
the silicon-based material, and also to reduce, or substantially
prevent, excessive viscosity build-up when the silicon-based
material reacts with CO.sub.2. Advantageously, many suitable
hydroxyl-containing solvents may be recycled, along with the
silicon-based material, if desired.
[0030] Examples of suitable hydroxy-containing solvents include,
but are not limited to, those comprising one or more hydroxyl
groups, such as, glycols and hydroxylated silicones. Suitable
glycols may include, for example, trimethylolpropane, glycerol,
ethylene glycol, diethylene glycol, triethylene glycol and
tetraethylene glycol, to name a few. Suitable hydroxylated
silicones include, for example,
1,3-bis(3-hydroxypropyl)tetramethyldisiloxane, or the
hydrosilylation reaction product of 1,1,3,3-tetramethyldisiloxane
and trimethylolpropane allylether. Hydroxy compounds may also be in
the form of phenols such as eugenol, isoeugenol,
2-allyl-6-methylphenol and the like.
[0031] In certain embodiments, the absorbent may comprise an amount
of water, e.g., so that all water need not be removed from the
process stream in order to utilize the absorbent and methods.
Indeed, in some embodiments, water is desirably present and in such
embodiments, can assist in the solubilization of reaction
products.
[0032] Optionally, the absorbent may also include other components,
such as, e.g., oxidation inhibitors to increase the oxidative
stability and anti-foaming agents. The use of oxidation inhibitors,
also called antioxidants, can be especially advantageous in those
embodiments of the invention wherein the functional groups comprise
amine groups.
[0033] The carbon dioxide absorbents provided herein are expected
to provide substantial improvement when utilized to remove CO.sub.2
from process gases, as compared to those currently commercially
available and/or utilized for this purpose. As such, a method of
reducing the carbon dioxide in a process stream is provided and
comprises contacting the process stream with the carbon dioxide
absorbents described herein. The process stream so treated may be
any wherein the level of CO.sub.2 therein is desirably reduced, and
in many processes, CO.sub.2 is desirably reduced at least in the
exhaust streams produced thereby. The process stream is typically
gaseous but may contain solid or liquid particulates, and may be at
a wide range of temperatures and pressures depending on the
application.
[0034] The carbon dioxide absorbents have low volatility, high
thermal stability and are either commercially available with, or
can be provided with, a high net capacity for CO.sub.2, and as
such, are appropriate for large scale implementation. And so, there
is also provided a power plant utilizing the present absorbents,
and method of utilizing the absorbents in a method for generating
electricity with reduced carbon dioxide emissions.
Examples 1-12
[0035] Reaction of silicon-based materials with CO.sub.2 in the
presence of a hydroxy-containing co-solvent.
[0036] To illustrate the ability of the hydroxy-containing
co-solvent triethylene glycol to enhance the CO.sub.2 absorption of
various silicon-based materials as well as provide a liquid medium,
the following Examples 1-12 were conducted. The silicon-based
materials were exposed to 1 atmosphere of CO.sub.2 in the presence
of, or not in the presence of, the hydroxyl-containing co-solvent
triethylene glycol (at 50 wt %, with the exception of example 4 at
75 wt %) at 40.degree. C. for 2 hours (h) with mechanical
stirring.
Comparative Example 1
[0037] Into a pre-tared, 25 mL, three-neck, round-bottom flask
equipped with a mechanical stirrer, gas inlet and a gas outlet and
heated with a temperature controlled oil bath, was charged 2.0707 g
of 1,3-Bis(3-aminopropyl)tetramethyldisiloxane. Dry CO.sub.2 gas
was introduced at a rate of 50 mL/min into the flask via a glass
tube positioned 10 mm above the stirring liquid surface. CO.sub.2
exposure continued for 2 h at 40.degree. C. after which time the
exterior of the flask was cleaned and the flask weighed. The total
weight gain of 0.3588 g corresponded to 71% of the theoretical
amount of weight that should have been gained if all the amine
groups had reacted with a stoichiometric amount of CO.sub.2. The
reaction product was also a solid.
Example 2
[0038] 2.0194 g of 1,3-Bis(3-aminopropyl)tetramethyldisiloxane and
2.0174 g of triethylene glycol were charged into a flask and
allowed to react with CO.sub.2 according to the procedure described
in Example 1. The total weight gain was 0.4089 g. This corresponded
to 114% of the theoretical amount of weight that should have been
gained if all the amine groups had reacted with a stoichiometric
amount of CO.sub.2. The reaction product was a liquid.
Comparative Example 3
[0039] 2.0653 g of aminoethylaminopropyl methylsiloxane oligomer
were charged into a flask and allowed to react with CO.sub.2
according to the procedure described in Example 1. The total weight
gain was 0.21 10 g. This corresponded to 37% of the theoretical
amount of weight that should have been gained if all the amine
groups had reacted with a stoichiometric amount of CO.sub.2. The
reaction product was a solid.
Example 4
[0040] 2.0168 g of aminoethylaminopropyl methylsiloxane oligomer
and 4.0292 g of triethylene glycol were charged into a flask and
allowed to react with CO.sub.2 according to the procedure described
in Example 1. The total weight gain was 0.4803 g. This corresponded
to 87% of the theoretical amount of weight that should have been
gained if all the amine groups had reacted with a stoichiometric
amount of CO.sub.2. The reaction product was a liquid.
Comparative Example 5
[0041] 2.0295 g of
1,3-Bis(3-aminoethylaminopropyl)tetramethyldisiloxane were charged
into a flask and allowed to react with CO.sub.2 according to the
procedure described in Example 1. The total weight gain was 0.3389
g. This corresponded to 64% of the theoretical amount of weight
that should have been gained if all the amine groups had reacted
with a stoichiometric amount of CO.sub.2. The reaction product was
a solid.
Example 6
[0042] 2.0240 g of
1,3-Bis(3-aminoethylaminopropyl)tetramethyldisiloxane and 2.0237 g
of triethylene glycol were charged into a flask and allowed to
react with CO.sub.2 according to the procedure described in Example
1. The total weight gain was 0.4777 g. This corresponded to 90% of
the theoretical amount of weight that should have been gained if
all the amine groups had reacted with a stoichiometric amount of
CO.sub.2. The reaction product was a liquid.
Comparative Example 7
[0043] 1.1090 g of
1,3,5,7-tetrakis(3-aminopropyl)tetramethylcyclotetrasiloxane were
charged into a flask and allowed to react with CO.sub.2 according
to the procedure described in Example 1. The total weight gain was
0.0621. This corresponded to 30% of the theoretical amount of
weight that should have been gained if all the amine groups had
reacted with a stoichiometric amount of CO.sub.2. The reaction
product was a solid.
Example 8
[0044] 1.0722 g of
1,3,5,7-tetrakis(3-aminopropyl)tetramethylcyclotetrasiloxane and
1.1028 g of triethylene glycol were charged into a flask and
allowed to react with CO.sub.2 according to the procedure described
in Example 1 The total weight gain was 0.3099 g. This corresponded
to 154% of the theoretical amount of weight that should have been
gained if all the amine groups had reacted with a stoichiometric
amount of CO.sub.2. The reaction product was a liquid.
Comparative Example 9
[0045] 1.0498 g of Tetrakis(3-aminopropyldimethylsiloxy)silane were
charged into a flask and allowed to react with CO.sub.2 according
to the procedure described in Example 1. The total weight gain was
0.1445 g. This corresponded to 87% of the theoretical amount of
weight that should have been gained if all the amine groups had
reacted with a stoichiometric amount of CO.sub.2. The reaction
product was a solid.
Example 10
[0046] 1.0662 g of Tetrakis(3-aminopropyldimethylsiloxy)silane and
0.1.1175 g of triethylene glycol were charged into a flask and
allowed to react with CO.sub.2 according to the procedure described
in Example 1. The total weight gain was 0.1956 g. This corresponded
to 116% of the theoretical amount of weight that should have been
gained if all the amine groups had reacted with a stoichiometric
amount of CO.sub.2. The reaction product was a liquid.
Comparative Example 11
[0047] 1.2135 g of
1,3-Bis(3,9-dimethyl-5,8,11-trioxa-2-azatetradecan-13-amine) were
charged into a flask and allowed to react with CO.sub.2 according
to the procedure described in Example 1. The total weight gain was
0.0742 g. This corresponded to 44% of the theoretical amount of
weight that should have been gained if all the amine groups had
reacted with a stoichiometric amount of CO.sub.2. The reaction
product was a solid.
Example 12
[0048] 1.0323 g of
1,3-Bis(3,9-dimethyl-5,8,11-trioxa-2-azatetradecan-13-amine) and
1.0368 g of triethylene glycol were charged into a flask and
allowed to react with CO.sub.2 according to the procedure described
in Example 1. The total weight gain was 0.0587 g. This corresponded
to 41% of the theoretical amount of weight that should have been
gained if all the amine groups had reacted with a stoichiometric
amount of CO.sub.2. The reaction product was a liquid.
[0049] The results of Examples 1-12 are summarized in Table 1,
below.
TABLE-US-00001 TABLE 1 Co- % of Physical solvent Theoretical state
of Example Amine present wt gain product 1
1,3-Bis(3-aminopropyl)tetramethyldisiloxane No 71 S comparative 2
1,3-Bis(3-aminopropyl)tetramethyldisiloxane Yes 114 L 3
Aminoethylaminopropyl methylsiloxane No 37 S comparative oligomer 4
Aminoethylaminopropyl methylsiloxane Yes 87 L oligomer 5 1,3-Bis(3-
No 64 S comparative aminoethylaminopropyl)tetramethyldisiloxane 6
1,3-Bis(3- Yes 90 L aminoethylaminopropyl)tetramethyldisiloxane 7
1,3,5,7-tetrakis(3- No 30 S comparative
aminopropyl)tetramethylcyclotetrasiloxane 8 1,3,5,7-tetrakis(3- Yes
154 L aminopropyl)tetramethylcyclotetrasiloxane 9
Tetrakis(3-aminopropyldimethylsiloxy)silane No 87 S comparative 10
Tetrakis(3-aminopropyldimethylsiloxy)silane Yes 116 L 11
1,3-Bis(3,9-dimethyl-5,8,11-trioxa-2- No 44 S comparative
azatetradecan-13-amine) 12 1,3-Bis(3,9-dimethyl-5,8,11-trioxa-2-
Yes 41 L azatetradecan-13-amine)
Examples 13-20
[0050] Reaction of a silicon-based material with CO.sub.2 in the
presence of various hydroxy-containing co-solvents.
[0051] To illustrate the ability of the hydroxy-containing
co-solvents triethyleneglycol dimethyl ether and triethyleneglycol
to enhance the CO.sub.2 absorption of the silicon-based material,
1,3-bis(3-aminopropyl)tetramethyldisiloxane, as well as provide a
liquid medium, the following Examples 13-20 were conducted. In
each, the silicon-based material
1,3-bis(3-aminopropyl)tetramethyldisiloxane was exposed to 1
atmosphere of CO.sub.2 in the presence of or not in the presence of
a hydroxyl-containing co-solvent (concentration?) at 40.degree. C.
for 2 hours (h) with mechanical stirring.
Comparative Example 13
[0052] Into a pre-tared, 25 mL, three-neck, round-bottom flask
equipped with a mechanical stirrer, gas inlet and a gas outlet and
heated with a temperature controlled oil bath, was charged 2.0707 g
of 1,3-Bis(3-aminopropyl)tetramethyldisiloxane. Dry CO.sub.2 gas
was introduced at a rate of 50 mL/min into the flask via a glass
tube positioned 10 mm above the stirring liquid surface. CO.sub.2
exposure continued for 2 h at 40.degree. C. after which time the
exterior of the flask was cleaned and the flask weighed. The total
weight gain of 0.3588 g corresponded to 71% of the theoretical
amount of weight that should have been gained if all the amine
groups had reacted with a stoichiometric amount of CO.sub.2. The
reaction product was also a solid.
Example 14
[0053] 2.0261 g of 1,3-Bis(3-aminopropyl)tetramethyldisiloxane and
2.1198 g of triethyleneglycol dimethyl ether were charged into a
flask and allowed to react with CO.sub.2 according to the procedure
described in Example 13. The total weight gain was 0.2984 g. This
corresponded to 83% of the theoretical amount of weight that should
have been gained if all the amine groups had reacted with a
stoichiometric amount of CO.sub.2. The reaction product was a
solid.
Example 15
[0054] 2.0366 g of 1,3-Bis(3-aminopropyl)tetramethyldisiloxane and
4.0306 g of triethyleneglycol dimethyl ether were charged into a
flask and allowed to react with CO.sub.2 according to the procedure
described in Example 13. The total weight gain was 0.3566 g. This
corresponded to 99% of the theoretical amount of weight that should
have been gained if all the amine groups had reacted with a
stoichiometric amount of CO.sub.2. The reaction product was a
solid.
Example 16
[0055] 2.0194 g of 1,3-Bis(3-aminopropyl)tetramethyldisiloxane and
2.0174 g of triethyleneglycol were charged into a flask and allowed
to react with CO.sub.2 according to the procedure described in
Example 13. The total weight gain was 0.4089 g. This corresponded
to 114% of the theoretical amount of weight that should have been
gained if all the amine groups had reacted with a stoichiometric
amount of CO.sub.2. The reaction product was a liquid.
Example 17
[0056] 2.0230 g of triethyleneglycol was charged into a flask and
allowed to react with CO.sub.2 according to the procedure described
in Example 13. The total weight gain was 0.0004 g. This
corresponded to <1% total weight gain. The reaction product was
a liquid.
Example 18
[0057] 2.0387 g of 1,3-Bis(3-aminopropyl)tetramethyldisiloxane and
1.0454 g of triethyleneglycol were charged into a flask and allowed
to react with CO.sub.2 according to the procedure described in
Example 13. The total weight gain was 0.4071 g. This corresponded
to 113% of the theoretical amount of weight that should have been
gained if all the amine groups had reacted with a stoichiometric
amount of CO.sub.2. The reaction product was a solid.
Example 19
[0058] 2.0178 g of 1,3-Bis(3-aminopropyl)tetramethyldisiloxane and
4.0734 g of triethyleneglycol were charged into a flask and allowed
to react with CO.sub.2 according to the procedure described in
Example 13. The total weight gain was 0.4203 g. This corresponded
to 118% of the theoretical amount of weight that should have been
gained if all the amine groups had reacted with a stoichiometric
amount of CO.sub.2. The reaction product was a liquid.
Example 20
[0059] 2.0186 g of 1,3-Bis(3-aminopropyl)tetramethyldisiloxane,
1.0419 g of triethyleneglycol and 0.2245 g water were charged into
a flask and allowed to react with CO.sub.2 according to the
procedure described in Example 13. The total weight gain was 0.3545
g. This corresponded to 99% of the theoretical amount of weight
that should have been gained if all the amine groups had reacted
with a stoichiometric amount of CO.sub.2. The reaction product was
a liquid.
[0060] The results of Examples 13-20 are summarized in Table 2,
below.
TABLE-US-00002 TABLE 2 Wt ratios (Amine:sol- CO.sub.2 uptake
Physical Example Co-solvent vent:water) (% theoretical) state 13
None 100:0:0 71 S (control) 14 Triethyleneglycol 50:50:0 83 S
dimethyl ether 15 Triethyleneglycol 33:67:0 99 S dimethyl ether 16
Triethyleneglycol 50:50:0 114 L 17 Triethyleneglycol 0:100:0 -- L
18 Triethyleneglycol 67:33:0 113 ~S 19 Triethyleneglycol 33:67:0
118 L 20 Triethyleneglycol 62:31:07 99 L
[0061] Table 2 shows that without a co-solvent,
1,3-bis(3-aminopropyl)tetramethyldisiloxane readily forms a solid
material (Example 13). When triethyleneglycol dimethyl ether is
added as a co-solvent (Examples 14, 15), solid reaction products
are still formed. When triethyleneglycol is added at a 1:1 weight
ratio (Example 16) a homogeneous reaction product is formed that
remains liquid throughout the capture process. Varying the ratio of
co-solvent to capture solvent results in varying degrees of
liquidity and viscosity. (Examples 17-20)
[0062] Table 2 further shows that the co-solvent alone does not
physically absorb a significant amount of CO.sub.2 (Example 17).
However, the mixed system allows for enhanced capture of CO.sub.2
via a synergistic action of the chemical capture process and
physi-sorption. Water may optionally be present to aid in
solubilizing the reaction products (Example 20).
Examples 21-33
[0063] Reaction of a silicon-based material with CO.sub.2 in the
presence of various hydroxy-containing co-solvents.
[0064] To illustrate the ability of various other
hydroxy-containing co-solvents (at 50 weight % concentration) to
enhance the CO.sub.2 absorption of the silicon-based material,
1,3-bis(3-aminopropyl)tetramethyldisiloxane, as well as provide a
liquid medium, the following Examples 21-33 were conducted. In
each, the silicon-based material
1,3-bis(3-aminopropyl)tetramethyldisiloxane was exposed to 1
atmosphere of CO.sub.2 in the presence of or not in the presence of
a hydroxyl-containing co-solvent at 40.degree. C. for 2 hours (h)
with mechanical stirring.
Comparative Example 21
[0065] Into a pre-tared, 25 mL, three-neck, round-bottom flask
equipped with a mechanical stirrer, gas inlet and a gas outlet and
heated with a temperature controlled oil bath, were charged 2.0349
g of 1,3-Bis(3-aminopropyl)tetramethyldisiloxane and 2.0472 g of
SF1488 (a silicone polyether available from Momentive Performance
Materials). Dry CO.sub.2 gas was introduced at a rate of 50 mL/min
into the flask via a glass tube positioned 10 mm above the stirring
liquid surface. CO.sub.2 exposure continued for 2 h at 40.degree.
C. after which time the exterior of the flask was cleaned and the
flask weighed. The total weight gain of 0.2739 g corresponded to
76% of the theoretical amount of weight that should have been
gained if all the amine groups had reacted with a stoichiometric
amount of CO.sub.2. The reaction product was a waxy yellow
solid.
Example 22
[0066] 2.0311 g of 1,3-Bis(3-aminopropyl)tetramethyl-disiloxane and
2.0506 g of a diol terminated disiloxane prepared via the
hydrosilylation of trimethylolpropane mono allyl ether with
tetramethyl disiloxane were charged into a flask and allowed to
react with CO.sub.2 according to the procedure described in Example
21. The total weight gain was 0.3491 g. This corresponded to 97% of
the theoretical amount of weight that should have been gained if
all the amine groups had reacted with a stoichiometric amount of
CO.sub.2. The reaction product was a viscous liquid.
Example 23
[0067] 2.0337 g of 1,3-Bis(3-aminopropyl)tetramethyl-disiloxane and
2.0653 g of tetrathylene glycol were charged into a flask and
allowed to react with CO.sub.2 according to the procedure described
in Example 21. The total weight gain was 0.4182 g. This
corresponded to 116% of the theoretical amount of weight that
should have been gained if all the amine groups had reacted with a
stoichiometric amount of CO.sub.2. The reaction product was a
moderately viscous liquid.
Example 24
[0068] 2.0745 g of 1,3-Bis(3-aminopropyl)tetramethyl-disiloxane and
2.0507 g of poly(propylene glycol) with a molecular weight of 725
were charged into a flask and allowed to react with CO.sub.2
according to the procedure described in Example 21. The total
weight gain was 0.3400 g. This corresponded to 92.5% of the
theoretical amount of weight that should have been gained if all
the amine groups had reacted with a stoichiometric amount of
CO.sub.2. The reaction product was a solid that formed very quickly
on introduction of the gas.
Example 25
[0069] 1.9957 g of 1,3-Bis(3-aminopropyl)tetramethyl-disiloxane and
2.0630 g of a 3:1 blend of tetrathylene glycol and the diol
terminated disiloxane from example B above, were charged into a
flask and allowed to react with CO.sub.2 according to the procedure
described in Example 21. The total weight gain was 0.3937 g. This
corresponded to 111% of the theoretical amount of weight that
should have been gained if all the amine groups had reacted with a
stoichiometric amount of CO.sub.2. The reaction product was a
moderately viscous liquid.
Example 26
[0070] 2.0385 g of 1,3-Bis(3-aminopropyl)tetramethyl-disiloxane and
1.9718 g of trimethyolpropane mono allyl ether were charged into a
flask and allowed to react with CO.sub.2 according to the procedure
described in Example 21. The total weight gain was 0.3876 g. This
corresponded to 107% of the theoretical amount of weight that
should have been gained if all the amine groups had reacted with a
stoichiometric amount of CO.sub.2. The reaction product was a
moderately viscous liquid.
Example 27
[0071] 2.0683 g of 1,3-Bis(3-aminopropyl)tetramethyl-disiloxane and
2.0709 g of eugenol were charged into a flask and allowed to react
with CO.sub.2 according to the procedure described in Example 21.
The total weight gain was 0.3449 g. This corresponded to 94% of the
theoretical amount of weight that should have been gained if all
the amine groups had reacted with a stoichiometric amount of
CO.sub.2. The reaction product was a viscous yellow liquid.
Example 28
[0072] 2.0291 g of 1,3-Bis(3-aminopropyl)tetramethyl-disiloxane and
1.9965 g of trimethylolpropane ethoxylate (4/15 EO/OH, Mn 170) were
charged into a flask and allowed to react with CO.sub.2 according
to the procedure described in Example 21. The total weight gain was
0.3640 g. This corresponded to 101% of the theoretical amount of
weight that should have been gained if all the amine groups had
reacted with a stoichiometric amount of CO.sub.2. The reaction
product was a very viscous yellow liquid.
Example 29
[0073] 2.0157 g of 1,3-Bis(3-aminopropyl)tetramethyl-disiloxane and
2.0675 g of pentaerythritol ethoxylate (3/4 EO/OH, Mn 270) were
charged into a flask and allowed to react with CO.sub.2 according
to the procedure described in Example 21. The total weight gain was
0.3855 g. This corresponded to 108% of the theoretical amount of
weight that should have been gained if all the amine groups had
reacted with a stoichiometric amount of CO.sub.2. The reaction
product was a very viscous liquid.
Example 30
[0074] 1.9999 g of 1,3-Bis(3-aminopropyl)tetramethyl-disiloxane and
2.0129 g of a 2:1 blend of tetraethylene glycol and eugenol were
charged into a flask and allowed to react with CO.sub.2 according
to the procedure described in Example 21. The total weight gain was
0.3773 g. This corresponded to 107% of the theoretical amount of
weight that should have been gained if all the amine groups had
reacted with a stoichiometric amount of CO.sub.2. The reaction
product was a viscous yellow liquid.
Example 31
[0075] 2.0391 g of 1,3-Bis(3-aminopropyl)tetramethyl-disiloxane and
2.0640 g of isoeugenol were charged into a flask and allowed to
react with CO.sub.2 according to the procedure described in Example
21. The total weight gain was 0.3464 g. This corresponded to 96% of
the theoretical amount of weight that should have been gained if
all the amine groups had reacted with a stoichiometric amount of
CO.sub.2. The reaction product was a viscous yellow liquid.
Example 32
[0076] 2.0379 g of 1,3-Bis(3-aminopropyl)tetramethyl-disiloxane and
2.0447 g of sulfolane were charged into a flask and allowed to
react with CO.sub.2 according to the procedure described in Example
21. The total weight gain was 0.3227 g. This corresponded to 89% of
the theoretical amount of weight that should have been gained if
all the amine groups had reacted with a stoichiometric amount of
CO.sub.2. The reaction product was a solid that formed very quickly
on introduction of the gas.
Example 33
[0077] 2.0118 g of 1,3-Bis(3-aminopropyl)tetramethyl-disiloxane and
2.0010 g of 2-allyl-6-methylphenol were charged into a flask and
allowed to react with CO.sub.2 according to the procedure described
in Example 21. The total weight gain was 0.2711 g. This
corresponded to 76% of the theoretical amount of weight that should
have been gained if all the amine groups had reacted with a
stoichiometric amount of CO.sub.2. The reaction product was a light
yellow liquid.
[0078] The results of Examples 21-33 are summarized in Table 3,
below.
TABLE-US-00003 TABLE 3 % of Physical Theoretical state of Example
Co-Solvent (50 wt %) wt gain product 21 SF1488 Momentive Silicone
polyether 76 S Comparative 22 a hydrosilylation reaction product of
1,1,3,3- 97 L tetramethyldisiloxane and trimethylolpropane allyl
ether 23 Tetraethylene glycol 116 L 24 Poly(propylene glycol) MW =
725 93 S 25 Mixture of tetraethylene glycol/1,3-bis(3- 111 L
hydroxypropyl)tetramethyldisiloxane 3:1 26 Trimethylolpropane allyl
ether 107 L 27 Eugenol 94 L 28 Trimethylolpropane ethoxylate Mn =
170 101 L 29 Pentaerythritol ethoxylate Mn = 270 108 L 30 2:1
Tetraethylene glycol/eugenol 107 L 31 Isoeugenol 96 L 32 Sulfolane
89 S comparative 33 2-allyl-6-methylphenol 76 L
Examples 34-50
High throughput Screening Experiments
[0079] The high throughput screening experiments were carried out
using a 27 well parallel reactor (React Vap III) from Pierce and a
Symyx Core Module for automated weighing in 8 mL glass vials. The
experiments were run using technical grade CO.sub.2 at 1 atm and
the flow was set at 1.2 mL/h (10000 cm.sup.2/min) by using a MKS
gas flow controller. Each formulation was tested in triplicate. The
co-solvents were purchased from Aldrich or Fisher Scientific and
used without further purification.
[0080] Each vial was loaded with a stirrer bar and preweighed using
the Symyx Core module. The vials were then loaded with the
corresponding compound (200-300 .mu.L) and the appropriate co
solvent (200-300 .mu.L). The resulting mixture was stirred for
15-20 min and treated with CO.sub.2 gas (1 atm) for 60-120 min at
the desired temperature (40 and 55.degree. C.). After the CO.sub.2
treatment, the reactor block was cooled down to room temperature
and all the vials were transferred to a Symyx Core Module.RTM. for
automated weighing. The physical state of each vial was visually
inspected and recorded. The CO.sub.2 adsorption performance was
reported as an average of the % weight gain after each CO.sub.2
treatment. The results of these experiments are shown in Table
4.
TABLE-US-00004 TABLE 4 % wt Physical Ex. Silicon-based Material
Co-Solvent Wt ratios* %** gain state*** 34
1,3-Bis(3-aminopropyl)tetramethyldisiloxane triethylene 10:90 175
3.1 L glycol 35 1,3-Bis(3-aminopropyl)tetramethyldisiloxane
triethylene 30:70 155 8.2 L glycol 36
1,3-Bis(3-aminopropyl)tetramethyldisiloxane triethylene 50:50 133
11.8 L glycol 37 1,3-Bis(3-aminopropyl)tetramethyldisiloxane N
methyl 50:50 118 10.4 L pyrrolidone 38
1,3-Bis(3-aminopropyl)tetramethyldisiloxane Tetraglyme 50:50 123
10.9 S Comp dimethyl ether 39 Aminoethylaminopropyl triethylene
10:90 165 4.6 L methylsiloxane oligomers glycol 40
Aminoethylaminopropyl triethylene 30:70 122 10.2 L methylsiloxane
oligomers glycol 41 Aminoethylaminopropyl triethylene 50:50 44 6.2
L methylsiloxane oligomers glycol 42 Aminoethylaminopropyl N methyl
50:50 56 7.8 S Comp methylsiloxane oligomers pyrrolidone 43
Aminoethylaminopropyl Tetraglyme 50:50 41 5.7 S Comp methylsiloxane
oligomers dimethyl ether 44 1,3,5,7-tetrakis(3- N methyl 50:50 84
7.9 S Comp aminopropyl)tetramethylcyclotetrasiloxane pyrrolidone 45
1,3,5,7-tetrakis(3- Tetraglyme 50:50 53 5.0 S Comp
aminopropyl)tetramethylcyclotetrasiloxane dimethyl ether 46 1,3-
triethylene 10:90 158 5.0 L
Bis(aminoethylaminomethyl)tetramethyldisiloxane gycol 47 1,3-
triethylene 30:70 117 11.1 L
Bis(aminoethylaminomethyl)tetramethyldisiloxane gycol 48 1,3-
triethylene 50:50 74 11.7 L
Bis(aminoethylaminomethyl)tetramethyldisiloxane gycol 49 1,3- N
methyl 50:50 59 9.3 S Comp
Bis(aminoethylaminomethyl)tetramethyldisiloxane pyrrolidone 50 1,3-
Tetraglyme 50:50 64 10.1 S Comp
Bis(aminoethylaminomethyl)tetramethyldisiloxane dimethyl ether
*Amine:solvent **of theoretical ***After absorption
[0081] Generally speaking, Table 4 shows that capped-hydroxy
compounds yielded solid reaction products while uncapped
co-solvents yielded soluble solutions. Amide solvent, NMP, was only
marginally successful as a solvent.
[0082] While only certain features of the invention have been
illustrated and described herein, many modifications and changes
will occur to those skilled in the art. It is, therefore, to be
understood that the appended claims are intended to cover all such
modifications and changes as fall within the true spirit of the
invention.
* * * * *