RELATED APPLICATION INFORMATION

[0001] This application claims priority under 35 U.S.C. § 119(e) to U. S. Provisional Application No. 61/900/147 filed November 5. 2013, the contents of which is hereby incorporated by reference in its entirety.

STATEMENT REGARDING FEDERALLY SPONSORED R&D

[0002] This invention was made with government support under Award No. DE-AR0000094 and Award No. DE-FG36-07NT43091 awarded by the Department of Energy. The government has certain rights in the invention.

BACKGROUND OF THE INVENTIO

[0003] The utility sector produces roughly a third of the CO? emissions in the United States. Conventional coal-fired power plants currently produce over 50% of the electricity in the United States. Even with dramatic growth of power generation from renewable sources, tins percentage is not expected to drop significantly in the next two decades. Therefore, capturing C0 ₂ from post-combustion flue gas is a major target in efforts to curb carbon emissions. The most mature technology for CO? capture is aqueous amine scrubbing, with monoethanoiamine (MEA) most commonly used as the baseline. Unfortunately, the MEA process would result in a 28% parasitic energy loss and roughly double the cost of electricity. The heat required to regenerate the aqueous MEA solution is a major contributor to this parasitic energy loss. Accordingly, suitable materials and methods are still needed for capturing CO?, from post-combustion flue gas.

SUMMARY OF THE INVENTION

[0004] In accordance with one embodiment, there is provided a method of removing carbon dioxide from a mixed gas, comprising exposing a phase-change ionic liquid (PCIL) in solid form io a gas comprising carbon dioxide, wherein the PCIL changes phase upon reaction with the carbon dioxide to form a liquid PCIL-C0 ₂ complex, and heating the liquid PCIL-C0 ₂ complex to produce carbon dioxide gas and regenerate the solid PCIL. [0005] in accordance with one embodiment, there is provided a method of removing carbon dioxide from a mixed gas stream, comprising passing a stream of gas comprising carbon dioxide through a first vessel containing an absorbent comprising a POL, wherein the POL changes phase upon reaction with the carbon dioxide to form a liquid PCIL-CO2 complex; transporting the liquid PGL-CO2 complex to a regenerator; heating the liquid POL-CO?, complex in the regenerator to produce carbon dioxide gas and regenerate the solid POL; and transporting the solid POL back to the first vessel.

[0006] The gas comprising carbon dioxide may be flue gas or exhaust gas produced frorn combustion of a fossil fuel, and in some embodiments is treated to remove water prior to contacting the POL. In certain embodiments, the POL comprises a cation and an aprotic heterocyclic anion. Preferred cations include tetraalkylphosphonium cations such as tetrabutylphosphonium, butyltriethylpbosphonium, tetraethylphosphonium, or tetrametbylphosphomum. Preferred anions include 2-(trifluoromethyl)pyrazolide, 6- bromo-benzimidazolide, benzo[d]inidazol-l-ide, indazoiide, or 2-cyanopyrfolide.

BRIEF DESCRIPTION OF THE DRAWINGS

[0007] Figure 1 is a schematic of a process of removing carbon dioxide from a mixed gas.

[0008] Figure 2 is a schematic of one embodiment of a system for removing carbon dioxide from a nixed gas stream.

[0009] Figure 3 illustrates the carbon dioxide uptake of tetrabutylphosphonium 2-(trifluoromethyl)pyrazolide and tetrabutylphosphonium cyanopyrrolide at 60°C.

[0010] Figure 4 illustrates the viscosities of tetrabutylphosphonium 2- (trifluoromethyf)pyrazolide and tetrabutylphosphonium cyanopyrrolide before and after reaction with carbon dioxide.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS

[0011] Disclosed herein are methods for C0 ₂ capture that use phase change ionic liquids (POLs) to remove the C0 ₂ from flue gas or other gas streams containing CO ₂ . Certain solid ionic materials have high C0 ₂ uptake and form a liquid when they react with C0 ₂ . When these same ionic materials are heated to regenerate the solid material by removing the carbon dioxide, part of the heat needed to release the C0 ₂ from the POL absorbent would be supplied by the heat of fusion of the POL as it solidifies. Since the heat of fusion of some salts is about half the typical heat of reaction of C0 ₂ with a functional group like an amine, the methods herein have the potential to cut the heai of regeneration by as much as a half. Utilization of the heat of fusion to assist in regeneration of the solid PCIL can substantially reduce the parasitic energy loss associated with post- combustion CO ₂ capture.

[0012] The term PCIL as used herein refers any of a number of complex ionic compounds in which, at a given temperature, the compound exists in the solid state but changes to a liquid upon forming a complex with CO ₂ . Otherwise stated, the PCIL compound has a higher melting point than the PCIL- CO _? , complex. In certain embodiments, the uncomplexed PCIL exists in the solid state at a temperature range of about 0°C-50°C and changes to the liquid state upon reversibiy binding with COi to fomi a PCIL-CO ₂ complex. In some embodiments, PCILs have a melting point, preferably greater than about 80°C, including greater than about 100°C, and greater than about 150°C, including about 100°C - 200°C. in some embodiments, PCILs have a heat of fusion (ΔΙ-I _fus ) of -30 to -2 kJ/mol, including about -20 to -10 kJ/mol. In some embodiments, the PCIL comprises an aprotic heterocyclic anion (AHA), where a heteroatom is nitrogen. Examples of preferred PCILs are provided in Table 1 below infra. Further examples of AHAs and ionic compounds that may be useful in PCILs are disclosed in WO 2011 /056895, which is hereby incorporated by reference in its entirety. Such AHAs that may be

wherein X is

A is N or CR

E is Ί or CFC

G is N or CR

J is N or CR ⁶ R\ R ² , R\ R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ^S , R ⁹ , and R ^{I 0} are independently halo, CN, CNO, NCO, NO,, R" , OR ¹ ', SR" , NR ^{! 2} R ^{I J} , -YC(0)ZR ^U , S0 ₂ R ^{! !} , SO3R ^{1 1} , or S0 ₂ NR ^{! 2} R ^{! 3} ;

Y is a single bond, optionally substituted hydrocarbyl, -N(R ^{I ;} K O, or S;

Z is a single bond, -N(R ¹² )-, O, or S;

each R" is H or optionally substituted C1.12 hydrocarbyl, and

each R ^{i :} and each R' ³ is independently H or optionally substituted C;. _e hydrocarbyl.

[0013] Preferred ring structures for the anion include pyrrolide, pyrazoiide and imidazolide. The simple mechanism of reaction of C0 ₂ with a typical AHA anion is shown in equ

(eqn. 1)

[0014] Preferred PCiLs have improved properties as compared to known amines regarding binding of C0 ₂ . When amines are tethered to the cation of an ionic compound, they react with C0 ₂ in the same stoichiometry as with amine molecules like monoethanolamine, namely that two amines are needed for each CO?. Although that capacity can be increased substantially to one amine for each CO? if the amine is tethered to the anion, some such tethered anions when complexed with carbon dioxide exhibit very high viscosities. PCiLs including AHAs, do not exhibit undesirably high viscosities when complexed with C0 ₂ and also bind about one mole of C0 ₂ for every mole of PCIL In some embodiments, the viscosity of a PCIL- C0 ₂ complex at 30°C is preferably less than about 2000 cP, including less than about 500 cP and less than about 300 cP.

[0015] Examples of preferred PCILs are below in Table 1.

TABLE 1

[0016] Although it has been found that the cation of the POL does not appear to play a significant role in determining C0 ₂ binding capacity, it can have an effect on physical properties such as melting point, in certain embodiments, teiraalkylphosphonium cations are chosen because they tend to have higher decomposition temperatures compared to other cations,

[0017] It should be noted thai the cations in the PClLs can be readily changed to other cations, including other tetraalkylphosphonium cations, accordingly, any of the anions 2-(trifluoroniethyl)pyrazolide, 6-bromo-benzimidazolide, benzo[d]imidazol-l -ide, indazolide, and 2-cyanopyrroMe can be paired with any of the cations tetrabutylphosphonium, butyltriethylphosphonium, tetraethylphosphonium, and teirameihylphosphoniiim, as well as other tetraalkvlphosphonmiris wherein the alkyls are the same or different and selected from C1-C4 hydrocarbons either straight chain or branched.

[0018] Additional cations that may be useful include quaternary nitrogen- containing cations, including cyclic, aliphatic, and aromatic quaternary nitrogen-containing cations such as n-alkyl pyridinium, a dialkyl pyrrolidinium, a dialkyl mndazolium, or an alkylararaonium of the formula RYxNHx wherein X is 0-3 and each R' is independently an alkyl group having 1 to 18 carbon atoms. In some embodiments, unsymmetrical cations may provide lower melting temperatures. Other phosphonium cations include, cyclic, aliphatic, and aromatic phosphonium cations, including those of the formula R".-. ·,Ρ! 1 , wherein X is 0-3, and each R" is an alkyl or aryi group such as an alkyl group having 1 to 18 carbon atoms or a phenyl group. Examples of sulforiium cations include, but are not limited to cyclic, aliphatic, and aromatic sulfonium cations. For example, the sulfonium cations include those of the formula R' SHx wherein X is 0-2 and each R" is an alkyl or aryl group such as an alkyl group having 1 to 18 carbon atoms or a phenyl group. Additional more specific examples may include, but are not limited to, ammonium, imidazolium, phosphonium, 1 -butyl-3-methyiimiclazolium, 1 -decyl-3-methylimidazoiium, l-dodecyl-3-methylimidazolium, l-ethyl-3-butyl imidazolium, i-hexyi-3- methylimidazoliuni, 1 -hexylpyndinium, l-methy-3-buty3 imidazolium, l-methy-3-decyl imidazolium, l-methy-3-dodecyl imidazolium, l-methy-3 -ethyl imidazolium, l-methy-3- hexadecyl imidazolium, l-methy-3-hexyl imidazolium, l -methy-3-octadecyl imidazolium, 1 -methy-3-octyl imidazolium, 1 -methy-3 -propyl imidazolium, l -octyl-3- methyliniidazoiiurn, 1-octylpyridmium, benzyl pyridinium, -butyl pyridinium, ethyl pyridinium, and ethylene pyridinium. Other examples of suitable cations are known in the art. For example, 1182006/0197053, US2008/0028777, and US2007/0144186, all of which are incorporated by reference in their entireties, describe a number of suitable cations, and any of these cations may be used with an anion described herein.

[0019] Recognizing that the large viscosity changes in previously considered CO-.-philic ionic liquids has its origins in hydrogen bonding networks that are set up in the reacted/complexed compounds, pyrrolide ions were designed that would circumvent this hydrogen-bonding mechanism. By varymg the functional groups attached to the pyrrolide ion it is possible to tune the strength of C0 ₂ bonding. [0020] Similar control can be exerted over the melting temperature by managing the intermolecular interaction differences between unreacted and reacted state. The solid state is a low entropy, low energy state, in which the free energy costs of high order (low entropy) are offset by the energetic stability associated with this order. The liquid is a higher entropy, higher energy state, in which the free energy cost of diminished intermolecular interactions are offset by higher entropy. By exploiting changes in these competing factors between the unreacted and reacted states, different melting points can be achie ved. In this case it is preferable for the reacted form of the material to be biased towards the liquid state; that is, to favor disorder due to weaker intermolecular interactions. One way to drive this change is by altering the reaction mechanism in such a way as to induce a significant conformational change in the product. For example, in the certain materials, changes from the more symmetric pyrrolide to the less-symmetric reacted form are sufficient to induce a modest melting point difference. In both forms the molecule remains planar due to π bonding interactions between anion and CO ₂ . Altering this π bonding to bias the product to a non-planar form should have a much more dramatic effect on melting point.

[0021] These factors may be used to perform simulations to determine candidate compounds which then may be tested in the laboratory. Additional experimental information may be found in Seo, et al, Phase-Change Ionic Liquids for Postcombustion CO ₂ Capture. Energy & Fuels, vol. 28, pp. 5968-77 (2014), the contents of which is incorporated by reference in its entirety.

[0022] In its simplest form, a method of removing C0 ₂ from a mixed gas stream includes exposing the gas to a solid PCIL. The solid PCIL reacts with the CO?, to form a liquid PCIL-C0 ₂ complex, thereby removing C0 ₂ from the mixed gas stream. The solid PCIL can be regenerated by heating to liberate the C0 ₂ gas, which can then be recovered.

[0023] A schematic of one embodiment of a process to remove C0 ₂ from a mixed gas stream is shown in Figure 3. A gas containing C0 ₂ 5 is fed into a first vessel referred to as an absorber 10. The C0 ₂ -containing gas may be from any source, such as flue gas or exhaust gas from the burning of a fossil fuel. The absorber 10 contains an absorbent and/or adsorbent comprising at least one PCIL. The PCIL is in solid form and reacts with C0 ₂ to form a liquid PCIL- C0 ₂ complex. During the process, as C0 ₂ - containing gas passes through the absorber there may be a combination of solid PCiL and liquid PCIL- C0 ₂ complex in the absorber 10. The reaction to form the PCIL- CQ ₂ complex is exothermic, such thai some embodiments of absorber 10 include a cooling jacket or other means to remove heat from the absorber. In certain embodiments, the temperature of the absorber 10 is maintained in the range of about 50°C - 90C, including about 60°C-80°C, and about 60°C-70°C.

[0024] The liquid PCIL- C0 ₂ complex can then be transported 15 to a second vessel referred to herein as a regenerator 20. The regenerator 20 is heated to release the C0 ₂ and regenerate the solid PCIL. In certain embodiments, the regenerator operates at temperatures above about 80°C, including over I00°C. In some embodiments, the regenerator is a spray tower wherein the liquid complex is sprayed into the vessel to enhance the liberation of carbon dioxide and concomitant solidification. Once it is liberated, the C0 ₂ leaves the regenerator 22. The C0 ₂ may be recovered 30 and compressed or otherwise treated. The regenerated solid PCIL can then be transported 25 back to the absorber 10 and reused.

[0025] The heat generated by the solidification of the PCIL (i.e. the AH _fus ) 2.7 also helps to heat the regenerator. The ability to use the natural heat released as part of regeneration of the solid reduces the energy input needed to heat the vessel. This reduces the amount of energy needed to operate the C0 ₂ scrubbing system, also called parasitic energy loss, as compared to systems that do not include phase-changing materials. In some embodiments, heat removed from the absorber may also be used to heat the regenerator.

[0026] In some embodiments, a single vessel is used for both reaction and regeneration. In such embodiments, the C0 ₂ -eontaming gas feed is diverted or otherwise discontinued from entering into the vessel, and the vessel is heated to liberate the CG ₂ gas and regenerate the solid PCIL. Once the regeneration has been completed to the desired extent, the vessel containing solid PCIL may be exposed to a C0 ₂ -containmg gas feed once again.

[0027] In some embodiments, the COj-coniaining gas stream is treated to remove water before it reaches the PCIL in the absorber 10.

[0028] One embodiment of an apparatus carrying out the methods described herein is found in Figure 2. The conditions and options noted above for Figure 1 are also applicable to Figure 2. The C0 ₂ -containing gas feed 5, which may be a flue gas, is passed through an optional cooler 7 to reduce the temperature of the gas, and may also be passed through an optional water removal or reduction system 9. Another possible option is for the cooler and water removal/reduction to take place in a single apparatus. Any of a wide variety of methods may be employed to remove water, including condensation or use of hydrophilic or hygroscopic materials.

[0029] The gas then passes into the absorber 10 where it is exposed to the solid PCTL. The absorber may be temperature controlled as discussed above. The C0 ₂ gas then reacts with POL to make a liquid PCiL-CG ₂ complex 15 (which may also be referred to as "rich ionic liquid" because it is rich in C0 ₂ ) which is then pumped out of the absorber 10 and into the regenerator 20.

[0030] The regenerator 20 is heated to release the CO and regenerate the solid PCTL. The AHfas heat generated by the solidification of the PCTL 27 also helps to heat the regenerator. The C0 ₂ 22 leaves the regenerator and is optionally compressed and/or dehydrated as needed 30. The regenerated solid PCIL (also referred to as "lean IL") can then be transported 25 back to the absorber 10 and reused. The lean IL may also be cooled prior to going back to the absorber if desired to help maintain the desired temperature in the absorber 10.

[0031 j The ability to use the natural heat released as part of regeneration of the solid reduces the energy input needed to heat the vessel. This reduces the amount of energy needed to operate the CO? scrubbing system, also called parasitic energy loss, as compared to systems that do not include phase-changing materials. In some embodiments, heat removed from the absorber may also be used to heat the regenerator.

[0032] As examples, [P444.4] [CF ₃ pyrazoiide] and [P4444] [cyanopyrrolide] are solids at room temperature. Their normal melting points (as measured by differential scanning calorimetry) are ~40 °C. At room temperature and with 1 bar C0 ₂ pressure the solids begin to melt. Because mass transfer to the solid was too slow to quickly measure equilibrium C0 ₂ uptakes of the solids, the solids were melted and the C0 ₂ uptake measured at 60 °C. Those absorption isotherms are shown in Figure 3. Clearly, the C0 ₂ uptake is extremely high, almost approaching 1 C0 ₂ molecule for each anion. Additionally, the viscosities as a function of temperature were measured before and after reaction with C0 ₂ . These data are shown in Figure 4. First, note that the viscosity of the mixture remains below 500 cP so that the liquid is capable of being transported using a pump. Second, note that measurements of the viscosity of the [ P44 [CF ₃ pyrazolide]/C ⁽ ¾ complex were possible down to 30 °C. It was only at 25 °C that the sample began to solidify. The viscosity for the CC -saturated [P4444] [cyanopyrrolide] was measurable down to 10 °C. Thus, the melting point of the PCIL/C0 ₂ complex appears to be approximately 1.5-30 °C below the melting point of the pure POL. These compounds demonstrate that the processes shown in Figures 1 and 2, with their potential large reductions in parasitic energy requirements, are possible.

[0033] While certain embodiments of the disclosure have been described, these embodiments have been presented by way of example only, and are not intended to limit the scope of the disclosure, indeed, the novel methods, systems, and devices described herein may be embodied in a variety of other forms. For example, embodiments of one illustrated or described process or apparatus can be combined with embodiments of another illustrated or described process or apparatus. Some embodiments have been described in connection with the accompanying drawings. However, it should be understood that the figures are not drawn to scale. Distances, angles, plumbing arrangements, etc. are merely illustrative and do not necessarily bear an exact relationship to actual dimensions and layout of the systems illustrated. Components can be added, removed, and/or rearranged. Furthermore, various omissions, substitutions and changes in the form of the methods, systems, and devices described herein may be made without departing from the spirit of the disclosure.

[0034] Conditional language, for example, among others, "can," "could," "might, ^" ' or "may," unless specifically stated otherwise, or otherwise understood within the context as used, is generally intended to convey that certain embodiments include, while other embodiments do not include, certain features, elements and/or steps. Thus, such conditional language is not generally intended to imply that features, elements and or steps are in any way required for one or more embodiments or thai one or more embodiments necessarily include logic for deciding, with or without user input or prompting, whether these features, elements and/or steps are included or are to be performed in any particular embodiment.