U.S. patent application number 12/879579 was filed with the patent office on 2012-03-15 for system and process for capture of acid gasses at elevated-pressure from gaseous process streams.
This patent application is currently assigned to BATTELLE MEMORIAL INSTITUTE. Invention is credited to Mark D. Bearden, David J. Heldebrant, Phillip K. Koech, John C. Linehan, James E. Rainbolt, Feng Zheng.
Application Number | 20120061613 12/879579 |
Document ID | / |
Family ID | 44483942 |
Filed Date | 2012-03-15 |
United States Patent
Application |
20120061613 |
Kind Code |
A1 |
Heldebrant; David J. ; et
al. |
March 15, 2012 |
SYSTEM AND PROCESS FOR CAPTURE OF ACID GASSES AT ELEVATED-PRESSURE
FROM GASEOUS PROCESS STREAMS
Abstract
A system, method, and material that enables the
pressure-activated reversible chemical capture of acid gasses such
as CO.sub.2 from gas volumes such as streams, flows or any other
volume. Once the acid gas is chemically captured, the resulting
product typically a zwitterionic salt, can be subjected to a
reduced pressure whereupon the resulting product will release the
captures acid gas and the capture material will be regenerated. The
invention includes this process as well as the materials and
systems for carrying out and enabling this process.
Inventors: |
Heldebrant; David J.;
(Richland, WA) ; Koech; Phillip K.; (Richland,
WA) ; Linehan; John C.; (Richland, WA) ;
Rainbolt; James E.; (Richland, WA) ; Bearden; Mark
D.; (Richland, WA) ; Zheng; Feng; (Richland,
WA) |
Assignee: |
BATTELLE MEMORIAL INSTITUTE
Richland
WA
|
Family ID: |
44483942 |
Appl. No.: |
12/879579 |
Filed: |
September 10, 2010 |
Current U.S.
Class: |
252/184 ;
558/260; 564/503 |
Current CPC
Class: |
B01D 2257/504 20130101;
B01D 53/78 20130101; B01D 53/77 20130101; B01D 2252/40 20130101;
B01D 53/40 20130101; B01D 53/1493 20130101; Y02C 10/06 20130101;
B01D 2252/30 20130101; B01D 2252/20431 20130101; Y02C 20/40
20200801; B01D 53/1475 20130101 |
Class at
Publication: |
252/184 ;
564/503; 558/260 |
International
Class: |
C07C 69/96 20060101
C07C069/96; C09K 3/00 20060101 C09K003/00; C07C 215/08 20060101
C07C215/08 |
Goverment Interests
STATEMENT REGARDING RIGHTS TO INVENTION MADE UNDER
FEDERALLY-SPONSORED RESEARCH AND DEVELOPMENT
[0001] This invention was made with Government support under
Contract DE-AC05-76RLO1830 awarded by the U.S. Department of
Energy. The Government has certain rights in the invention.
Claims
1. A method for removing CO.sub.2 from a gaseous volume comprising
the steps of: contacting a dry gaseous volume containing CO.sub.2
with at least one CO.sub.2 binding organic compound containing a
neat (anhydrous) tertiary alkanolamine that chemically binds
CO.sub.2 to form a zwitterionic product at a pressure greater than
100 psi and removing said zwitterionic alkylcarbonate product from
said gaseous stream or volume.
2. The method of claim 1 further comprising the step of
depressurizing said zwitterionic alkylcarbonate to release said
chemically bound CO.sub.2 and regenerate said CO.sub.2 binding
organic compound.
3. The method of claim 1, wherein said binding organic compound is
a liquid.
4. The method of claim 1, wherein said tertiary alkanolamine is
selected from the group consisting of: N,N-Dimethylethanolamine
(DMEA); N,N-Diethylethanolamine (DEEA), N,N-Diisopropylethanolamine
(DIPEA); 2-(dimethylamino)-2-methyl-1-propanol (2-DMAM-PrOH); and
combinations thereof.
5. The method of claim 1, wherein the zwitterionic product is an
alkylcarbonate.
6. A method for chemically binding and removing CO.sub.2 from a
gaseous volume comprising the step of: binding CO.sub.2 in said
gaseous volume using at least one CO.sub.2 binding organic compound
containing a neat tertiary amine that when mixed with a primary or
secondary alcohol chemically binds CO.sub.2 in said volume to form
a zwitterionic alkylcarbonate product that removes the CO.sub.2
from said volume or stream.
7. A system for removal of CO.sub.2 from a gaseous volume or
stream, characterized by: at least one CO.sub.2 binding organic
compound comprising a neat tertiary alkanolamine that forms a
zwitterionic product when contacted by CO.sub.2 at a pressure above
ambient that chemically binds and removes CO.sub.2 from said
volume.
8. The system of claim 7, wherein the total system pressure is 100
psi.
9. The system of claim 7, wherein the tertiary amine is a tertiary
ethanolamine selected from the group consisting of:
N,N-Dimethylethanolamine (DMEA); N,N-Diethylethanolamine (DEEA),
N,N-Diisopropylethanolamine (DIPEA);
2-(dimethylamino)-2-methyl-1-propanol (2-DMAM-PrOH); and
combinations thereof.
10. The system of claim 7, wherein said binding organic compound is
a liquid.
11. The system of claim 7, wherein said binding organic compound
further comprises a polar/aprotic non-aqueous solvent of up to
about 50 wt % selected from the group consisting of:
dimethylsulfoxide, dimethylformamide, acetone, and combinations
thereof.
12. The system of claim 7, wherein the zwitterionic product is an
alkylcarbonate.
13. A pressure swing reversible acid gas capture agent having the
structure: wherein n is any carbon based chain and R is a carbon
based chain or a carbon containing alcohol in the absence of water.
##STR00004##
14. A Method for removing acid gasses from a gaseous volume
characterized by the step of: contacting a gaseous volume
containing an acid gas with at least one acid gas binding organic
compound that chemically binds with the acid gas to form a
zwitterionic product at a pressure greater than 100 psi; removing
said zwitterionic product from said gaseous stream or volume; and
exposing said zwitterionic product to a lower pressure to release
said acid gas and regenerate said acid gas binding organic
compound.
Description
FIELD OF THE INVENTION
[0002] The present invention relates generally to organic solvents
that perform (pressure activated) chemically selective capture of
acid gases from gaseous product streams in the absence of water.
More particularly, the invention is a system and process for
capture of CO.sub.2 at elevated pressure from gaseous process
streams.
BACKGROUND OF THE INVENTION
[0003] Acid gases such as carbon dioxide have been implicated as
major and rapidly expanding contributors to climate change over the
last decade. As such, significant effort has been applied to the
capture and sequestration of carbon dioxide (CO.sub.2). CO.sub.2
capture from pre-combustion, post-combustion, and flue gas sources,
as well as contained human living space environments (e.g.,
submarines). Many of these existing systems utilize aqueous
solutions containing primary, secondary or tertiary alkanolamines
such as monoethanolamine (MEA) or methyl diethanolamine (MDEA) that
chemically react with CO.sub.2 and water to form thermally stable
bicarbonate salts. However, aqueous solutions containing these
capture agents have a low capture capacity (.about.7 wt %) and thus
readily reach saturation. Additionally, these aqueous solutions are
generally corrosive to steel and other common materials of
construction. This corrosivity limits the alkanolamine
concentration in water and requires the use of corrosion
inhibitors. The limited alkanolamine concentration requires higher
circulation rates and more energy expenditure for acid gas capture
than would otherwise be necessary.
[0004] Physical absorbents are also commonly used as CO.sub.2
capture agents, but are known to have a low selectivity for
CO.sub.2 unless CO.sub.2 pressures are very high and the gas stream
has a large amount of CO.sub.2. These physical sorbents are often
times irreversible or regenerable only after significant thermal or
chemical treatment. Non-amine based capture agents including, e.g.,
polyethylene glycol (e.g., Selexol.RTM.), cryogenic methanol (e.g.,
Rectisol.RTM.), and N-methylpyrrolidone (e.g., Purisol.RTM.) also
capture CO.sub.2 via physical adsorption by dissolution into the
liquid. However, these sorbents typically suffer from low weight
capture capacities (<10 wt %) and are typically used at total
gas pressures near 600 psig (41.2 atm). See Fundamentals of Natural
Gas Processing, Arthur Kidnay & William Parrish, CRC Press,
Boca Raton, Fla. pages 100-104, 110-113. Accordingly, new
approaches are needed that solve CO.sub.2 selectivity and capacity
issues associated with conventional capture agents and adsorbent
technologies. The present invention meets these needs.
SUMMARY OF THE INVENTION
[0005] The present invention provides a system, method and
materials that enable the pressure-activated reversible chemical
capture of acid gasses such as CO.sub.2 from gas volumes such as
streams, flows or any other volume. Surprisingly, treating a dry
gas stream using neat alkanolamines greatly increases the capture
capacity of the amine and reduces the energy required for
regeneration. In the case of CO.sub.2, contact with the resulting
product is typically but not always limited to a zwitterionic salt,
that can be subjected to a reduced pressure whereupon the resulting
zwitterions decompose and release the captured CO.sub.2 thereby
regenerating the alkanol to its original active state. Surprisingly
the zwitterionic salt like analogous ionic liquids has a
disproportionately high solubility for CO.sub.2 compared to aqueous
solutions of alkanolamines, thus reducing the amount of these
compounds need to capture a given quantity of CO.sub.2. This
invention includes this process as well as the materials and
systems for carrying out and enabling this process.
[0006] In one embodiment the process involves contacting a gaseous
volume containing CO.sub.2 with at least one CO.sub.2 binding
organic compound containing a neat (water free) tertiary
alkanolamine that chemically binds CO.sub.2 to form a zwitterionic
product at a pressure greater than ambient pressure, preferably
greater than 100 psig; and removing the zwitterionic product from
the gaseous stream or volume. If desired the zwitterionic product
can then be subjected to a reduction in pressure to release the
chemically bound CO.sub.2 and regenerate the CO.sub.2 binding
organic compound.
[0007] The equipment used for the gas liquid contact to absorb the
acid gases from the bulk gas stream is the same as that used
conventionally for gas liquid contacting as is familiar to those
skilled in the art. Examples are gas/liquid counterflow absorption
vessels containing an arrangement of trays, packing material, spray
nozzles, and liquid distributors. Other examples are concurrent
contactors such as Venturi scrubbers, spray towers; compact devices
such as Higee contactors, or emulsifiers. Thus, this invention can
incorporate any systems that can be used for efficient gas liquid
contact. Similarly, for fluid regeneration and separation of acid
gas from the capture agent, pressure letdown valves, flash tanks,
centrifugal devices, mist eliminators, and similar equipment used
for separation of the acid gas from the liquid capture agent can be
used.
[0008] Depending upon the exact desires of the user a variety of
modifications and alterations to this general embodiment may be
had. In one embodiment the binding organic compound is a liquid,
selected from the group consisting of: N,N-Dimethylethanolamine
(DMEA); N,N-Diethylethanolamine (DEEA), N,N-Diisopropylethanolamine
(DIPEA); 2-(dimethylamino)-2-methyl-1-propanol (2-DMAM-PrOH); and
combinations thereof. In some applications the zwitterionic product
is an alkylcarbonate.
[0009] In another embodiment binding CO.sub.2 in said gaseous
volume or stream includes using at least one CO.sub.2 binding
organic compound containing a primary or secondary alcohol and a
neat tertiary amine that when mixed, chemically binds CO.sub.2 in
said volume or stream to form a zwitterionic alkylcarbonate product
that removes the CO.sub.2 from the volume or stream.
[0010] A system for performing these methods includes at least one
acid gas binding organic compound (in the absence of water) that
forms a zwitterionic product when contacted by an acid gas at a
pressure above ambient that chemically binds and removes the acid
gas from the volume. In one embodiment of the invention the acid
gas binding organic liquid is an amine, preferably an alkanolamine.
Examples of acid gas binding organic compounds include tertiary
alkanolamines like N,N-Dimethylethanolamine (DMEA);
N,N-Diethylethanolamine (DEEA), N,N-Diisopropylethanolamine
(DIPEA); 2-(dimethylamino)-2-methyl-1-propanol (2-DMAM-PrOH); or
other types of alkanolamines. These materials form zwitterionic
products such as salts and alkylcarbonates. In addition to these
materials various alcohols and or polar/aprotic non-aqueous
solvents such as but not limited to dimethylsulfoxide,
dimethylformamide, acetone, may also be included.
[0011] A preferred example of the material utilized as the
reversible acid gas capture agent has the structure: Wherein n is
any carbon-based chain and R and R.sub.2 are any carbon-based chain
or carbon containing alcohol. The reversible acid gas capture agent
reverts between a non-ionic form in the absence of CO.sub.2 to an
ionic alkylcarbonate in the presence of CO.sub.2 under elevated
pressures. The general reaction is shown below:
##STR00001##
[0012] Various advantages and novel features of the present
invention are described herein and will become further readily
apparent to those skilled in this art from the following detailed
description. In the preceding and following descriptions we have
shown and described only one preferred embodiment of the invention,
by way of illustration of the best mode contemplated for carrying
out the invention. As will be realized, the invention is capable of
modification in various respects without departing from the
invention. Accordingly, the drawings and description of the
preferred embodiment set forth hereafter are to be regarded as
illustrative in nature, and not as restrictive.
BRIEF DESCRIPTION OF THE DRAWINGS
[0013] FIGS. 1a-1d show exemplary materials for use in system and
process of the present invention.
[0014] FIG. 2 is a single component system showing chemical
reaction between an exemplary tertiary alkanolamine and CO.sub.2 at
elevated CO.sub.2 pressure.
[0015] FIG. 3 is a .sup.13C NMR spectrum of a DMEA solution showing
formation of a zwitterionic DMEA-CO.sub.2 alkylcarbonate
species.
[0016] FIG. 4 shows the chemical and physical uptake of CO.sub.2 in
neat DMEA solution as a function of pressure.
[0017] FIG. 5 plots conductance values in DMEA solution as a
function of CO.sub.2 pressure.
[0018] FIG. 6 plots the conductance of DMEA as a function of
CO.sub.2 under repeated contact at pressures from 0 to 180 psi.
[0019] FIG. 7 shows a two component system involving reaction of an
exemplary tertiary amine with a primary alcohol and CO.sub.2 at
elevated CO.sub.2 pressure.
DETAILED DESCRIPTION
[0020] The following description includes the preferred best mode
of one embodiment of the present invention. It will be clear from
this description of the invention that the invention is not limited
to these illustrated embodiments but that the invention also
includes a variety of modifications and embodiments thereto.
Therefore the present description should be seen as illustrative
and not limiting. While the invention is susceptible of various
modifications and alternative constructions, it should be
understood, that there is no intention to limit the invention to
the specific form disclosed, but, on the contrary, the invention is
to cover all modifications, alternative constructions, and
equivalents falling within the spirit and scope of the invention as
defined in the claims.
[0021] In one embodiment of the present invention a material,
system and process for pressure reversible selective chemical
binding of CO.sub.2 is described. This invention allows the
CO.sub.2 to be chemically bound at a pressure greater than ambient
(STP) conditions and to be released by lowering the pressure. This
pressure swing release enables the capture material to be
regenerated to future use in a much more simplistic way than in
other applications that currently exist in the prior art. In one
exemplary embodiment neat alkanolamines are utilized to form a low
molecular weight hybrid (chemical and physical) CO.sub.2 scrubber
that chemically captures CO.sub.2 and regenerates the capture agent
using a pressure-swing, providing an attractive gas capture system
from the vantage point of chemical selectivity, weight capacity,
and non-thermal regeneration. The chemical selectivity provided by
the invention for capture of CO.sub.2 is coupled with the ease and
energy savings provided by pressure reversal for release and
recovery of CO.sub.2.
[0022] The invention could be utilized in a variety of applications
including natural gas sweetening (decontamination) and other
CO.sub.2 scrubbing processes. Because CO.sub.2 scrubbing processes
from natural gas operate under elevated pressures, e.g., from about
300 psi to about 1,000 psi. the ability to absorb CO.sub.2 at these
elevated pressures combined with facile release at standard
temperature and pressure (STP) constitutes a model technique for
capture and recovery of CO.sub.2 from such sources. Further, the
ability to release CO.sub.2 under pressure saves money for
compression costs for sequestration. The invention provides the
first pressure-reversible zwitterionic liquid that can provide
direct replacement for conventional CO.sub.2 capture processes. Two
embodiments of the invention are described hereafter.
[0023] In one embodiment, organic CO.sub.2 binding liquids
containing neat tertiary alkanolamines include both amine and
alcohol functionalities in a single structural moiety (i.e., single
component systems). Single organic CO.sub.2 binding liquid systems
are preferred over dual component systems described hereafter
containing an amine and an alcohol as separate compounds due to
their lower vapor pressures, which are better suited to industrial
applications. However in other applications other configurations
may be desired and appropriately created.
[0024] FIG. 1(a)-1(d) shows exemplary structure of tertiary
alkanolamines that capture CO.sub.2 at elevated pressures.
Exemplary tertiary alkanolamines include, but are not limited to,
e.g., N,N-Dimethylethanolamine (DMEA), N,N-Diethylethanolamine
(DEEA), N,N-Diisopropylethanolamine (DIPEA) and
2-(dimethylamino)-2-methyl-1-propanol (2-DMAM-PrOH). These liquid
compounds are available commercially. Neat N,N-Dimethylethanolamine
(DMEA) shows marked CO.sub.2 capture capacity and is expected to be
an efficient CO.sub.2 capture agent for industrial
applications.
[0025] FIG. 2 shows the reaction scheme of a single component
system involving the chemical reaction between an exemplary
tertiary alkanolamine (DMEA) with CO.sub.2 at elevated CO.sub.2
pressure in the absence of water. Ethanolamines tested in
conjunction with the invention were purified via distillation and
dried/stored over 3 .ANG. molecular sieves to remove water. To
investigate the STP binding efficiency of ethanolamines, neat
solutions of each were bubbled with CO.sub.2 for 1 hour.
.sup.13C-NMR and conductivity experiments allow for quantitative
and qualitative measure of DMEA absorption of CO.sub.2, both
chemical and physical, as well as regeneration of the DMEA from the
bound form (DMEA-CO.sub.2) upon simple depressurization.
[0026] FIG. 3 shows a typical .sup.13C-NMR spectrum of a DMEA
solution showing formation of a zwitterionic DMEA-CO.sub.2
alkylcarbonate species, evidenced by peaks positioned at 125 ppm
and between 156 and 158 ppm, respectively, which are attributed to:
1) dissolved CO.sub.2 and 2) a zwitterionic alkylcarbonate
DMEA-CO.sub.2 moiety, respectively. The .sup.13C NMR spectrum of
this solution shows peaks at 125 ppm and 156 ppm, which are
attributed to dissolved CO.sub.2 and the zwitterionic
alkylcarbonate DMEA-CO.sub.2 (shown in FIG. 2), respectively. Under
STP conditions, none of these materials in the absence of water
absorbed CO.sub.2, physically or chemically at standard temperature
and pressure, as determined by gravimetric uptake and/or
.sup.1H/.sup.13C NMR spectroscopy. At elevated pressures (100-500
psi), however, DMEA successfully captures CO.sub.2 via two modes
simultaneously: chemical binding as the zwitterion, DMEA-CO.sub.2,
and physical absorption.
[0027] FIG. 4 shows the chemical and physical wt % of CO.sub.2
uptake in neat DMEA solution as a function of pressure. TABLE 1
lists calculated values for chemical carboxylation and physical
absorption as a function of pressure.
TABLE-US-00001 TABLE 1 Carbon dioxide uptake in neat DMEA at
various pressures. CO.sub.2 Chemical Physical pressure
absorption.sup.a absorption.sup.a,b Total Material (psi)/ (MPa)
X.sub.CO2.sup.c wt. % X.sub.CO2.sup.c wt. % mole % wt. % DMEA
100/0.69 0.169 7.7% 0.060 2.9% 22.9% 10.6% 200/1.38 0.218 9.7%
0.145 6.7% 36.3% 16.4% 300/2.07 0.244 10.7% 0.204 9.1% 44.8% 19.9%
500/3.45 0.260 11.4% 0.191 8.6% 45.1% 20.0% .sup.acalculated from
.sup.13C NMR integrations of pressurized reactions; values are the
average to two experiments. .sup.bmoles or grams of physically
absorbed CO.sub.2 divided by the sum of absorbed CO.sub.2, DMEA and
DMEA-CO.sub.2. .sup.cmole fraction.
[0028] Chemical carboxylation was calculated by integration of the
relative --CH.sub.2O-- carbons of DMEA-CO.sub.2 and DMEA,
respectively. In the figure, formation of the DMEA-CO.sub.2 moiety
increases as a function of applied gas pressure. Results in TABLE 1
show that DMEA chemically captures up to 7.7 wt. % carbon dioxide
at pressures as low as 100 psi and 9.7, 10.7 and 11.4 wt. % at 200,
300 and 500 psi respectively. Physically absorbed CO.sub.2 also
increases with increased gas pressure, exhibiting 2.9 wt. % at 100
psi to 6.7, 9.1 and 8.6 wt. % at 200, 300 and 500 psi,
respectively. Because carbon dioxide shows relatively high
solubility in ionic liquids and zwitterionic liquids, increasing
the ionic nature of the DMEA/DMEA-CO.sub.2 moieties in solution at
higher pressures may facilitate physical CO.sub.2 absorption.
[0029] As shown in TABLE 1 and in FIG. 4, at 100 psi the amount of
physically absorbed CO.sub.2 is approximately one-third that of the
chemically absorbed CO.sub.2. At elevated pressures, the same ratio
(physical absorbed?) is two-thirds or higher. The combined
chemical/physical CO.sub.2 capacity of DMEA is 10.6 wt. % at 100
psi followed by a significant jump to 16.4, 19.9 and 20 wt. % at
200, 300 and 500 psi, respectively. For reference, CO.sub.2
capacities were compared with CO.sub.2 capacities from conventional
capture agents including, e.g., dimethyl (poly)ethylene glycol
DEPEG, because of the similarity of DEPEG to SELEXOL.RTM.. TABLE 2
compares capture capacities for uptake of CO.sub.2.
TABLE-US-00002 TABLE 2 Comparison of the CO.sub.2 uptake capacities
of DMEA and DEPEG, a Selexol .TM. derivative. CO.sub.2 Total
CO.sub.2 Absorption pressure DMEA DEPEG.sup.a (psi) X.sub.CO2.sup.b
wt. % X.sub.CO2.sup.b wt. %.sup.c 100 0.229 10.6% 0.18 3% 200 0.363
16.4% 0.29 5% 300 0.448 19.9% 0.37 7% 500 0.451 20.0% 0.55 13%
.sup.aData taken/calculated from Gainar et al. (Fluid Phase
Equilibr., 1995, 109, 281). .sup.bmole fraction. .sup.cEstimated
from average molecular weight of mixture.
[0030] As shown in the table, at lower pressures (.ltoreq.300 psi),
DMEA absorbs appreciably more CO.sub.2 than DEPEG per mole of
solvent while at 500 psi DMEA shows evidence of an absorbance
plateau. DMEA exhibits a substantial capacity advantage for
CO.sub.2 over DEPEG (1.5.times. to 3.5.times.) at lower pressures.
Thus mole capacities of DMEA rival those of DEPEG, a Selexol.RTM.
derivative, at pressures .ltoreq.300 psi, while the weight
capacities of DMEA is higher than those of DEPEG up to 500 psig.
While results show DMEA is limited to .about.20 wt. % CO.sub.2
uptake, this feature adds to the utility of the material. As the
zwitterionic salt remains dissolved in the DMEA solution
(.about.3:1 ratio of DMEA:DMEA-CO.sub.2 at a chemical mole fraction
of 0.26), overall solution viscosity remains relatively low such
that the mixture can be pumped through capillary tubes with
diameters as small as 300 .mu.m. Further, when DMEA/DMEA-CO.sub.2
solutions are depressurized, rapid decarboxylation occurs and the
mixture cleanly and easily reverts to DMEA. This is evident by the
disappearance of the alkylcarbonate and dissolved CO.sub.2 peaks
and persistence of the DMEA signals in .sup.13C NMR spectroscopy.
Thus, DMEA represents a CO.sub.2 sorbent which effectively absorbs
CO.sub.2 both chemically and physically under pressure and
successfully decarboxylates at STP to yield DMEA, avoiding the need
for costly thermal regeneration.
[0031] Of the chemical and physical absorption of CO.sub.2 into
DMEA, only chemical reaction leads to a solution whose conductance
is significantly altered. Effect of chemical CO.sub.2 addition on
solvent polarity was measured by the conductivity of DMEA over a
CO.sub.2 atmosphere at various pressures. Anhydrous DMEA showed a
conductance of 3 .mu.S/cm when introduced to a high-pressure
conductance cell. The cell was pressurized with CO.sub.2 at 15 psi
increments and the solution conductance was recorded.
[0032] FIG. 5 plots conductance values in a DMEA solution as a
function of CO.sub.2 pressure. Diffusion and/or chemical addition
of CO.sub.2 into DMEA proved slow at low pressures; at 15 psi,
vigorous stirring for 18 hours was required to reach chemical
equilibrium (i.e., established by an unvarying conductance).
However, equilibrium was attained more rapidly at higher pressures,
an observation attributed to physical CO.sub.2 saturation reached
at lower pressures. At a pressure of from 45 psi to 60 psi, about
3.5 hours was required to reach equilibrium; less than 30 minutes
was needed to reach equilibrium at pressures of 150 psi, 165 psi,
and 180 psi. Conductance of the solution rose from 3 .mu.S/cm to
890 .mu.S/cm at CO.sub.2 pressures from 0 psi to 180 psi. At each
pressure increase, temperature of the cell briefly increased by
3.degree. C. to 6.degree. C., indicating the chemical fixation of
CO.sub.2 by DMEA is slightly exothermic or the heat of dissolution
is exothermic. The significant increase in conductance as a
function of pressure confirms that the interaction of DMEA with
CO.sub.2 involves a chemical reaction to form an ionic species and
not simply a physical dissolution.
[0033] The ability to regenerate DMEA was also tested. Anhydrous
DMEA was carboxylated with CO.sub.2 at a pressure of 180 psi and
depressurized over five cycles. FIG. 6 plots the conductance of
DMEA for the repeated contacts with CO.sub.2 at pressures ranging
from 0 to 180 psi. As shown in the figure, conductance of the
DMEA:DMEA-CO.sub.2 solution for each cycle repeatedly reaches 890
.mu.S/cm (.+-.4 .mu.S/cm) at 180 psi and falls to 42 .mu.S/cm
(.+-.3 .mu.S/cm) at 0 psi. A small residual conductance (42
.mu.S/cm) observed at the end of each cycle was reduced to 7
.mu.S/cm following an N.sub.2 purge of the solution, confirming
that complete chemical decarboxylation can easy be achieved. These
conductance measurements yield no discernable deterioration in the
chemical CO.sub.2-binding uptake capacity of DMEA from repeated
carboxylation/decarboxylation cycles. While this experiment does
not unambiguously verify repeatable physical carbon dioxide uptake
by DMEA, we surmise that gaseous dissolution remains unchanged
after numerous cycles based on the chemical uptake repeatability.
TABLE 3 compares carboxylation properties of DMEA, DEEA, DIPEA, and
2-DMAM-PrOH, respectively.
TABLE-US-00003 TABLE 3 Carbon dioxide uptake by anhydrous
alkanolamines at elevated pressures (25.degree. C.). CO.sub.2
Chemical.sup.a Physical.sup.a,c Total Select .sup.13CNMR Material
(psi). X.sub.CO2.sup.b wt. % X.sub.CO2.sup.b Wt. % wt. % signals
(ppm).sup.d DMEA 300 0.244 10.7% 0.204 9.1% 19.8% 62.3
(--CH.sub.2OCO.sub.2--), 156.23 (--OC(O)O--) DEEA 300 0.209 7.2%
0.223 8.7% 15.9% 62.7 (--CH.sub.2OCO.sub.2--), 158.5 (--OC(O)O--)
DIPEA 300 0.140 4% 0.430 12% .sup. 16% 66.1
(--CH.sub.2OCO.sub.2--).sub., 159.1 (--OC(O)O--) 2-DMAM-PrOH 300
--.sup.e --.sup.e --.sup.e --.sup.e --.sup.e 70.0
(--CH.sub.2OCO.sub.2--), 158.5 (--OC(O)O--) .sup.acalculated from
.sup.13C-NMR integrations of pressurized reactions; values are the
average to two experiments. .sup.bmole fraction. .sup.cmoles/grams
of physically absorbed CO.sub.2 divided by the sum of absorbed
CO.sub.2, chemically bound alkanolamine and free alkanolamine.
.sup.dreferenced to dissolved CO.sub.2 set at 125 ppm except for
2-MDMA-PrOH. .sup.ecould not be determined; see text for
details.
[0034] As shown in TABLE 3, DMEA shows significant CO.sub.2 uptake
at pressures from 100 psi to 500 psi. Other alkanolamines listed in
the table (e.g., DEEA, DIPEA and 2-DMAM-PrOH) exhibit distinctly
different carboxylation properties under similar conditions.
[0035] Increasing the functionalization of the amine moiety with
electron-donating substituents that increase basicity was found to
decrease the chemical binding capacity for CO.sub.2. For example,
results show chemical binding of CO.sub.2 decreases from DMEA to
DEEA to DIPEA by from about 4 to 5 mole % each. While chemical
binding of CO.sub.2 is observed for 2-DMAM-PrOH, CO.sub.2
pressurization of this low melting point (mp=19-20.degree. C.)
liquid results in partial solidification that precludes accurate
measurement of CO.sub.2 uptake capacities via NMR spectroscopy. To
account for the decreasing chemical binding trend for CO.sub.2 of
DMEA>DEEA>DIPEA, relative polarity effects of these solvents
were considered. As described herein, chemical binding of CO.sub.2
by DMEA, DEEA, or DIPEA results in the formation of highly polar
zwitterions, whereas the organic solvents themselves have
relatively low polarities. Stabilization of the polar, highly
charged zwitterions is thus impacted by the intrinsic polarity of
the solvent medium. TABLE 4 lists absorption maxima for Reichardt's
dye used as a molecular probe (given its acute absorption maximum
sensitivity to small polarity changes) to assess polarity in the
DMEA, DEEA, and DIPEA media measured using UV-VIS spectroscopy,
along with absorption maxima in other common organic solvents.
TABLE-US-00004 TABLE 4 Absorption maxima of Reichardt's dye in
alkanolamines DMEA, DEEA and DIPEA and select common organic
solvents. Solvent TOL CH2Cl2 DIPEA CH3CN DEEA i-PrOH DMEA EtOH MeOH
Reichardt's 806 692 624 617 605 592 580 550 516 dye,
.lamda..sub.max (nm) -------------------- increasing polarity
--------------------.fwdarw.
[0036] DMEA (with the smallest N-substituents) is the most polar of
the selected alkanolamines, followed by DEEA, and then DIPEA, whose
bulkier aliphatic N-substituents decrease the polarity of the
solvent. The increasing chemical binding capacity for CO.sub.2 of
DMEA>DEEA>DIPEA is attributed to more effective stabilization
of the corresponding zwitterionic alkylcarbonate associated with
the increasing solvent polarity. This stabilizing polarity effect
overshadows the basicity effect of the alkanolamines, highlighting
an important principle for these types of liquids with regard to
chemical CO.sub.2 binding capacity. For physical uptake of
CO.sub.2, the opposite trend is observed, with
DIPEA>DEEA>DMEA. CO.sub.2 shows greater physical solubility
in aliphatic, non-polar organic solvents than in polar media. Here
the increased physical absorption of CO.sub.2 in DIPEA over the
more polar DMEA and DEEA is attributed to the affinity of dissolved
CO.sub.2 for non-polar organic solvents.
[0037] In another embodiment of the invention, a two component
system for CO.sub.2 capture involves a tertiary amine (e.g.,
triethylamine) paired with a primary or a secondary alcohol at
elevated pressures (above STP) to form ammonium alkylcarbonate
ionic liquids, as shown in Equations [1] and [2]:
CO.sub.2+Base+ROHBaseH.sup.+ROCO.sub.2.sup.- [1]
K.sub.eq=[BaseH.sup.+][ROCO.sub.2.sup.-]/P.sub.CO2[Base][ROH][
2]
[0038] Tertiary amines show little-to-no binding of CO.sub.2 in
combination with alcohols at STP. Thus, captured CO.sub.2 can be
easily stripped by depressurizing the system.
[0039] FIG. 7 shows the carboxylation of methanol with tertiary
amines and other bases at elevated CO.sub.2 pressures, e.g., near
10 atm. TABLE 5 shows the reactivity of methanol with several
exemplary tertiary amines and other bases at the elevated CO.sub.2
pressure of 10 atm.
TABLE-US-00005 TABLE 5 Carbonation of methanol with various
tertiary amines IR (C.dbd.O) .sup.13C NMR pKa R.sub.3
Conversion.sup.a cm.sup.-1 ppm (DMSO) Triethylamine 75% 1654
52.3.sup.b 9.0 160.1.sup.c Diisopropylethylamine 92% 1647 51.1 18.6
158.8 (MeCN) DABCO.sup.d 64% 1650 49.1 8.9 160.0 DMAP.sup.e 64%
1651 52.4 160.5 DBU.sup.f 98% 1642 52.2 24 159.8 (MeCN)
2,6-Lutidine No reaction ~4 Pyridine No reaction 3.4
.sup.aConversion based on amine as determined by in situ .sup.13C
NMR of 2M base in methanol under 10 atm CO.sub.2. .sup.bResonance
of methyl carbon in CH.sub.3OC(O)O.sup.-. .sup.cResonance of
carbonate carbon in CH.sub.3OC(O)O.sup.-.
.sup.d1,4-diazabicyclo[2.2.2]octane.
.sup.e4-(dimethylamino)pyridine.
.sup.f1,8-Diazabicyclo[5.4.0]undec-7-ene.
[0040] Tertiary amines produced ammonium methylcarbonate salts at a
high conversion (.about.159 ppm .sup.13C NMR). The alkylcarbonate
peak is indicative of the chemical binding of CO.sub.2 (as compares
with physical dissolution, which involves a CO.sub.2 peak at 125
ppm). At the pressures used in this study, there was also
substantial dissolved CO.sub.2 observed in the .sup.13C NMR
spectra. The strongest bases such as DBU and Diisopropylethylamine
(Hunig's base) showed the highest conversion, followed by TEA,
DABCO and DMAP. Hunig's base, which has the same basicity as TEA,
has 17% more bound CO.sub.2. DABCO and DMAP bind less CO.sub.2
likely due to steric bulk. Lutidine and Pyridine showed no
reactivity to form alkyl carbonates at this pressure most likely
due to their much-reduced basicity compared to tertiary amines.
Ammonium alkylcarbonate salts listed in TABLE 5 decompose back to
the corresponding amine, methanol, and CO.sub.2 upon return of
CO.sub.2 pressure to atmospheric conditions, however stronger bases
such as DBU need thermal regeneration and do not decarboxylate upon
reduction in pressure.
[0041] Carboxylations were also performed in MeCN solvent rather
than methanol. TABLE 6 lists carbonation results of various
alcohols with TEA and CO.sub.2 in MeCN.
TABLE-US-00006 TABLE 6 Carboxylation of various alcohols with
triethylamine and CO.sub.2 R Conversion.sup.a CH.sub.3-- 75%
CH.sub.3CH.sub.2-- 75% 1-octanol 25% ##STR00002## 65%.sup.b
##STR00003## 35%.sup.c i-Propanol 25% t-Butanol No Reaction Phenyl
No Reaction a) Conversion based on NEt.sub.3. b) Initial product is
ClCH.sub.2CH.sub.2OCO.sub.2-. This product cleanly cyclizes to
ethylene carbonate. c) Reaction was performed in CH.sub.3CN. Only
one hydroxyl is carbonated.
[0042] Primary and secondary alcohols readily convert to
corresponding alkyl carbonates, whereas tertiary alcohols do not.
Results are attributed to steric crowding of the alcohol. Data also
show the degree of carboxylation of the alcohol decreases as the
alcohol chain length increases and subsequently becomes less polar.
The decrease in polarity is attributed to the lack of a polar
solvent that can stabilize the transition states of the molecules
during the carboxylation process. For example, trifluoroethanol
(considered to have a steric bulk equivalent with that of ethanol,
but with a much lower pKa) is unreactive toward CO.sub.2. Phenol
doesn't carboxylate under these conditions, which is likely due to
it being too acidic to bind CO.sub.2. Data in TABLES 5 and 6
suggest short linear alcohols and tertiary amines are preferred
combinations for a high-pressure CO.sub.2 capture solvent system,
but is not limited thereto.
[0043] A first challenge in designing neat trialkylamine and
alcohol blends to perform capture in the absence of solvent is to
use alcohols and bases that are non-volatile and to form liquid
ammonium alkylcarbonates (not solids as in the case of methanol)
that are cheap. We set out to find a non-volatile tertiary amine
and alcohol that would mitigate material loss and improve costs.
The amine and alcohol were bifunctionalized to make them less
volatile. As CO.sub.2 is introduced over an organic molecule, it
causes volumetric expansion and a decrease in polarity as the mole
fraction of CO.sub.2 increases. CO.sub.2 binding requires a highly
polar medium to stabilize the polar transition states and the
zwitterionic alkylcarbonate. Polarity data measured for
alkanolamines demonstrates that a CO.sub.2 pressure near 150 psi
decreases the polarity. A drop in polarity promotes dissolution of
CO.sub.2 into the alkanolamine, not the desired chemical binding.
DMEA however is sufficiently polar to stabilize these polar species
and subsequently is a good candidate to react with CO.sub.2 at a
low pressure (i.e., 150 psi) condition.
[0044] Decomposition of the alkylcarbonate salts by
depressurization is highly advantageous for high-pressure CO.sub.2
gas capture as the pressure swing avoids use of an energy intensive
thermal solvent regeneration cycle. The demonstrated pressure
desorption of the chemically bound CO.sub.2 from ammonium
alkylcarbonates parallels the energy requirements for the release
of physically absorbed CO.sub.2 by industrial materials such as
SELEXOL.RTM. and RECTISOL.RTM.. These high-pressure anhydrous
alkanolamines can potentially be superior to physical sorbents
because they contain the economical pressure swing yet they contain
a highly chemically selective CO.sub.2 capture.
[0045] The following example provides a further understanding of
the invention. Dissolved CO.sub.2 appears at 125 ppm in .sup.13C
NMR spectra in multiple organic solvents while the alkylcarbonate
(R--O--CO.sub.2.sup.-) peak appears at 158 ppm. The carbonyl signal
is attributed to the alkylcarbonate, as carbamates do not form for
the tertiary amine. While primary and secondary amines can and do
react with carbon dioxide to yield carbamates, tertiary amines do
not react directly with CO.sub.2, although bicarbonate salts can
form in the presence of water. .sup.13C NMR chemical shifts confirm
that chemical CO.sub.2 binding to an alkanolamine (in the absence
of water) proceeds via the alcohol moiety of DMEA as opposed to the
tertiary amine. The appearance of a resolved --CH.sub.2O--
methylene signal at 63 ppm, downfield from the alcohol methylene of
DMEA, is indicative of the effects of .beta.-carboxylation as
opposed to N-carboxylation. To investigate the extent to which DMEA
will absorb CO.sub.2, neat solutions of DMEA were pressurized at
100, 200, 300 and 500 psi of CO.sub.2 for 18 hours, loaded into a
PEEK NMR tube and analyzed. Carboxylation experiments at higher
pressures were not performed as CO.sub.2 begins to liquefy above
500 psi. Under these conditions CO.sub.2 is likely to phase
separate from the DMEA/DMEA-CO.sub.2 mixture and hamper NMR
interpretation. Both DMEA-CO.sub.2 and dissolved CO.sub.2 were
observed at all pressures and the relative quantities of each
calculated from .sup.13C NMR integrations. Extent of both chemical
carboxylation and physical absorption as a function of pressure
were calculated (see TABLE 1 and FIG. 4) using the relative
integration of the --CH.sub.2O-- carbons of DMEA-CO.sub.2 and DMEA.
Physical absorption was found by comparing the relative integration
of the carbonyl carbons of CO.sub.2 and DMEA-CO.sub.2.
[0046] Neat solutions of alkyl ethanolamines (DMEA, DEEA, and
DIPEA) absorb and chemically bind carbon dioxide at elevated
pressures by formation of alkylcarbonates. Through both chemical
binding and physical absorption DMEA captures up to 45 mole % (20
wt. %) carbon dioxide, while DEEA captures up to 43 mole % (16 wt.
%) and DIPEA captures up to 57 mole % (16 wt. %) carbon dioxide
(300 psi). The increasing chemical uptake capacity trend of
DMEA>DEEA>DIPEA is attributed to solvent polarity effects
while the physical CO.sub.2 absorption trend of
DIPEA>DEEA>DMEA is explained by the affinity of carbon
dioxide for non-polar organic media. DMEA shows the greatest wt. %
uptake of carbon dioxide and chemically binds CO.sub.2 under
pressure more effectively than the other tertiary ethanolamines to
form the thermodynamically unstable zwitterionic alkylcarbonate
salt DMEA-CO.sub.2. DMEA captures up to 45 mole % (20 wt. %) of
CO.sub.2 at 500 psi via combined chemical binding and physical
absorption. Carbon dioxide weight capacities of DMEA rival those of
DEPEG, a SELEXOL.RTM. derivative, at pressures 300 psi.
DMEA-CO.sub.2, DEEA-CO.sub.2 and DIPEA-CO.sub.2 are characterized
by high-pressure .sup.13C NMR and give rise to .sup.13C resonances
analogous to previously studied zwitterionic alkylcarbonates. The
zwitterion DMEA-CO.sub.2 regenerates CO.sub.2 and DMEA upon
depressurization. This natural decarboxylation when pressure is
release is advantageous for high-pressure gas-capture systems as
the sorbent can be regenerated by an economical pressure swing as
opposed to a more costly thermal swing. Repeated CO.sub.2
absorption/release experiments show no decline in the chemical
binding CO.sub.2 uptake capacity of DMEA over 5 cycles.
[0047] Tertiary amines combined with alcohols chemically and
selectively bind CO.sub.2 under mild pressures to form
thermodynamically unstable alkylcarbonate salts. The carboxylations
of numerous amine and alcohol pairs can be tracked in situ using IR
and NMR spectroscopy. Alkanolamines also capture CO.sub.2 under
elevated pressures as zwitterionic alkylcarbonate salts. The degree
of alcohol carboxylation is limited by the polarity of the solvent
as well as the basicity of the amine. Ammonium alkylcarbonate salts
decarboxylate into their corresponding alcohols and amines unless
under pressures near 10 ATM. This natural decarboxylation when
pressure is released is advantageous for high-pressure gas-capture
systems because the sorbent can be regenerated by an economical
pressure swing instead of the more costly thermal swing.
[0048] While preferred embodiments of the present invention have
been shown and described, it will be apparent to those of ordinary
skill in the art that many changes and modifications may be made
with various material combinations without departing from the
invention in its true scope and broader aspects. The appended
claims are therefore intended to cover all such changes and
modifications as fall within the spirit and scope of the
invention.
* * * * *