Patent Description:
Emission of carbon dioxide is considered the main cause of the greenhouse effect and global warming. In the Kyoto Protocol the United Nations Framework Convention on Climate Change has set targets for the reduction of greenhouse gas emissions.

One method of reducing atmospheric CO<NUM> emissions is through its capture and subsequent geological storage. In post combustion capture, the CO<NUM> in flue gas is first separated from nitrogen and residual oxygen using a suitable solvent in an absorber. The CO<NUM> is then removed from the solvent in a process called stripping (or regeneration), thus allowing the solvent to be reused. The stripped CO<NUM> is then liquefied by compression and cooling, with appropriate drying steps to prevent hydrate formation. Post combustion capture in this form is applicable to a variety of CO<NUM> sources including power stations, steel plants, cement kilns, calciners, biogas plants, natural gas processing, methane reforming and smelters.

Aqueous amine solutions and alkanolamine solutions in particular, have been investigated as solvents in post combustion CO<NUM> capture. The capture process involves a series of chemical reactions that take place between water, the amine and carbon dioxide. Amines are weak bases, and may undergo acid-base reactions. Once dissolved into the amine solution, the aqueous CO<NUM> reacts with water and the neutral form of the amine react to generate carbamate, protonated amine, carbonic acid (H<NUM>CO<NUM>), aqueous bicarbonate (HCO<NUM> -) ions and aqueous carbonate (CO<NUM> <NUM>-) ions.

CO<NUM> desorption is achieved by heating of an aqueous amine solution containing CO<NUM>. The two major effects of heating are to reduce the physical solubility of CO<NUM> in the solution, and to reduce the pKa of the amine resulting in a concomitant reduction in pH and in CO<NUM> absorption capacity, the net effect of which is CO<NUM> release. The extent of the reduction in pKa is governed by the enthalpy of the amine protonation reaction which in turn is governed by the amine chemical structure. All the other reactions, including carbamate formation, have small reaction enthalpies and are insensitive to temperature. Typically, the enthalpy of amine protonation is four to eight times larger than the enthalpies of the carbonate reactions and two to four times larger than the enthalpy of carbamate formation. It is the lowering of the pH upon heating that drives the reversal of carbamate and carbonate/bicarbonate formation during desorption, rather than any significant reduction in stability.

The cyclic capacity (αcyclic) of an aqueous amine solution is defined as the moles of CO<NUM> that can be absorbed and released per mole of amine by cycling the absorbent between low temperature (αrich) and high temperature (αlean): αcyclic=αrich-αlean. In terms of chemistry, this cyclic capacity is primarily governed by the change in amine pKa with temperature. The larger this cyclic capacity, the more efficient the amine. <NUM> wt % monoethanolamine, which is currently employed in industrial CO<NUM> capture, possesses an undesirable cyclic capacity of approximately αcyclic=<NUM> (<NUM>-<NUM>).

<CIT> describes a process for absorption of an acid gas which involves contacting the acid gas with a benzylamine compound and a cosolvent which reduces the vapour pressure of the benzylamine. The use of certain cosolvents also ameliorates the problem precipitate formation due to low solubility of the anion formed from reaction of the benzylamine compound with carbon dioxide.

<CIT> discloses aqueous compositions for capturing an acid gas such as CO<NUM>. The aqueous compositions comprise an organic salt and an amine compound. A wide range of suitable amine compounds are disclosed, including compounds with a primary amine group (-NH<NUM>) tethered to an N-heterocycle by an ethylene (-CH<NUM>-CH<NUM>-) or propylene (-CH<NUM>-CH<NUM>-CH<NUM>-) linker.

<CIT> discloses compositions for capturing an acid gas such as CO<NUM>. The compositions comprise a primary or secondary amine in combination with either an azabicyclo compound or a N-heteroaromatic ring compound. Examples <NUM>-<NUM> disclose aqueous compositions comprising piperazine in combination with an aminopyridine compound in which an amine group (-NH<NUM>, -NHCH<NUM> or -N(CH<NUM>)<NUM>) is directly bonded to a pyridine ring.

There remains a need to identify amines and systems which provide improved properties and/or reduce problems in carbon dioxide capture and release.

The invention provides a process for absorbing carbon dioxide from a gas stream containing carbon dioxide, comprising contacting the gas stream with an absorbent comprising an aqueous composition comprising at least 10wt% water and a substituted heteroaromatic compound selected from formula Ia, Ib, Ic, Id and mixtures of two or more thereof:
<CHM>
<CHM>
wherein.

The invention also provides a composition of absorbed carbon dioxide comprising:.

In one set of embodiments the concentration of substituted heteroaromatic compound is 1wt% to 80wt% of the aqueous composition, preferably 10wt% to 80wt% of the aqueous composition.

In one set of embodiments the amount of water in the aqueous composition is at least <NUM> wt%.

The process of the invention may also be carried out using a further absorbent for carbon dioxide in addition to the substituted heteroaromatic compound. The weight ratio of the substituted heteroaromatic compound to further absorbent may, for example, be from <NUM>:<NUM> to <NUM>:<NUM>.

The substituted heteroaromatic compound of the composition provides a high cyclic capacity for carbon dioxide allowing efficient capture and desorption of carbon dioxide while also providing a low vapour pressure in aqueous solution and good solubility of the substituted heteroaromatic compound and species formed on absorption of carbon dioxide. The aqueous composition may therefore be used without a requirement for specific co-solvents and provides flexibility in formulating aqueous compositions for carbon dioxide capture and release.

We have found that the long term stability of the substituted heteroaromatic compound during CO<NUM> capture, particularly where R<NUM> is methylene in accordance with the invention, is enhanced in the presence of a further amine of higher basicity than the substituted heteroaromatic compound. In a preferred embodiment the absorbent further comprises an amine selected from tertiary amines and primary and secondary sterically hindered amines and mixtures thereof having a higher basicity than the substituted heteroaromatic compound. In particular, in the case of the present invention where R<NUM> is methylene (such as for (aminomethyl)pyridines), the further amine selected from tertiary amines and primary and secondary sterically hindered amines and mixtures thereof typically has a pKa of at least <NUM> at <NUM>. A pKa of <NUM> is about <NUM> above the pKa of (aminomethyl)pyridines, specifically each of <NUM>-(aminomethyl)pyridine, <NUM>-(aminomethyl)pyridine and <NUM>-(aminomethyl)pyridine.

As used herein, except where the context requires otherwise, the term "comprise" and variations of the term, such as "comprising", "comprises" and "comprised", are not intended to exclude further additives, components, integers or steps.

Examples of the invention are described with reference to the attached drawings.

The aqueous absorbent composition for absorption of carbon dioxide from the gas stream comprises at least 10wt% water and a substituted heteroaromatic compound selected from formula Ia, Ib, Ic, Id and mixtures of two or more thereof:
<CHM>
<CHM>
wherein.

Preferably formula I is of formula Ia:
<CHM>
<CHM>
wherein.

Still more preferably the substituted heteroaromatic compound is selected from the group consisting of formula IIa, IIb, IIc and mixtures of two or more thereof:
<CHM>
wherein R<NUM> is methylene.

Examples of substituted heteroaromatic compounds include <NUM>-(aminomethyl)pyridine, <NUM>-(aminomethyl)pyridine, <NUM>-(aminomethyl)pyridine or a mixture of two or more thereof.

The absorbent composition need not include ionic liquids or organic salts such as imidazolium cation or quaternary ammonium salts and will typically include a water content of more than <NUM> wt% of the absorbent composition such as at least <NUM> wt%.

Compositions of the substituted heteroaromatic compound, particularly the (aminomethyl)pyridines, have lower susceptibility to thermal and oxidative degradation than a <NUM> wt% MEA solution due to the inherent chemical stability imparted by the heteroaromatic ring structure. Preferably the cyclic absorption capacity of the solution for CO<NUM> is comparable to that of a tertiary or sterically hindered amine solution and the rate of absorption of the target gas is comparable to or better than a 30wt% MEA solution.

At least one of the substituted heteroaromatic compounds may constitute the total of the carbon dioxide absorbent compound or may be present in solution with other suitable carbon dioxide absorbent compounds so that the total gas absorbent compounds comprise one or more gas absorbent compounds in addition to the substituted heteroaromatic compound. The substituted heteroaromatic compound preferably comprises at least <NUM> wt%, more preferably <NUM> wt% to <NUM> wt%, still more preferably <NUM> wt% to <NUM> wt%, even more preferably <NUM> wt% to <NUM> wt%, more preferably <NUM> wt% to <NUM> wt%, such as <NUM> wt% to <NUM> wt%, <NUM> wt% to <NUM> wt% or <NUM> wt% to <NUM> wt% relative to the total weight of the solution. In some embodiments the concentration of the substituted heteroaromatic compound in the aqueous composition is from <NUM> wt% to <NUM> wt% such as <NUM> wt% to <NUM> wt%, <NUM> wt% to <NUM> wt% or <NUM> wt% to <NUM> wt%. The high solubility of the substituted heteroaromatic compound allows high loadings to be used in aqueous solution and also provides a solution stable intermediate in the carbon dioxide absorption process. It therefore provides significant practical advantages in this respect when compared with benzyl amine and its derivatives.

The total wt% of the at least one absorbent compound (including the substituted heteroaromatic compound) in solution is preferably at least <NUM> wt%, more preferably at least <NUM> wt%, still more preferably at least <NUM> wt%, even more preferably at least <NUM> wt% and yet even more preferably at least 50wt% relative to the total weight of the solution. This component will typically consist of the substituted heteroaromatic compound and optionally one or more compounds selected from amines and in the preferred embodiment at least one of the aminomethyl substituted heteroaromatic compounds and one or more amines selected from tertiary amine or sterically hindered primary or secondary amine which has a higher basicity than the substituted heteroaromatic compounds.

In one set of embodiments the absorbent composition may comprise:.

Further components may be present such as solvents, solutes or other materials.

When the additional amine absorbent for carbon dioxide is present, the weight ratio of the substituted heteroaromatic to further amine may, for example, be in the range of from <NUM>:<NUM> to <NUM>:<NUM> such as <NUM>:<NUM> to <NUM>:<NUM> or <NUM>:<NUM> to <NUM>:<NUM>.

In one embodiment the solution contacted with the gas stream comprises one or more additional carbon dioxide gas absorbing compounds selected from amines and imidazoles in addition to the substituted heteroaromatic compound. The one or more additional amines may be selected from primary, secondary and tertiary amines.

Examples of suitable amines include primary amines such as monoethanolamine, ethylenediamine, <NUM>-amino-<NUM>-methyl-<NUM>-propanol, <NUM>-amino-<NUM>-methylethanolamine and benzylamine; secondary amines such as N-methylethanolamine, piperazine, piperidine and substituted piperidine, <NUM>-piperidinemethanol, <NUM>-piperidineethanol, <NUM>-piperidinemethanol, <NUM>-piperidineethanol, diethanolamine, diglycolamine and diisopropanolamine; and tertiary amines such as N-methyldiethanolamine, N-piperidinemethanol, N-piperidineethanol, N,N-dimethylaminoethanol and <NUM>-quinclidinol; imidazole and N-functionalised imidazole and amino acids such as taurine, sarcosine and alanine.

The process is particularly effective in capture of CO<NUM> in the presence of a further amine component selected from tertiary amines and sterically hindered primary and secondary amines.

We have found through pilot plant testing that (aminomethyl)heteroaromatics, particularly the (aminomethyl)pyridines, degrade slowly when the gas stream contains a significant oxygen component which is often the case in combustion gas streams. The resulting product of oxidation is an imine which is a dimer. The formation of the dimer is understood to occur according to the scheme shown below:
<CHM>.

The mode of degradation is considered to be unique to aminomethyl substituted aromatics and aminomethyl substituted heteroaromatics as the same dimer stability arising through conjugation with the aromatic ring is not possible for alkyl ckains. The above scheme and stabilisation of the imine is consistent with a synthetic scheme reported for the preparation of more complex heterocyclics such as aromatic and heteroaromatic substituted benzimidazoles in <NPL>. The resulting imine is favoured as it forms a stable conjugated pi-bonding arrangement. This stabilisation does not extend to aminoalkylsubstituted heteroaromatics in which the alkyl linking group is ethyl or longer chain alkyl which undergo degradation via similar pathways to aliphatic amines such as the formation of carboxylic acids, aldehydes and amino acids (<NPL>)).

We have found that formation of the imine and resulting degradation of the aminomethyl-substituted heteroaromatic is inhibited in the presence of an amine, particularly a tertiary amine or sterically hindered primary or secondary amine which has a higher basicity than the aminomethyl-substituted heteroaromatic. For example a pKa at least <NUM> higher than the pKa of the aminomethylheteroaromatic. In the case of (aminomethyl)pyridines the pKa of <NUM>-(aminomethyl)pyridine, <NUM>-(aminomethyl)pyridine and <NUM>-(aminomethyl)pyridine at <NUM> is <NUM>. It is preferred that the further amine, particularly a sterically hindered amine or tertiary amine, have a pKa of at least <NUM>, such as a pKa of at least <NUM>, a pKa of <NUM> to <NUM> or pKa of <NUM> to <NUM>. It is considered that the higher basicity adsorbs protons from the acid gas in solution thereby inhibiting the initial step in the degradation process. In practice the combined use of an (aminomethyl)pyridine with an amine selected from the group consisting of tertiary amines and sterically hindered primary and secondary amines and mixtures thereof of higher basicity, such as <NUM>-amino-<NUM>-methyl-<NUM>-propanol bas been found to very dramatically reduce the imine formation and resultant degradation of the (aminomethyl)pyridine.

As used herein the term "sterically hindered amine" is defined as those compounds containing at least one primary or secondary amino group attached to either a secondary or tertiary carbon atom. In one embodiment the sterically hindered amine is a secondary amino group attached to either a secondary or tertiary carbon atom or a primary amino group attached to a tertiary carbon atom. Examples of suitable sterically hindered amines and tertiary amines include those shown in the following table with the corresponding pKa at <NUM>.

Other suitable tertiary amines and sterically hindered amines of the required basicity will be readily apparent to those skilled in the art having regard to the above reference degradation mechanism and method of inhibition of imine formation.

Accordingly in a preferred aspect the further amine optionally present in the composition is present in an amount of <NUM> wt% to <NUM> wt% the absorbent. In a further aspect the absorbent comprises:.

In a further embodiment the absorbent comprises:.

The tertiary and sterically hindered amines are typically soluble in the composition at the desired concentration at <NUM>. Preferably the tertiary and sterically hindered amines are water soluble at <NUM>.

In a further embodiment, the solution comprises an amine absorbent selected from imidazole and more preferably an N-functionalised imidazole. Suitable N-functionalised imidazoles may be found in <CIT>.

The suitable N-functionalised imidazoles disclosed in <CIT> are of formula (<NUM>):
<CHM>
wherein.

Specific examples of such compounds include the <NUM>-N-(C<NUM> to C<NUM> alkyl) imidazoles such as <NUM>-butyl imidazole.

In some, embodiment the solution comprises a combination of N-functionalised imidazoles and one or more amines in addition to the substituted heteroaromatic compound.

The one or more amines which may be used in addition to the N-functionalised imidazoles may be selected from the group consisting of primary, secondary and tertiary amines including the specific examples of such amines referred to above.

In another aspect of the disclosure, a process for removing carbon dioxide gas from a gas mixture includes: contacting a gas mixture that is rich in carbon dioxide with an absorbent solution, as described above, to form a target gas rich solution and a gas mixture that is lean in target gas; and desorbing the carbon dioxide gas from the solution. There is further provided use of a substituted heteroaromatic compound in aqueous solution at a concentration of at least <NUM>% by weight, based on the total weight of the solution, for absorbing carbon dioxide from a gas stream. Desorbing the carbon dioxide may be facilitated by an increase in temperature, reduction in pressure, change in pH or combination of these factors. It is a significant advantage of the invention that the cyclic capacity of CO<NUM> brought about by these changes is generally speaking higher for the substituted heteroaromatic compound used in the process of the invention than the molar equivalent of other absorbents such as monoethanolamine.

In one aspect of the invention there is further provided a composition of absorbed carbon dioxide comprising:.

Preferably, the concentration of the absorbed carbon dioxide is at least two times (and even more preferably at least five times) the equilibrium concentration when the solution is exposed to air at below the boiling point of the aqueous solvent, thus representing the absorbed carbon dioxide concentration in the solvent during the absorption process as previously described. The background amount of CO<NUM> will generally be less than <NUM>% by weight based on the total weight of the solution. In one embodiment the absorbed carbon dioxide will constitute at least <NUM>% by weight based on the total weight of the solution on absorption of the gas, more preferably at least <NUM>%, and still more preferably at least <NUM>% absorbed carbon dioxide by weight based on the total weight of the solution.

In one embodiment the solution comprises one or more amines in addition to the substituted heteroaromatic compound. The additional amines may, for example, be selected from primary, secondary and tertiary amines optionally including N-functionalised imidazoles such as those of formula (<NUM>).

In a set of embodiments the total of the absorbent component and water constitute at least <NUM>%, preferably at least <NUM>%, more preferably at least <NUM>%, still more preferably at least <NUM>% and even more preferably at least <NUM>% (such as at least <NUM>%) by weight of the total composition.

<FIG> provides an illustration of an embodiment of a process for capture of carbon dioxide from a flue gas stream. The process (<NUM>) includes an absorption reactor (<NUM>), for absorbing CO<NUM> from a flue gas stream, and a desorption reactor (<NUM>) for desorbing CO<NUM>.

The absorption reactor (<NUM>) includes a first inlet (<NUM>), a second inlet (<NUM>), a first outlet (<NUM>), and a second outlet (<NUM>), and a gas absorption contact region (<NUM>). The first inlet (<NUM>) of the absorption reactor (<NUM>) is a flue gas inlet through which a CO<NUM> rich flue gas enters the absorption column (<NUM>). The second inlet (<NUM>) is an absorbent solution inlet for the aqueous absorbent (such as the substituted heteroaromatic absorbent solutions herein before described) through which a CO<NUM> lean absorbent enters the absorption column (<NUM>). The CO<NUM> rich flue gas and the CO<NUM> lean absorbent contact in the gas absorption contact region (<NUM>). In this region the CO<NUM> in the CO<NUM> rich flue gas is absorbed into the absorbent solution where it is bound in solution to form a CO<NUM> lean flue gas and a CO<NUM> rich absorbent solution.

In conducting the process of the invention the aqueous composition may comprise a mixture of optionally substituted heteroaromatic compounds.

The local environment of the solution may be altered in the absorption column to favour the absorption reaction, e.g. to increase absorption of CO<NUM> into solution where it is bound to the substituted heteroaromatic compound. Such alterations of the local environment may include a change in pH, a change in solution temperature, a change in pressure etc. Alternatively, or additionally, the solution may include other compounds which assist in the absorption of CO<NUM>. These compounds may alter the affinity or absorption capacity of the substituted heteroaromatic compound for CO<NUM>, or these compounds may also absorb CO<NUM>.

If additional compounds are added to the absorbent solution in the absorption reactor (<NUM>), the process may additionally include means to remove these compounds.

The absorption of CO<NUM> from the CO<NUM> rich flue gas into the absorbent solution results in a CO<NUM> lean gas and a CO<NUM> rich absorbent solution. The CO<NUM> lean gas may still include some CO<NUM>, but at a lower concentration than the CO<NUM> rich flue gas, for example a residual concentration of CO<NUM>.

The CO<NUM> lean gas leaves the absorption column (<NUM>) through the first outlet (<NUM>), which is a CO<NUM> lean gas outlet. The CO<NUM> rich absorbent solution leaves the absorption column through the second outlet (<NUM>), which is a CO<NUM> rich absorbent outlet.

The aqueous composition may, if desired, include solvents in addition to water in order to modify solubility of the substituted aromatic compound and/or other absorbents which may be present composition. Examples of co-solvents may, for example, be selected from the group consisting of glycols and glycol derivatives. For example, the co-solvents may be selected from the group consisting of glycol ethers, glycol ether esters, glycol esters, long chain short chain aliphatic alcohols such as C<NUM> to C<NUM> alkanols, long chain aliphatic alcohols, long chain aromatic alcohols, amides, esters, ketones, phosphates, organic carbonates and organo sulfur compounds.

Desorption reactor (<NUM>) includes an inlet (<NUM>), a first outlet (<NUM>), a second outlet (<NUM>), and a gas desorption region (<NUM>). The CO<NUM> rich absorbent outlet (<NUM>) of the absorption column (<NUM>) forms the inlet (<NUM>) of the desorption column (<NUM>). Desorption of CO<NUM> from the CO<NUM> rich solution occurs in the gas desorption region (<NUM>).

Desorption of CO<NUM> from the CO<NUM> rich solution may involve the application of heat or a reduction in pressure to favour the desorption process. Furthermore, additional compounds may be added to the CO<NUM> rich solution to enhance the desorption process. Such compounds may alter the solution environment, for example by changing solution pH or altering another parameter to favour the desorption reaction.

Removal of CO<NUM> from the CO<NUM> rich solution results in the formation of a CO<NUM> lean gas stream and a CO<NUM> lean absorbent solution. The CO<NUM> lean absorbent solution may still include some CO<NUM>, but at a lower concentration than the CO<NUM> rich solution, for example a residual concentration of CO<NUM>.

The CO<NUM> gas stream is taken off via the first outlet (<NUM>), which is a CO<NUM> outlet. The CO<NUM> lean absorbent solution is taken off via the second outlet (<NUM>), which is a CO<NUM> lean absorbent solution outlet. The CO<NUM> lean absorbent is then recycled and fed through the second inlet (<NUM>) to the absorption column (<NUM>).

The invention may be used to absorb carbon dioxide from gas streams having a wide range of carbon dioxide concentration such as from <NUM> volume % to <NUM> volume % carbon dioxide. The invention is of particularly practical use in the absorption of carbon dioxide from gas streams, such as flue gas stream, resulting from combustion for fossil fuels such as coal, oil and gas. Typically the carbon dioxide content of such gas streams is in the range of from <NUM> volume % to <NUM> volume %. The invention is particularly suited to the capture of carbon dioxide from combustion of fossil fuels and having a carbon dioxide content in the range of from <NUM> volume % to <NUM> volume %. Levels of carbon dioxide in the range from <NUM> volume % to <NUM> volume % are typically present in the flue gas stream from combustion of fuel gas, fuel oil and coal.

The invention may also be used in capture of other acid gases together with carbon dioxide, such as sulfur dioxide, which may be present in gas streams from combustion of fossil fuels from specific geological sources. The process of the invention provides removal of a substantial amount of CO<NUM> from the gas stream. For example, in some embodiments, greater than or equal to <NUM>% by volume (vol%), specifically greater than or equal to <NUM> vol%. Following removal of carbon dioxide from the gas stream in accordance with the invention the lean carbon dioxide gas stream from fossil fuel combustion typically contains no more than about <NUM> volume % carbon dioxide and more preferably no more than <NUM> volume % carbon dioxide.

The chemical abbreviations used in the specification have the following meaning:.

<NUM>-AMPy, <NUM>-AMPy, and <NUM>-AMPy were evaluated for CO<NUM> mass transfer rates together with blends of the amines with monoethanolamine (MEA), <NUM>-amino-<NUM>-methyl-<NUM>-propanol (AMP), and N,N-dimethylethanolamine (DMEA).

AMPy's have larger CO<NUM> absorption rates than MEA at low CO<NUM> loadings. Above <NUM> CO<NUM> loading, CO<NUM> absorption rates fall below MEA. AMPy's absorption rates are faster than sterically hindered and tertiary amine absorbents. Equimolar blending with MEA results in faster CO<NUM> absorption rates at low CO<NUM> loadings at a similar overall concentration to MEA while maintaining a similar absorption rate to MEA at high CO<NUM> loadings above <NUM>.

AMPy's and their blends were evaluated here for their CO<NUM> absorption rates using a wetted-wall column contactor.

A general schematic of the Wetted Wall Column (WWC) apparatus is shown in <FIG> and an expanded view of the column portion of the WWC is shown in <FIG>. The WWC apparatus (<NUM>) is comprised of a first portion (<NUM>) comprising a hollow stainless steel column (<NUM>) extending from a base (<NUM>) having an inlet (<NUM>) for gas stream containing carbon dioxide and received in a second housing portion (<NUM>) comprising a temperature controlled jacket (<NUM>) and a gas outlet (<NUM>). The column (<NUM>) has an effective height and diameter of <NUM> and <NUM> respectively. About <NUM> of amine solution within in a submerged reservoir held in a temperature controlled water bath is pumped up the inside (<NUM>) of the column (<NUM>) before exiting through small outlet holes (<NUM>) in the top (<NUM>) of the column (<NUM>). The exiting liquid falls under gravity over the outside (<NUM>) of the column (<NUM>) forming a thin liquid film before collecting at the base (<NUM>) of the column portion (<NUM>). The solution is returned from an outlet (<NUM>) on the base (<NUM>) to a reservoir in a closed loop configuration. Thus, the liquid flowing over the outside (<NUM>) of column (<NUM>) is constantly replenished with fresh amine solution from the reservoir. The temperature of the column (<NUM>) and surrounding gas space (<NUM>) is controlled by a glass jacket (<NUM>) connected to the water bath.

The total liquid flow rate within the apparatus was maintained at <NUM>. min-<NUM> (<NUM>. s-<NUM>) as indicated by a calibrated liquid flow meter. A mixed CO<NUM>/N<NUM> gas was prepared by variation of Bronkhorst mass flow controllers for CO<NUM> and N<NUM> respectively to achieve a total gas flow rate of <NUM> min-<NUM>. Prior to entering the column (<NUM>) the gas stream is passed through a <NUM>/<NUM>" steel coil and saturator located in a water bath. Liquid and gas flow rates were selected to achieve a constant smooth and ripple free liquid film on the outside of the column (<NUM>). The absorption flux into the amine solutions, NCO2, was measured as a function of dissolved CO<NUM> loadings from <NUM>-<NUM> moles CO<NUM>/total mole amine and over a range of CO<NUM> partial pressures spanning <NUM> - <NUM> kPa. The composition of the gas stream prior to and exiting the housing (<NUM>) was monitored via a Horiba VA-<NUM> IR gas analyser. CO<NUM> loaded amine solutions were prepared by bubbling a pure CO<NUM> gas stream into a known volume of amine solution and the resulting mass change in the solution used to indicate CO<NUM> loading. A tower of condensers was connected to the outlet of the flask to ensure loss of amine and water vapour was minimised.

The amount of CO<NUM> absorbing into the amine liquid was determined from the CO<NUM> content of the gas stream entering (bottom) and exiting (top) the housing (<NUM>). The former was measured while bypassing the absorption column with the gas stream passing directly to the gas analyser. The absorption flux, expressed in millimoles (mmoles) of CO<NUM> absorbed per second per unit area of contact between liquid amine and gas, was determined over a range of CO<NUM> partial pressures in each of the amine solutions and CO<NUM> loadings.

CO<NUM> mass transfer co-efficients, KG, incorporate the processes of physical absorption and chemical reaction, into a single value. Ideally, absorbents with larger CO<NUM> mass transfer rates result in smaller absorption equipment and significant cost reductions.

KG values as a function of CO<NUM> loading are presented in <NUM>, <FIG>. From the curves in the figures CO<NUM> mass transfer is faster in <NUM>-AMPy solutions at low CO<NUM> loadings compared to MEA at similar concentrations. The absorption rate declines with increasing CO<NUM> loading and is <NUM>% lower than MEA towards higher loadings of <NUM>. In practice this does not present an issue due to the faster absorption at low CO<NUM> loading which offsets the lower rate at high loading. The larger cyclic capacity also means the AMPy's tend to more easily be stripped to low loadings where the mass transfer is shown in Table <NUM>.

The trend in KG at low CO<NUM> loadings follows <NUM>-AMP > <NUM>-AMPy > <NUM>-AMPy. The superior reactivity of <NUM> and <NUM>-AMPy over <NUM>-AMPY respectively is believed to extend from the increased basicity of the amines. CO<NUM> mass transfer is similar among the AMPy's at high CO<NUM> loadings. Equimolar blends of <NUM> <NUM>-AMPY with DMEA and AMP result in lower CO<NUM> mass transfer rates than <NUM> MEA over the entire CO<NUM> loading range. A similar blend of <NUM>-AMPy with MEA results in increased CO<NUM> mass transfer at low CO<NUM> loadings (~<NUM>% at <NUM> CO<NUM> loading) and similar CO<NUM> mass transfer at high loadings.

Importantly, blending with DMEA and AMP results in similar viscosities to standalone AMPy absorbents at similar concentrations and low (or zero) CO<NUM> loading. Viscosity of the <NUM>-AMPy/AMP blend increases with CO<NUM> loading similarly to the standalone <NUM> <NUM>-AMPy absorbent while the viscosity of the blend with DMEA increases at a slower rate (~<NUM>% lower viscosity at <NUM> loading). Viscosity of the <NUM>-AMPy/MEA blend is substantially lower at all CO<NUM> loadings (~<NUM>% lower viscosity at <NUM> CO<NUM> loading). A number of the AMPy/MEA blends exhibited similar or larger CO<NUM> mass transfer rates than the standalone absorbents indicating that blended absorbents are useful.

The larger physical CO<NUM> solubility in the AMPy's makes up for the lower reaction kinetics.

The table shows the larger enthalpy of reaction for the AMPy's which leads to more CO2 release with increasing temperature. This contributes to the good cyclic capacity of the substituted heteroaromatic compounds.

From the data in Table <NUM> the first protonation constants of AMPy, log K prot, are similar to MEA and BZA and fall within a suitable range for CO<NUM> capture processes. Importantly, the large and desired protonation enthalpy (ΔH°) observed for BZA is largely maintained in the AMPy derivatives (-<NUM> to -<NUM>). This large enthalpy is a unique feature and is responsible for the superior cyclic capacity compared to other non-aromatic and cyclic amine absorbents.

The larger cyclic capacity of the (aminomethyl)pyridines produces lower operating energy requirements of the process. As a result less absorbent is required to capture the same amount of CO<NUM> thereby lowering circulation rates and reboiler duties.

Benzylamine (BZA) has been found to form solid precipitate salts in the presence of CO<NUM>, particularly at high concentrations of BZA in the liquid phase, limiting the optimum operating concentration to < 30wt% (~ <NUM>). It was also found that BZA has the propensity to form small amounts of solid precipitates in the gas phase due to non-ideal liquid behaviour leading to elevated vapour pressures above those predicted by Raoult's law at low CO<NUM> loadings. As part of the absorbent screening process concentrated aqueous <NUM>-AMPy was evaluated for its potential to form solid precipitates in the presence of CO<NUM> at high concentrations. While similar in structure to BZA the incorporation of a second nitrogen group into the aromatic ring was found to increase solubility of the carbamate product in aqueous solution. A simple bubble reactor was utilised to determine the precipitation propensity while passing a pure CO<NUM> gas stream at atmospheric pressure into a concentrated <NUM>-AMPy solution held at ambient temperature. A concentration of 80wt% <NUM>-AMPy was achieved before precipitation of the carbamate salt was observed. While a precipitate was observed, it is unlikely this will occur in the pilot plant given the aggressive conditions employed in the simple lab based study. Furthermore, similar precipitation behaviour has been observed for other common aqueous amines in highly concentrated solutions but which are operated successfully in pilot plants.

The capacity of an absorbent solution for CO<NUM> is a vital requirement for absorbent development. CO<NUM> capacity drives the optimum absorbent concentration, energy requirements, and liquid equilibrium (VLE) measurements are typically used to determine absorption capacities, cyclic capacities (temperature dependence), and absorption enthalpies (temperature dependence of CO<NUM> solubility at a given CO<NUM> loading). Vapour liquid equilibrium also can be predicted from knowledge of the equilibrium constants for CO<NUM>/H<NUM>O chemistry, amine protonation, carbamate stability, and physical CO<NUM> solubility (Henry's constant). VLE data can also be used to regress equilibrium constants for carbamate stability which can be used to verify those determined from independent NMR studies (rarely available for bespoke absorbents).

The vapour liquid equilibrium apparatus used here incorporates a sealed stainless steel reactor (<NUM> independent vessels) and high pressure CO<NUM> gas delivery system. Absorbent liquid (<NUM> mls) is placed into vessels and evacuated several times to remove any residual CO<NUM> gas that may be present. The vessels are charged with high pressure nitrogen (~<NUM> BAR absolute pressure) before the mass is recorded using a milligram balance. Once weighed the vessel pressure sensor is attached and the entire vessel placed into an oven at the desired temperature (<NUM>, <NUM>, <NUM>∘C). Following overnight equilibration, the initial pressure of the vessel (now incorporating contributions from N<NUM> and H<NUM>O) is recorded and the vessel charged with CO<NUM> (~<NUM> BAR absolute pressure). The vessel is weighed and the mass of CO<NUM> dosed into the vessel recorded. The vessel is returned the oven and equilibrated for <NUM> hours or until steady state is reached (indicated by no further changes in pressure). Samples from the vessel headspace are then analysed by gas chromatography to determine the gas phase CO<NUM> partial pressure. The liquid phase CO<NUM> loading is then determined by mass balance calculation.

The results for <NUM> <NUM>-AMPy are shown in Table <NUM> below:.

A concentrated <NUM>-AMPy absorbent operating at <NUM> was selected as the base case given its simplicity. Alternative blends incorporating equimolar concentrations of monoethanolamine (MEA) and <NUM>-amino-<NUM>-methyl-<NUM>-propanol (AMP) with <NUM>-AMPy (i.e. <NUM> <NUM>-AMPY + <NUM> MEA or <NUM> AMP respectively) were selected to provide rapid kinetic or improved thermodynamics while minimising the cost of the absorbent inventory for large scale evaluation in a pilot plant.

<FIG> of the drawings shows the model estimated reboiler duties as a function of the ratio of liquid and gas flow rates (L/G) for an isobaric stripping column with a range of aqueous absorber solutions including <NUM> <NUM>-AMPy and various ratios of <NUM>-AMPy and AMP (with <NUM> wt% MEA included for comparison). These represent some of the more practically useful formulations in terms of energy requirement, with formulations incorporating MEA having poorer energy performance. There is little impact from the addition of AMP. AMP was, however, found to have a significant positive effect on mass transfer.

Operation of the aqueous <NUM> <NUM>-AMPy absorbent was completed over about <NUM> month in a pilot plant of general operation shown in <FIG>. A parametric study was undertaken to estimate the CO<NUM> stripping energy requirement as a function of operating parameters for a traditional absorber-stripper process design. Overall favourable results were found for the energy requirement as shown in the figure below.

Unlike the previously tested formulation based on BZA, no operational issues were encountered with an aqueous solution of <NUM> <NUM>-AMPy. No precipitation or foaming events occurred nor were there any issues regarding volatility.

As can be seen in <FIG> the energy requirement using aqueous solutions of (aminomethyl)pyridines such as <NUM> <NUM>-AMPy is much lower than for monoethanolamine (MEA).

Extended pilot plant trials have been undertaken using a <NUM> tonne/day CO<NUM> capture plant located at a brown coal power station. The capture plant was operated with a flue gas slip-stream of flow rate <NUM><NUM>/hr directly taken from the power station.

The campaign with <NUM> mol/L Aqueous <NUM>-AMPy was operated for a duration of approximately <NUM> hours. During operation the performance of the plant was assessed in terms of reboiler energy requirement and the degradation of the amine was monitored. The single dominant degradation product formed was also identified and characterised. Minimum reboiler duties of <NUM> and <NUM> GJ/tonne CO<NUM> without and with use of the rich split process configuration respectively were achieved. This is compared to <NUM> GJ/tonne CO<NUM> for <NUM> mol/L monoethanolamine (MEA) in both configurations.

In laboratory testing under accelerated degradation conditions the dominant degradation product formed was found to be an imine dimer of <NUM>-AMPy. Monitoring of loss of amine and formation of the imine was undertaken during the campaign by infrared (IR) spectroscopy and high performance liquid chromatography (HPLC). Additional analysis of plant samples by <NUM>C and <NUM>H-NMR spectroscopy confirmed that the previously identified imine was the primary degradation product in the plant.

<FIG> is a plot of the trend in amine and imine concentration during the pilot plant campaign.

During the pilot plant trial the degradation reaction mechanism was investigated in the laboratory by breaking the overall reaction down into the possible individual chemical transformations and testing if they occurred. The determined mechanism proceeds via a protonated <NUM>-AMPy molecule and loss of an ammonium ion followed by oxidation. The complete of degradation mechanism of <NUM>-AMPy to an imine via reaction with oxygen is shown in the following Scheme.

Based on the degradation mechanism of the above scheme it was considered that if <NUM>-AMPy was formulated with a stronger base to reduce the formation of protonated <NUM>-AMPy during CO<NUM> absorption, its degradation could be suppressed. AMP was chosen as the amine for formulation as it has the required basicity and is known to be robust in CO<NUM> capture applications. AMP does not react directly with CO<NUM> but rather acts as a base to preferentially accept the protons released when <NUM>-AMPy reacts. Simulations indicated that the concentrations used in the absorbent of aqueous <NUM> mol/L <NUM>-AMPy and <NUM> mol/L <NUM>-amino-<NUM>-methyl-<NUM>-proponal (AMP) were optimal to reduce degradation and maintain capture performance.

A pilot plant campaign was conducted with the aqueous absorbent of Example 5b for <NUM> hours. It was possible to conduct a much longer campaign as the degradation of the absorbent was much slower than the absorbent of Example 5a. The same reboiler energy requirements were achieved as in Example 5a. <FIG> shows the concentrations of <NUM>-AMPy, AMP and imine over the duration of the campaign. The rate of imine formation was orders of magnitude lower than seen in the trial of Example 5a. In addition, the overall rate of degradation of was found to be <NUM> times slower than <NUM> mol/L MEA.

The formation of the imine dimer and inhibition of degradation is a unique property of aminomethylaromatic systems and in particular enhances the performance on aminomethyl substituted heteroaromatics. Aminoalkylpyridine with longer bridging chains such as ethyl and propyl between the amino and pyridine group do not form the imine and degrade via chain loss and more traditional mechanism that form products that cannot be easily regenerated.

<FIG> <NUM>-AMPy, AMP and imine concentrations measured during the pilot plant campaign by IR spectroscopy over <NUM> hours of operation.

In contrast with the reduction in the concentration of <NUM>-AMPy shown in <FIG> the composition of Example 5b, consisting of aqueous <NUM> mol/L <NUM>-AMPy and <NUM> mol/L <NUM>-amino-<NUM>-methyl-<NUM>-proponal (AMP) (32wt% <NUM>-AMPy, <NUM> wt% AMP and <NUM> wt% water), showed little reduction in the concentration of the amines over the period of <NUM> hours operation of the pilot plant under the same conditions.

The pilot plant was also operated with <NUM> mol/L (30wt%) aqueous monoethanolamine (MEA) for approximately <NUM> hours. This allowed optimum reboiler duties to be identified for each absorbent via parametric study. These optimum reboiler duties and rates of amine degradation are shown in Table <NUM> below and are for the standard plant configuration (no rich split). Note that the MEA degradation information is taken from literature as it was only run for a short duration in the pilot plant.

Aniline and aminopyridine compounds lack the basicity required to effectively act as CO<NUM> absorbents. The pKa of their conjugate acids is smaller than or similar to that of CO<NUM> in aqueous solution (<NUM> at <NUM>, T J Edwards,G Maurer,J Newman,J M Prausnitz; AlChE J. ,<NUM>,<NUM> (<NUM>)). The pKa of the conjugate bases is shown in Table <NUM> below. Thus they are unable to accept protons from CO<NUM> ionisation. In addition they will only directly react with CO<NUM> to form a carbamate in the presence of a strong base (<NPL>)). This lower basicisity compared to aliphatic amines is due to the delocalisation of the lone pair of electrons on the nitrogen into the aromatic ring. <NUM>-Aminopyridine is a special case due to the larger pKa of its conjugate acid, which is in a suitable range for CO<NUM> absorption. This is due to resonance structure stabilisation of the ion, but this stabilisation renders it unable to react directly with CO<NUM> to form a carbamate (<NPL>)).

Relationship between structural rigidity and CO<NUM> capture performance.

The enthalpy of protonation is an important parameter in aqueous amine absorbents. The larger the enthalpy of protonation the larger the CO<NUM> cyclic capacity that can be achieved via a temperature swing process. A relationship exists between the enthalpy and entropy of protonation and it is described in the publication <NPL>). In summary, the more structurally rigid a molecule, the more negative the enthalpy of protonation and smaller and/or more negative the entropy of protonation. This effect is due to reduced internal degrees of freedom resulting in smaller entropy changes upon protonation. Thus aminomethyl substituted heteroaromatic groups have more favourable enthalpy of protonation properties than longer alky chain bridging groups such as ethyl or propyl bridging groups or aliphatic amines. <FIG> compares the enthalpy and entropy of protonation of a range of amines. The red squares are allow comparison of <NUM> different aminomethyl aromatic compounds to <NUM>-phenyethylamine to illustrate this relationship.

As shown in Example 5b the presence of AMP in the absorber composition inhibited the formation of the imine produced by dimerization of the AMPy derivative formed on absorption of CO<NUM>. Other bases including amines of higher pKa than the (aminomethyl)pyridine may also be used in this role. Preferred bases are tertiary and sterically hindered amines which are stable and provide a proton accepting role on CO<NUM> absorption. The average pKa of <NUM>-(aminomethyl)pyridine, <NUM>-(aminomethyl)pyridine and <NUM>-(aminomethyl)pyridine at <NUM> is <NUM>.

Suitable bases typically have a pKa at least <NUM> units higher than the pKa of the (aminomethyl)pyridines, that is about <NUM> units higher than <NUM> (this represents a <NUM>. 5x increased selectivity for protons). Examples of suitable tertiary and sterically hindered amines include those specified in Table <NUM> together with the pKa at <NUM>.

Claim 1:
A process for absorbing carbon dioxide from a gas stream containing carbon dioxide, comprising contacting the gas stream with an absorbent comprising an aqueous composition comprising at least 10wt% water and a substituted heteroaromatic compound selected from formula Ia, Ib, Ic, Id and mixtures of two or more thereof:
<CHM>
<CHM>
wherein
R<NUM> is methylene;
R<NUM> is an optional carbon substituent selected from the group consisting of C<NUM> to C<NUM> alkyl, hydroxy, hydroxy-C<NUM> to C<NUM> alkyl, C<NUM> to C<NUM> alkoxy, C<NUM> to C<NUM> alkoxy-(C<NUM> to C<NUM> alkyl); and
n is <NUM>, <NUM> or <NUM>.