Non-aqueous solvents for removing acid gases from process gas streams for high pressure applications

A non-aqueous solvent system using a nitrogen base and organic diluent addresses the limitations of aqueous systems by achieving efficient and cost-effective acid gas removal with reduced energy consumption and smaller footprints.

JP7825554B2Active Publication Date: 2026-03-06RES TRIANGLE INST
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Patent Information

Application Number
JP2022532640
Authority / Receiving Office
JP · JP
Patent Type
Patents
Current Assignee / Owner
Priority Date
2019-12-11
Filing Date
2020-12-09
Publication Date
2026-03-06
Estimated Expiration
2040-12-09

AI Technical Summary

Technical Problem

Existing solvent systems for removing acid gases from gas streams, particularly aqueous systems, face high energy requirements, corrosion, and large process footprints, leading to high capital and operating costs, with limitations in deep removal of acid gases due to solubility constraints.

Method used

A non-aqueous solvent system comprising a chemical absorption component with a nitrogen base and a physical absorption component with an organic diluent, designed for high-pressure operations, allowing for deep acid gas removal with reduced energy consumption by utilizing a combination of chemical and physical absorption mechanisms.

Benefits of technology

The solvent system achieves high-capacity acid gas removal with reduced energy requirements, lower corrosion rates, and smaller process footprints, enabling efficient regeneration and cost-effective operation compared to conventional aqueous solvents.

✦ Generated by Eureka AI based on patent content.

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Abstract

A non-aqueous solvent system configured for removing acid gases from a gas stream includes a solution formed from a chemical absorbing component and a physical absorbing component. The chemical absorbing component includes a nitrogen base, the nitrogen base being structured to react with a portion of the acid gas. The physical absorbing component includes an organic diluent that is unreactive with the acid gas and structured to absorb a portion of the acid gas at pressures above atmospheric pressure. The solvent system has a solubility in water of less than about 10 g of solvent per 100 mL of water.
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Description

[Technical Field]

[0001] (CROSS-REFERENCE TO RELATED APPLICATIONS) This application claims the benefit of U.S. Provisional Patent Application No. 62 / 946,737, filed December 11, 2019, the entire contents of which are incorporated herein by reference.

[0002] (Technical field) The present invention relates to a solvent system for removing acid gases from gas streams, as well as to an apparatus and method for using such a system. For example, the solvent system may be used to remove carbon dioxide (CO), carbonyl sulfide (COS), carbon disulfide (CS), sulfur oxide (SO), and the like in high pressure applications. x ) or a combination thereof. [Background technology]

[0003] The separation or removal of acid gases from gas streams is a critical step in various industrial processes. For example, acid gases are removed from process streams in the production of syngas and natural gas. These gases often contain some degree of acid gas contamination, either from the natural gas source or as a by-product of upstream chemical reactions in syngas production. Examples include CO2, COS, CS2, H2S, SO x , NO x These acid gases, such as HCl, are removed from the product gas to meet required pipeline specifications, downstream gas purity demands, or to prevent catalyst poisoning in downstream processes.

[0004] In a typical solvent-based process, the process gas stream to be treated is passed through a liquid solvent that interacts with acidic compounds (e.g., CO2 and SO2) in the gas stream and separates them from non-acidic components. The solvent becomes enriched in the acid gas components, which are then removed under a variety of operating conditions so that the solvent can be reused for additional acid gas removal.

[0005] Typically, separation processes involve an absorber and desorber with a solvent circulating to remove acid gases. Several commercially available solvents exist for such applications, which can be classified as aqueous (water-rich) and non-aqueous (water-poor). Typically, aqueous systems use water as a diluent and contain 20-50 wt. % of the reactants to remove acid gases from the process gas stream, while non-aqueous solvents contain 10-60 wt. % of the active reactants with minimal amounts of water to remove acid gases from the process gas stream.

[0006] The underlying removal mechanism of solvent systems can be classified as either physical absorption or chemical absorption. Physical absorption utilizes pressure to dissolve acid gas molecules into a liquid solvent. The amount of acid gas dissolved in a physical solvent increases proportionally with increasing pressure. When the pressure is reduced, the acid gas is released from the gas-rich physical solvent. That is, acid gases can be released by flashing the gas from the gas-rich solvent at low pressure. The energy required to release the acid gas from the physical solvent and recover the solvent for reuse is relatively low. However, physical solvents typically do not work well for deep removal (i.e., removal of high concentrations of acid gas, e.g., greater than 90 wt. % or greater than 95 wt. %) or low concentrations of acid gas due to solubility limitations at low partial pressures.

[0007] Chemical absorption involves the reaction of acid gas species with a chemical absorption solvent, forming a chemical bond between the acid gas and the solvent. The substantially exothermic absorption occurs very rapidly and allows for deep removal of acid gases as long as the solvent contains enough reactants to react with the acid gas up to its reaction limit. The reaction limit is usually determined by the stoichiometric ratio of the chemical absorption solvent to the acid gas species. This stoichiometric ratio can also be used to determine the amount of chemical absorption solvent required to remove acid gas pollutants per unit volume.

[0008] Reversing a chemisorption reaction generally requires at least the amount of energy returned to the rich solvent produced by the forward reaction, not to mention the energy required to raise the gas-rich chemisorption solvent to a temperature at which the reverse reaction can occur to any appreciable extent and maintain conditions for the reverse reaction to be completed to any appreciable extent. Therefore, chemisorption solvents require relatively large amounts of energy to dissociate the chemical bonds between the solvent and the acid gas. Energy usage for chemisorption in aqueous solvent systems is further increased because more energy is used to heat and vaporize excess water within the aqueous system.

[0009] Most commercially available solvents are physical or chemical aqueous solvents. Aqueous solvents are widely used in many acid gas removal applications. However, the use of aqueous solvents has drawbacks such as high corrosion rates, high energy requirements for solvent regeneration, and large process footprints, all of which lead to high investment costs.

[0010] In view of the above, it would be desirable to provide a solvent system for acid gas removal applications that can reduce capital and operating costs. Summary of the Invention

[0011] In a first aspect of the present invention, a non-aqueous solvent system configured to remove acid gases from a gas stream includes a solution formed from a chemical absorption component including a nitrogen base, where the nitrogen base is structured such that it reacts with a portion of the acid gases, and a physical absorption component including an organic diluent that is unreactive with the acid gases and structured such that it absorbs a portion of the acid gases at pressures above atmospheric pressure. The solvent system has a solubility in water of less than about 10 g of solvent per 100 mL of water.

[0012] In a feature of the first aspect, the nitrogen base is selected from the group consisting of 1,4-diazabicyclo-undec-7-ene ("DBU"); 1,4-diazabicyclo-2,2,2-octane; piperazine ("PZ"); triethylamine ("TEA"); 1,1,3,3-tetramethylguanidine ("TMG"); 1,8-diazabicycloundec-7-ene; monoethanolamine ("MEA"); diethylamine ("DEA"); ethylenediamine ("EDA"); 1,3-diaminopropane; 1,4-diaminobutane; hexamethylenediamine; 1,7-diaminoheptane; diethanolamine; diisopropylamine ("DIPA"); 4-aminopyridine; The organic diluent may comprise pentylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, tert-octylamine, dioctylamine, dihexylamine, 2-ethyl-1-hexylamine, 2-fluorophenethylamine, 3-fluorophenethylamine, 3,5-difluorobenzylamine, N-methylbenzylamine, 3-fluoro-N-methylbenzylamine, 4-fluoro-N-methylbenzylamine, imidazole, benzimidazole, N-methylimidazole, 1-trifluoroacetylimidazole, 1,2,3-triazole, 1,2,4-triazole, or mixtures thereof. The organic diluent may be selected from the group consisting of alcohols, ketones, aliphatic hydrocarbons, aromatic hydrocarbons, nitrogen heterocycles, oxygen heterocycles, aliphatic ethers, cyclic ethers, esters, and mixtures thereof.

[0013] In another aspect of the first embodiment, the chemisorption component can be present in a concentration ranging from 1 to 50% by weight of the total system. Further, the physisorption component can be present in a concentration ranging from 40 to 95% by weight of the total system. The system can further comprise water.

[0014] In a second aspect of the present invention, a method for removing acid gases from a gas stream includes introducing a non-aqueous solvent system comprising a physical absorption component and a chemical absorption component into an absorption vessel operating at a pressure above atmospheric pressure, and introducing a gas stream comprising acid gases into the absorption vessel such that the gas stream passes in fluid contact with the non-aqueous solvent system, whereby the acid gases are removed from the gas stream by the solvent system.

[0015] A third aspect of the present invention is a method for reducing the amount of energy required for solvent regeneration of a non-aqueous solvent system (NASS) in an acid gas scrubbing process relative to the amount of energy required for solvent regeneration of a conventional aqueous solvent, comprising using a NASS as described above to remove acid gases from a process stream in an absorption vessel operating at a pressure above atmospheric pressure but less than 60 bar, thereby forming an acid gas-containing NASS. The present invention also includes introducing the acid gas-containing NASS into a pressure relief vessel, the pressure relief vessel operating at a temperature and pressure where the operating pressure of the pressure relief vessel is lower than the operating pressure of the absorption vessel, whereby acid gases absorbed by the physical absorption component of the NASS are released from the acid gas-containing NASS upon introduction into the pressure relief vessel, and the operating temperature of the pressure relief vessel is such that acid gases absorbed by the chemical absorption component of the acid gas-containing NASS are released from the acid gas-containing NASS, thereby providing regenerated NASS that is substantially free of acid gases and can be reused in the gas scrubbing process. Using the above method, the energy used to provide the regenerated NASS is reduced relative to the energy used to provide a regenerated form of aqueous solvent in the acid gas scrubbing process.

[0016] It is to be understood that both the foregoing general description and the following detailed description of the invention are exemplary, but are not restrictive, of the invention.

[0017] A more complete understanding of the present invention and many of the attendant advantages thereof will be readily obtained as the same becomes better understood by reference to the following detailed description when considered in connection with the accompanying drawings, in which: [Brief explanation of the drawings]

[0018] [Figure 1] FIG. 1 is a schematic diagram of the components of an exemplary solvent system. [Figure 2] FIG. 1 is a schematic flow diagram of an exemplary system for removing CO2 from a gas stream. [Figure 3] FIG. 1 is an exemplary calculation for determining the reboiler heat duty of a solvent-based chemical absorption component. [Figure 4] FIG. 1 is a schematic flow diagram of the absorber column used in the testing. [Figure 5] Figure 5A is a line graph showing CO2 concentration over time using an exemplary solvent system in Example 1. Figure 5B is a line graph showing CO2 concentration over time using an aMDEA substitute in Example 1. Figure 5C is a line graph showing CO2 concentration over time using water in Example 1. [Figure 6] FIG. 1 is a schematic diagram showing the experimental setup of Example 2, including the reactor and batch vessel. [Figure 7] 1 is a line graph showing the vapor-liquid equilibrium curve for an exemplary embodiment of the solvent system, aMDEA®, sulfolane, and DEPG. [Figure 8] 1 is a line graph showing the estimated regeneration energy for producing CO2 at different pressures for an exemplary embodiment of the solvent system and aMDEA. [Figure 9] 1 is a bar graph showing calculated energy savings for various syngas feed pressures. DETAILED DESCRIPTION OF THE INVENTION

[0019] Described herein are non-aqueous solvent systems configured to remove acid gases from gas streams. The term "acid gas" is intended to refer to any gas component that can form an acid when mixed with water. Non-limiting examples of acid gases encompassed by the present invention are CO2, SO2, COS, CS2, and NO2. x For simplicity, the invention will be described below with particular reference to CO. However, it should be understood that the invention encompasses methods and systems for removing any acid gas component from a gas stream.

[0020] In certain embodiments, the solvent system is regenerable in that acid gases can be released from the solvent, the solvent recycled, and additional acid gases separated from the further gas mixture.

[0021] The solvent system includes a solution of a chemical absorbing component and a physical absorbing component. The chemical absorbing component comprises a nitrogen base, the nitrogen base being structured to react with a portion of the acid gas. The physical absorbing component comprises an organic diluent that is unreactive with the acid gas and is structured to absorb a portion of the acid gas at pressures above atmospheric pressure.

[0022] The organic diluent may be, but is not necessarily, a relatively acidic component. As used herein, the term "relatively acidic component" is understood to be interchangeable with the term "acidic component" and to mean a material having an acidity greater than that of water, preferably substantially greater than that of water. For example, in some embodiments, the diluent may have a pKa of less than about 15, less than about 14, less than about 13, less than about 12, less than about 11, or less than about 10. In other embodiments, the organic diluent is not a relatively acidic component and does not have a pKa within the above range. For example, the organic diluent may have a pKa of greater than about 15 in certain embodiments.

[0023] In certain embodiments, the organic diluent used in the solvent system may generally be selected from the group consisting of alcohols, ketones, aliphatic hydrocarbons, aromatic hydrocarbons, nitrogen heterocycles, oxygen heterocycles, aliphatic ethers, cyclic ethers, esters, and mixtures thereof. In more specific embodiments, the diluent may be selected from polyethylene glycol dialkyl ethers. For example, the diluent may be selected from the group consisting of polyglycol dimethyl ether and polyglycol dibutyl ether, such as diethylene glycol dibutyl ether, triethylene glycol dibutyl ether, tetraethylene glycol dibutyl ether, or mixtures thereof. In embodiments, the diluent generally has a low vapor pressure and low viscosity. Removal of acid gases using a diluent or physical absorption component is achieved by direct contact between the acid gas and the diluent.

[0024] The nitrogen base can be characterized as any nitrogen base having a proton that can be donated from nitrogen, which reacts with acid gases via a carbamate pathway, avoiding reaction with acid gases to form carbonate esters. In certain embodiments, the nitrogen base component can be almost any nitrogen base that meets this requirement, including, but not limited to, primary amines, secondary amines, diamines, triamines, tetraamines, pentamines, cyclic amines, cyclic diamines, amine oligomers, polyamines, alcohol amines, guanidines, amidines, and the like. In some embodiments, the nitrogen base can have a pKa of about 8 to about 15, about 8 to about 14, about 8 to about 13, about 8 to about 12, about 8 to about 11, or about 8 to about 10. In certain embodiments, the nitrogen base component has a pKa of less than about 11.

[0025] Primary amines are understood to be compounds of formula NH2R, where R is C1-C 20 It can be a carbon-containing group, including but not limited to alkyl. Secondary amines are understood to be compounds of the formula NHR1R2, where R1 and R2 are C1-C 20 are independent carbon-containing groups, including but not limited to alkyl, where R, R1, and R2 are C1-C 20One or more hydrogen atoms on R, R1, and R2 may be optionally replaced with one or more substituents. For example, one or more hydrogen atoms on R, R1, or R2 may be optionally substituted with C1-C6 alkyl, optionally substituted C1-C6 alkoxy, optionally substituted C2-C6 alkyl, optionally substituted C1-C6 alkoxy, optionally substituted C2-C6 alkyl, optionally substituted C1-C6 alkyl, optionally substituted C2 ... 10 Alkenyl; optionally substituted C2-C 10alkynyl; optionally substituted alkaryl; optionally substituted arylalkyl; optionally substituted aryloxy; optionally substituted heteroaryl; optionally substituted heterocycle; halogen (e.g., Cl, F, Br, I); hydroxyl; alkyl halides (e.g., CF3, 2-Br-ethyl, CH2F, CH2CF3, and CF2CF3); optionally substituted amino; optionally substituted alkylamino; optionally substituted arylamino; optionally substituted acyl; CN; NO2; N3; CH2OH; CONH2; C1-C3 alkylthio; sulfate; sulfonate; sulfonate ester (e.g., methanesulfonyl); phosphonate; phosphate; phosphonate; mono-, di-, or triphosphate ester; trityl or monomethoxytrityl; CF3S; CF3SO2; or silyl (e.g., trimethylsilyl, dimethyl-t-butylsilyl, and diphenylmethylsilyl). Cyclic amines are amines in which the nitrogen atom forms part of a ring structure, and may include, but are not limited to, aziridine, azetidine, pyrrolidine, piperidine, piperazine, pyridine, pyrimidine, amidine, pyrazole, and imidazole. Cyclic amines may have one or more rings and may be optionally substituted with one or more substituents as described above. In some embodiments, the nitrogen base has a guanidine structure, which is optionally substituted with one or more substituents as described above. In some embodiments, the nitrogen base has an amidine structure, which is optionally substituted with one or more substituents as described above. In some embodiments, the nitrogen base may be a diamine. In some embodiments, the nitrogen base may be a primary or secondary alcoholamine. Alcoholamines, also known as aminoalcohols, contain both an alcohol group and an amine group. The amine group of the alcoholamine may be any type of amine as disclosed herein. In some embodiments, the alcoholamine is a primary, secondary, or tertiary alcoholamine.

[0026] In certain embodiments, primary or secondary amine can be selected from the amine functionalized with fluorine-containing alkyl aromatic group.In certain embodiments, amine can be selected from the group consisting of 2-fluorophenethylamine; 3-fluorophenethylamine; 4-fluorophenethylamine; 2-fluoro-N-methylbenzylamine; 3-fluoro-N-methylbenzylamine; 4-fluoro-N-methylbenzylamine; 3,5-difluorobenzylamine; D-4-fluoro-α-methylbenzylamine; L-4-fluoro-α-methylbenzylamine.

[0027] In certain embodiments, the nitrogen base is 1,4-diazabicyclo-undec-7-ene ("DBU"); 1,4-diazabicyclo-2,2,2-octane; piperazine ("PZ"); triethylamine ("TEA"); 1,1,3,3-tetramethylguanidine ("TMG"); 1,8-diazabicycloundec-7-ene; monoethanolamine ("MEA"); diethylamine ("DEA"); ethylenediamine ("EDA"); 1,3-diaminopropane; 1,4-diaminobutane; hexamethylenediamine; 1,7-diaminoheptane; diethanolamine; diisopropylamine ("DIPA"); 4-aminopyridine; pentyl The nitrogen base may be selected from the group consisting of amines, hexylamines, heptylamines, octylamines, nonylamines, decylamines, tert-octylamines, dioctylamines, dihexylamines, 2-ethyl-1-hexylamines, 2-fluorophenethylamines, 3-fluorophenethylamines, 3,5-difluorobenzylamines, N-methylbenzylamines, 3-fluoro-N-methylbenzylamines, 4-fluoro-N-methylbenzylamines, imidazoles, benzimidazoles, N-methylimidazoles, 1-trifluoroacetylimidazoles, 1,2,3-triazoles, 1,2,4-triazoles, and mixtures thereof. In certain embodiments, the nitrogen base may be guanidine or amidine. In certain embodiments, the nitrogen base may be N-methylbenzylamine.

[0028] One particular solvent system is shown in Figure 1. As shown in Figure 1, in the solvent system, the nitrogen base can be N-methylbenzylamine and the organic diluent can be one or a combination of diethylene glycol dibutyl ether, triethylene glycol dibutyl ether, or dibutyl ether of tetraethylene glycol.

[0029] In some embodiments, the solvent system may include a mixture comprising a nitrogen base and a diluent, and these components may be present in approximately equal proportions by molar concentration (i.e., equimolar amounts). In certain embodiments, the diluent is present in excess. For example, the molar ratio of diluent to nitrogen base can be from about 1:1 to about 100:1, e.g., from about 1.1:1 to about 20:1, 1.1:1 to about 15:1, 1.1:1 to about 10:1, 1.1:1 to about 5:1, 1.1:1 to about 3:1, from about 2:1 to about 20:1, from about 2:1 to about 15:1, 2:1 to about 10:1, from about 2:1 to about 5:1, from about 3:1 to about 20:1, from about 3:1 to about 15:1, from about 3:1 to about 10:1, from about 4:1 to about 20:1, from about 4:1 to about 15:1, from about 4:1 to about 10:1, from about 5:1 to about 20:1, from about 5:1 to about 15:1, or from about 5:1 to about 10:1.

[0030] In embodiments, the solvent system may include a mixture comprising a chemical absorbing component and a physical absorbing component, and these components may be present in approximately equal weight percent. In certain embodiments, the physical absorbing component is present in excess. For example, the chemical absorbing component may be present at a concentration ranging from about 1 to about 50 weight percent based on the weight of the total system, such as about 5 to about 30 weight percent of the total system, about 10 to about 20 weight percent of the total system, or about 10 to about 15 weight percent of the total system. In embodiments, the physical absorbing component may be present at a concentration ranging from 40 to 95 weight percent of the total system, such as 50 to 90 weight percent of the total system, or 70 to 90 weight percent of the total system. In embodiments, the solvent system may further include water. The water may be present at a concentration ranging from about 1 to about 10 weight percent of the total system. In an exemplary embodiment, the components may be present at a concentration of 1 to 20 weight percent chemical absorbing component, 70 to 98 weight percent physical absorbing component, and 1 to 10 weight percent water.

[0031] In embodiments, the solvent system may be formulated with a combination of a hydrophobic amine species that chemically reacts with CO2 and a hydrophobic organic solvent that physically absorbs CO2. The solvent system may perform at equal or greater capacity than commercially available acid gas scrubbing solvents. In embodiments, the solvent system may be used to remove CO2 from syngas streams. The solvent system may be a suitable candidate to replace commercially available aqueous amine-based acid removal solvents, such as activated methyldiethanolamine (aMDEA).

[0032] As described in the exemplary section below, exemplary embodiments of the solvent system are capable of performing deep CO removal similar to commercially available aMDEA while reducing the amount of energy required for solvent regeneration. In exemplary embodiments, N-methylbenzylamine (NMBA) can be used as a nitrogen base to chemically bind CO, and an organic diluent comprising polyethylene glycol dibutyl ether can be used to physically absorb CO at high pressure. A simple flash tank, requiring little energy, is sufficient to release the physically adsorbed portion of CO.

[0033] Without wishing to be bound by any particular theory, it is believed that the use of additional components can be useful in reducing or preventing the precipitation of solids in the solvent system. In some embodiments, the solvent system may further comprise one or more additional components. Additional components may be added, for example, to increase the solubility of the captured CO2 product in the solvent system, thus avoiding the formation of precipitates. However, in other embodiments, solid formation may be desirable, and such formation may be enhanced by varying the concentration of one or more solvent system components.

[0034] In some embodiments, the solvent system is useful for capturing CO from gas streams. In additional embodiments, the solvent system is useful for capturing CO from gas streams at pressures above atmospheric pressure. For example, the operating pressure of the absorber vessel can be from about 2 bar to about 60 bar.

[0035] The gas stream can be a mixed gas stream having one or more other components in addition to CO2. When the solvent system contacts the gas mixture containing CO2, the chemical absorption component of the solvent system chemically reacts with the CO2 and binds the CO2 in solution. The physical absorption component of the solvent system uses pressure to dissolve the CO2. The amount of acid gas that dissolves in the physical absorption solvent increases proportionally with increasing pressure.

[0036] In some embodiments, the solvent system has high CO removal. For example, the solvent system may be useful for capturing or removing greater than about 80% by weight of CO present in a process gas stream. For example, the solvent system may capture or remove greater than about 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%, or up to 100% by weight of the CO present in a process gas stream. As used herein, the term "deep removal" refers to the capture or removal of greater than about 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%, or up to 100% by weight of the CO present in a process gas stream. The term deep removal also applies to acid gases other than CO. In embodiments, the solvent system may be useful for capturing or removing near or substantially all of the CO present in the process gas stream. For example, after contact with the solvent system, the gas stream from which the CO has been captured or removed (the "lean gas stream") may have CO present in an amount of about 1500 ppm or less. For example, CO may be present in the lean gas stream in an amount of about 500 ppm to about 1500 ppm. In embodiments, CO may be present in the lean gas stream in an amount of about 500 ppm, 600 ppm, 700 ppm, 800 ppm, 900 ppm, 1000 ppm, 1100 ppm, 1200 ppm, 1300 ppm, 1400 ppm, or 1500 ppm or less.

[0037] In some embodiments, the solvent system can be used for partial CO removal. For example, the solvent system can be useful for capturing or removing from about 30% to about 70% by weight of the CO present in the process gas stream. For example, the solvent system can capture or remove about 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, or 70% by weight of the CO present in the process gas stream.

[0038] In certain embodiments, the diluent (i.e., the physical absorption component) is selected to have low miscibility with water. For example, in some embodiments, the diluent has a solubility of about 10 g / 100 mL or less in water at 25° C. (i.e., about 10 g of solvent per 100 mL of water). In other embodiments, the diluent has a solubility of about 0.01 g / 100 mL or less, about 0.1 g / 100 mL or less, about 0.5 g / 100 mL or less, about 1 g / 100 mL or less, about 1.5 g / 100 mL or less, about 2 g / 100 mL or less, about 2.5 g / 100 mL or less, about 3 g / 100 mL or less, about 4 g / 100 mL or less, about 5 g / 100 mL or less, about 6 g / 100 mL or less, about 7 g / 100 mL or less, about 8 g / 100 mL or less, or about 9 g / 100 mL or less in water at 25° C. In some embodiments, the diluent is completely immiscible with water. Use of a diluent with low water solubility may result in a solvent system that exhibits one or more of the following properties: it may require less energy to regenerate; it may have high CO removal capacity; it may be able to tolerate water in the gas stream; and / or it may be possible to separate it from water without a significant energy penalty.

[0039] In additional embodiments, the nitrogen base component (i.e., the chemisorption component) of the solvent system is similarly selected to have low miscibility with water. In preferred embodiments, the nitrogen base is more miscible with the diluent than with water. In some embodiments, the nitrogen base has high solubility in the diluent. Examples of such nitrogen bases include, but are not limited to, aliphatic amines having one or more hydrocarbon chains composed of three or more carbons and aliphatic amines having one or more hydrocarbon chains composed of three or more carbons with one or more fluorine atoms substituted for hydrogen in the hydrocarbon chain. While diluents and / or nitrogen bases that are low in miscibility with water are preferred, it should be noted that the present invention also encompasses solvent systems in which the diluent, nitrogen base, and / or combination thereof are at least partially miscible with water.

[0040] In embodiments, the solvent system has a dynamic viscosity in the range of 1 mPas to 20 mPas at a temperature of 10 to 60° C. For example, the dynamic viscosity can be about 1 mPas to about 10 mPas, about 1 mPas to about 8 mPas, or about 1 mPas to about 4 mPas. In embodiments, the solvent system has a vapor pressure in the range of about 0.02 mbar to about 0.03 mbar at 20° C.

[0041] In some embodiments, the solvent system is tolerant to the presence of water. In certain embodiments, the solvent system tolerates about 30% or less by volume of water. For example, in some embodiments, the solvent system tolerates about 25% or less by volume, about 20% or less by volume, about 15% or less by volume, about 10% or less by volume, about 5% or less by volume, about 2% or less by volume, or about 1% or less by volume of water. In some embodiments, tolerant to the presence of water means that there is little or no degradation in the performance of the solvent system up to the indicated volume of water. In some embodiments, the solvent system maintains at or near its initial capacity for CO2 removal up to the indicated volume of water.

[0042] In embodiments, CO captured using the solvent system of the present invention can be released to regenerate the solvent system for reuse. It is desirable that the solvent system be regenerative under mild conditions (e.g., at relatively low temperatures and pressures). In some embodiments, the release of CO and corresponding regeneration of the solvent system is achieved by reducing the pressure of the solution and heating it. When the pressure is reduced, the physically absorbed CO is released from the physical absorption component of the solvent system. When the solution containing chemically bound CO is heated, the chemical reaction with the chemical absorption component is reversed, releasing the chemically bound CO. The released CO provides a concentrated CO stream.

[0043] In some embodiments, the present application relates to a solvent system and process for removing CO from a gas stream. This process applies to any gas stream containing CO. For example, in detailed embodiments, the process relates to a method for removing CO from fossil fuel combustion flue gas, natural gas mixtures, or mixtures of breathing gases from a CO-containing enclosed environment. The process includes passing the mixed gas stream through a solvent system comprising a diluent and a nitrogen base component. In some embodiments, the process further relates to regenerating the solvent system to release CO. In some embodiments, regenerating the solvent system includes heating the solvent system at a temperature sufficient to release CO. In some embodiments, the process includes heating the solvent system at a temperature of about 200° C. or less, e.g., about 185° C. or less, about 150° C. or less, or about 125° C. or less. In preferred embodiments, the process includes heating the solvent system at a temperature of about 100° C. or less, e.g., about 95° C. or less, about 90° C. or less, about 85° C. or less, about 80° C. or less, about 75° C. or less, or about 70° C. or less. In some embodiments, CO can be released at ambient temperature.

[0044] In some embodiments, regenerating the solvent system involves reducing the pressure of the solvent system to release the CO2 absorbed at a relatively high pressure. In some embodiments, the process involves reducing the pressure of the solvent system to about 60 bar or less, e.g., about 40 bar or less, about 20 bar or less, or about 5 bar or less. In certain embodiments, the pressure is reduced to atmospheric pressure. In certain embodiments, the CO2 is captured in the non-aqueous phase under conditions where water accumulates as a separate, lower density phase. This phase is sent to a regenerator along with the enriched non-aqueous phase and regenerated at a lower temperature than the corresponding enriched aqueous phase alone. It may then be phase separated from the lean regeneration solvent before being sent back to the absorber.

[0045] In some embodiments, the present application relates to a method for deep removal of acid gases from a gas stream. The method includes introducing a non-aqueous solvent system comprising a physical absorption component and a chemical absorption component into an absorber vessel operating at a pressure above atmospheric pressure. The method includes introducing a gas stream comprising acid gases into the absorber vessel, such that the gas stream passes in fluid contact with the non-aqueous solvent system, whereby 90% by weight of the acid gases are removed from the gas stream by the solvent system. In embodiments, the absorber vessel operates at a pressure of about 2 to 60 bar. For example, the pressure can be about 10 to 30 bar. In embodiments, at least 95% by weight of the acid gases are removed from the gas stream. For example, at least 97%, at least 98%, or at least 99% by weight of the acid gases are removed from the gas stream. In some embodiments, the gas stream has an initial concentration of acid gases when introduced into the absorber vessel and a reduced concentration of acid gases after passing through the absorber vessel, the reduced concentration of acid gases being 750 ppm to 1500 ppm. The reduced concentration of acid gases can be 1500 ppm or less.

[0046] In certain embodiments, about 100% of the CO is removed from the CO-rich solvent system when the solvent system is regenerated, although in other embodiments, less than 100% of the CO is removed from the CO-rich solvent system. In embodiments, about 50-100% of the captured CO is removed from the CO-rich solvent system, e.g., about 75%-100%, about 80%-100%, about 90%-100%, about 95%-100%, or about 98%-100%. For example, in some embodiments, at least about 98%, 95%, 90%, 85%, 80%, 75%, 70%, 60%, or 50% of the captured CO is removed from the CO-rich solvent system.

[0047] In some embodiments, a system for removing CO from a gas stream is provided. A schematic diagram of an exemplary system of the present invention is shown in FIG. 2. The CO removal system 10 includes an absorber 12 configured with an inlet for receiving a gas stream. The gas stream may come directly from a combustion chamber of a boiler system, for example, at a power plant. The gas stream may or may not pass through other cleaning systems before entering the CO removal system. The absorber may be any chamber containing a solvent system for removing CO and equipped with an inlet and outlet for the gas stream, where the gas stream may be contacted with the solvent system. Within the absorber, the CO may be transferred from the gas phase to the liquid phase according to the principles described herein. The absorber may be of any type; for example, the absorber may comprise a spray tower absorber, a packed bed absorber (including a counterflow tower or a crossflow tower), a tray tower absorber (with a variety of tray types including bubble cap trays, sieve trays, impingement trays, and / or float valve trays), a venturi absorber, or an ejector absorber.

[0048] The temperature and pressure within the absorber can be controlled. For example, in one embodiment, the temperature of the absorber can be maintained from about -10°C or thereabouts to about 60°C. For example, the temperature of the absorber can be about 0°C to about 60°C, about 30°C to about 60°C, or about 50°C to about 60°C. In an embodiment, the pressure of the absorber is maintained at a pressure above atmospheric pressure. For example, the pressure of the absorber can be maintained at a pressure of about 5 bar to about 60 bar, about 10 bar to about 60 bar, about 30 bar to about 60 bar, about 10 bar to about 30 bar, about 5 bar to about 20 bar, or about 10 bar to about 20 bar. In an embodiment, the absorber can be maintained at or near atmospheric pressure. Accordingly, the absorber can be equipped with a heating / cooling system and / or a pressure / vacuum system.

[0049] Within the absorber, the gas stream, comprising a diluent and a nitrogen base component, is passed through a solvent system in fluid contact. The solvent system interacts with the CO2 present in the gas stream through chemical and physical absorption, capturing CO2 from the remaining components of the gas. The resulting CO2-free gas stream is released from the absorber via an outlet. The solvent system continues to interact with the CO2 entering the absorber as the mixed gas stream passes through, continuing until the absorber is "rich" in CO2. The absorber is optionally connected to one or more processing devices. For example, the absorber may be configured with a means for delivering the solvent system to a unit, where water may be decanted, centrifuged, or otherwise removed from the system. In embodiments, the solvent system may absorb more than one type of acid gas from the gas stream. For example, the solvent system may absorb CO2 and sulfur-type acid gases. In this exemplary embodiment, the absorber may be connected to one or more processing units that separate the CO and sulfur species acid gases into two streams to achieve a high purity (greater than 90% by weight) CO stream and a stream having a purity of greater than 50% sulfur species.

[0050] At any stage of the CO2 capture process, the solvent system may be regenerated. Accordingly, the system includes an additional regeneration system 14 for releasing the captured CO2 via a separate CO2 gas stream, thus regenerating the solvent system. The regeneration system is configured to receive a supply of "rich" solvent from the absorber and, once the CO2 has been separated from the "rich" solvent, return the regenerated solvent to the absorber. The regeneration system may simply comprise a chamber operating at a lower pressure than the absorber, having a heating unit for heating the solvent system to a temperature sufficient to release CO2 gas, together with a release valve for allowing CO2 to be removed from the regeneration system. It may also be a distillation column operating at a lower pressure than the absorber and having substantially the same design as described above for the absorption column. The regenerator may be coupled to one or more units as needed. For example, the regenerator may be configured with a means for delivering the solvent to a unit where water can be decanted, centrifuged, or otherwise removed from the system.

[0051] The exhausted CO2 can be output to storage or other intended use. The regenerated solvent can be returned to the absorber, ready to absorb CO2 from the gas stream again.

[0052] In some embodiments, the present application relates to a method for reducing the amount of energy required for solvent regeneration of a non-aqueous solvent system (NASS) in an acid gas scrubbing process. The regeneration energy savings are proportional to the amount of energy required for solvent regeneration of conventional aqueous amine-based solvents. The solvent system described herein can be used to remove acid gases from a gas stream in an absorption vessel operating at a pressure greater than atmospheric pressure and less than 60 bar, thereby forming an acid gas-containing NASS. The acid gas-containing NASS can be introduced into a pressure relief vessel operating at a pressure lower than the operating pressure of the absorption vessel. The reduction in pressure leads to the acid gases absorbed by the physical absorption component of the NASS being released from the acid gas-containing NASS. The pressure relief vessel is heated to a temperature such that the acid gases absorbed by the chemical absorption component of the acid gas-containing NASS are released, thereby providing regenerated NASS that can be reused in the gas scrubbing process. The energy used to provide the regenerated NASS is reduced compared to the energy used to provide a regenerated form of aqueous solvent in the acid gas scrubbing process. In embodiments, the proportion of acid gas absorbed by the physisorption component of the NASS is greater than the proportion of acid gas absorbed by the chemical absorption component of the NASS. The ratio of acid gas absorbed by the physisorption component to the chemical absorption component ranges from 1.5:1 to 30:1. For example, the ratio can be 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, or 10:1.

[0053] Calculations can be performed to estimate the amount of energy savings that can be achieved during solvent regeneration by using the solvent system described herein compared to commercially available aqueous amine-based systems. Figure 3 provides an illustration of an exemplary calculation for determining the reboiler heat duty of the chemical absorption component of the solvent system. The calculation includes the sensible heat required to heat the solvent to the regeneration temperature, the heat of vaporization required to remove the absorbed acid gas from the physical absorption component, and the heat of absorption required to remove the absorbed acid gas from the chemical absorption component. As explained in the Examples section below, the heat of absorption of the chemical absorption component significantly affects the reboiler heat duty.

[0054] The solvent systems described herein offer advantages over existing acid gas scrubbing solvents. In embodiments, the regeneration energy required to release captured CO2 is reduced relative to commercially available aqueous absorption solvents. Furthermore, in embodiments, the relatively low viscosity of the solvent system allows for pumping cost savings compared to commercially available higher viscosity solvents, such as aMDEA. Furthermore, in embodiments, the solvent system has high operating capacity at relatively low temperatures, thus allowing for a reduced process footprint, reduced operating costs, and minimized solvent emissions.

[0055] Many modifications and other embodiments of the inventions set forth herein will come to mind to one skilled in the art to which these inventions pertain having the benefit of the teachings presented in the foregoing descriptions and the associated drawings. It is understood, therefore, that the invention is not to be limited to the specific embodiments disclosed, and that modifications and other embodiments are intended to be included within the scope of the appended claims. Although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation. [Example]

[0056] (Evaluation of CO2 removal efficiency) The CO2 removal efficiency of an exemplary embodiment of the solvent system was compared to that of a commercially available aMDEA® (an aqueous alkaline amine solution manufactured and sold by BASF, Ludwigshafen, Germany) using a single-pass, gas-liquid contact high-pressure absorption column. Figure 4 provides a schematic of the absorption column used in the test. N2 and CO2 mass flow controllers were used to control the composition of the gas entering the bottom of the absorption column. The absorption column was constructed using 1-inch OD SS pipe insulated with ceramic fiber insulation, with a 4-L SS sump attached to the bottom of the column. The absorption column was packed with approximately 300 grams of 0.16-inch Pro-Pak® protruding random metal packing with a packing height of 3.5 m. The solvent was metered and delivered to the top of the absorber by a diaphragm pump. The solvent and CO2-containing gas contacted each other within the absorption column, and the CO2-rich liquid solvent was collected in the absorber sump while the CO2-free gas was discharged from the top of the column. The absorber off-gas was cooled using a condenser to remove carryover solvent collected by the knock-out pot. A slip stream of dry, solvent-free gas was extracted and fed to the CO2 analyzer before the knock-out pot to reduce the response lag time caused by the vessel. The remaining gas exited the system through a back-pressure regulator at the outlet of the knock-out pot to maintain a constant pressure in the column. Pressure relief valves were installed throughout the gas supply locations to prevent overpressure of the system. Temperature and pressure at various locations were monitored via temperature probes (TE) and pressure indicators (PI), respectively.

[0057] An exemplary solvent system used in the testing was a blend of N-methylbenzylamine (NMBA), polyglycol dibutyl ether, and water, with a concentration of about 10.5 wt.% NMBA, about 5.2 wt.% water, and the remainder polyglycol dibutyl ether. Because the composition of aMDEA® is proprietary and not publicly available, a blend of 62.6 wt.% MDEA, 5.37% piperazine, and the remainder water was created and used as a surrogate compound for aMDEA®.

[0058] CO2 removal efficiency experiments were performed by pressurizing the system to 20 bar(a) (300 psia) using a 20% by volume CO2 in N2 mixture. Once the target pressure was reached and the CO2 analyzer read a constant CO2 concentration of approximately 20% at the absorber outlet, the gas flow rate was adjusted to 200 sccm. Fresh solvent was fed into the column at a controlled rate to capture CO2 from the gas mixture. CO2 absorption was performed at room temperature.

[0059] A summary of the various solvents evaluated and their CO2 removal performance is shown in Table 1. Water (Run A1) was used to determine performance via physical absorption of CO2 in water under high-pressure conditions. Results suggest that only 30% of the CO2 was absorbed using water, compared to the required deep removal of over 99% of the CO2. aMDEA substitutes were tested at liquid flow rates of 2.4 g / min and 3.3 g / min (Runs A2 and A3, respectively), resulting in deep CO2 capture of over 99%. Reducing the aMDEA substitute liquid flow rate to 2.4 g / min produced a treated gas stream with a higher CO2 concentration of 1100 ppm compared to 800 ppm at the higher flow rate of 3.3 g / min. An exemplary solvent system, Run A4, demonstrated removal efficiencies comparable to those reported for aMDEA substitutes at similar liquid flow rates. Note that the exemplary solvent system experiment was terminated before a stable CO2 profile was achieved due to solvent pump control issues. Figures 5A-5C are line graphs showing CO2 concentration over time using an exemplary solvent system (Figure 5A), aMDEA substitute (Figure 5B), and water (Figure 5C). Based on the results, it is expected that CO2 levels as low as 750-800 ppm can be achieved at steady state using the exemplary solvent system.

[0060] [Table 1] [Example]

[0061] (CO2 gas-liquid equilibrium study) The CO gas-liquid equilibrium of an exemplary embodiment of the solvent system was measured in a computer-controlled stirred reactor modified with an automated gassing system supplied by Chemisens. Figure 6 shows a schematic diagram of the experimental setup, including the reactor and batch vessel. The reactor was a 260 mL cylindrical stainless steel vessel equipped with a propeller agitator and four blades for mixing both the liquid and gas phases. The agitation speed could be varied to the desired value with an accuracy of ±1 rpm. The reactor temperature was maintained at the desired isothermal conditions by a propylene glycol bath. The reactor pressure was monitored by a pressure transducer (PI-301) with an accuracy of ±0.03% FSO. The reactor was connected to a solenoid valve (HV-305) to supply the desired gas to the reactor at isothermal conditions from a 178 mL batch vessel. A mass flow controller, solenoid valve (HV-250), and pressure transducer (PI-302) were installed between the valve (HV-305) and the batch vessel to control the flow rate and monitor the pressure in the reactor inlet section. The pressure in the batch vessel was measured by a pressure transducer (PI-221). A flow control valve (FCV-230) was used to control the flow rate from the batch vessel to the manifold and reactor by opening the solenoid valve (HV-211). Gas to the batch vessel was supplied from the appropriate gas cylinder via the valve (HV-210). In addition, a series of solenoid valves (HV-225, HV-331, HV-334, HV-332, and HV-333) were used to purge the system with nitrogen (N2), and a vacuum was applied to degas the solvent and evacuate the system before the experiment. The reactor setup was placed in an incubator maintained at a constant temperature of 30 °C to avoid temperature fluctuations.

[0062] To measure the CO2 isotherm, 100 mL of solvent was loaded into the SS reactor and degassed. Degassing was performed by purging the cell with N2 and then applying vacuum for 7-8 cycles. After degassing, CO2 was injected into the reactor and allowed to reach vapor-liquid equilibrium, indicated by a constant pressure reading in the reactor cell. The experiment continued with subsequent injections until the total reactor pressure reached approximately 300 psia.

[0063] The CO vapor-liquid equilibrium (VLE) of an exemplary embodiment of the solvent system was measured and plotted in Figure 7. Figure 7 also includes VLE curves for aMDEA®, sulfolane (a cyclic sulfone of formula (CH)SO), and DEPG (a mixture of dimethyl ethers of polyethylene), where aMDEA is a chemical absorption solvent, while sulfolane and DEPG are physical absorption solvents. The exemplary embodiment of the solvent system is a hybrid solvent capable of absorbing CO by both chemical absorption and physical absorption modes.

[0064] Chemical absorption solvents can achieve deep scrubbing of CO2 at low CO2 concentrations, but their absorption capacity is limited by the available amines in the solvent that chemically react with CO2. Chemical absorption is independent of system pressure. In tests, aMDEA exhibited a saturation capacity of approximately 0.2 mol CO2 / mol solvent at 600 kPa. Increasing the pressure did not improve CO2 loading beyond the saturation point due to the limited physical solubility of CO2 in water.

[0065] Physical solvents generally remove CO2 poorly from dilute gas streams. However, as system pressure increases, absorption capacity increases linearly. Exemplary embodiments of the solvent system were able to achieve deep CO2 capture even when CO2 concentrations were relatively low. Also, increasing pressure was able to increase CO2 removal capacity.

[0066] The ability to perform CO absorption over a wide pressure range is an advantage of the solvent systems described herein compared to aMDEA and other amine-based aqueous solvents. This advantage is particularly relevant for removing CO from high-pressure gases, such as CO-containing syngas streams. Because the solvent systems have a higher CO removal capacity at high pressures (i.e., they can absorb more CO from the gas stream), less solvent is required to remove the same amount of CO. Therefore, the footprint of the scrubbing process can be reduced because less solvent inventory can be used. Furthermore, because of the regeneration capabilities of the solvent systems described herein, the packed column regenerator can be replaced with a smaller flash vessel equipped with a heating coil to regenerate the solvent system. This replacement reduces equipment costs and simplifies operations.

[0067] In the solvent system described herein, the chemical absorption component maintains the deep scrubbing capability enabled by chemical absorbents, but the regeneration energy is much less than with aqueous amine-based solvents such as aMDEA, which function solely by chemical absorption. In the described solvent system, the majority of the CO2 is removed by flashing rather than heating because it is captured by the physical absorption component (rather than the chemical absorption component) of the solvent system. Calculations show a 30% energy savings for each kg of CO2 removed from the enriched solvent due to the use of a flash tank to regenerate the solvent rather than the aMDEA regeneration process.

[0068] Calculations were performed to evaluate the impact of target CO2 product pressure on the energy use of solvent regeneration. Figure 8 is a line graph showing the estimated regeneration energy to produce CO2 at different pressures for an exemplary embodiment of the solvent system and aMDEA. The calculations used a basis of removing 100 mol-CO2 from the solvent. For the solvent system, it was assumed that a portion of the CO2 was removed by flashing (for the physical absorption component) and the remaining portion was removed by providing heat for regeneration (for the chemical absorption component). The amount of CO2 removed by flashing was calculated as the CO2 loading (X) at an initial pressure of 10 bar(a). CO2) and the CO2 loading at a particular flash pressure. It was assumed that no energy was required to remove the CO2 by flashing. The energy required to remove the remaining CO2 was calculated using the heat of absorption of CO2 (dH for solvent systems). abs,NAS = 80kJ / mol-CO2, dH for aMDEA abs,aMDEA The heat of absorption of the components was determined by multiplying the amine in the formula (=60 kJ / mol-CO2) by the amount of remaining CO2. The heat of absorption of the components was measured for the amine in the formula using a calorimeter. Based on calculations, when producing pure CO2 at atmospheric pressure, a regeneration energy reduction of up to 40% can be achieved by using a solvent system. The energy saving effect of the solvent system begins to decrease as the target CO2 product pressure increases and reaches an equilibrium point at 5 bar (a) aMDEA. This result is due to the smaller portion of physically bound CO2 being removed at higher regeneration pressures and the greater energy required to regenerate chemically bound CO2. Note that these estimates only consider the heat of absorption, while the sensible heat required to heat the solvent to the regeneration temperature is not included, as the contribution of sensible heat is estimated to be relatively small (less than 20%) to the overall energy requirement and similar for various solvents.

[0069] The effect of syngas feed pressure on energy use for regeneration was also investigated. Figure 9 is a bar graph showing the calculated energy savings for various syngas feed pressures. For the calculations, the feed gas pressure was varied from 30 to 100 bar in 10 bar increments. The target pressure for regeneration CO2 was fixed at 1 bar. Calculations showed that the solvent system described herein required less regeneration energy than aMDEA as the feed gas pressure increased. The calculations used the same approach as above to determine the energy required for solvent regeneration. As above, the calculations also determined the amount of energy required to regenerate chemically absorbed CO2. The calculations assumed a CO2 concentration of 20% by volume at all syngas pressures. For the solvent system, as the syngas pressure increased, the majority of the CO2 was absorbed by physical absorption, and therefore, the majority of the absorbed CO2 was removed by flashing. In contrast, the CO2 saturation limit for aMDEA is 0.2 mol CO2 / mol solvent, regardless of pressure. Therefore, most of the absorbed CO2 must be thermally removed (i.e., the ratio of the initial pressure to the final pressure). CO2 (This is a small difference).

[0070] In the case of the solvent system described herein, the chemical absorption component allows the solvent system to achieve deep CO2 scrubbing similar to that achieved by aMDEA. Furthermore, the physical absorption component provides additional CO2 removal capacity at high pressures, where the removal capacity of chemical absorption solvents, including aMDEA, is limited by the CO2-amine reaction stoichiometry. To regenerate a solvent system, most of the CO2 can be removed by simply flushing the solvent, while only a small portion of the chemically bound CO2 needs to be thermally removed. The situation is reversed for aMDEA, as the majority of the CO2 is removed by thermal regeneration. Therefore, utilizing a solvent system offers the potential for reducing energy usage in such applications.

[0071] Numerous modifications and variations of the present invention are possible in light of the above teachings. It is therefore to be understood that, within the scope of the appended claims, the invention may be practiced otherwise than as specifically described herein.

Claims

1. 1. A non-aqueous solvent system configured for removing acid gases from a gas stream, the solvent system comprising: a chemical absorbing component comprising a nitrogen base, the nitrogen base having a structure such that it reacts with a portion of the acid gas; a physical absorption component comprising an organic diluent that is non-reactive with the acid gas and structured to absorb a portion of the acid gas at pressures above atmospheric pressure; a solution formed by wherein the solvent system has a water solubility of less than 10 g of solvent per 100 mL of water, and the organic diluent comprises a polyethylene glycol dialkyl ether; wherein the chemical absorption component is present in a concentration ranging from 10 to 60% by weight of the total system; wherein the nitrogen base is 1,4-diazabicyclo-undec-7-ene ("DBU"); 1,4-diazabicyclo-2,2,2-octane; piperazine ("PZ"); triethylamine ("TEA"); 1,1,3,3-tetramethylguanidine ("TMG"); 1,8-diazabicycloundec-7-ene; monoethanolamine ("MEA"); diethylamine ("DEA"); ethylenediamine ("EDA"); 1,3-diaminopropane; 1,4-diaminopropane; Nobutane; Hexamethylenediamine; 1,7-Diaminoheptane; Diethanolamine; Diisopropylamine ("DIPA"); 4-Aminopyridine; Pentylamine; Hexylamine; Heptylamine; Octylamine; Nonylamine; Decylamine; tert-Octylamine; Dioctylamine; Dihexylamine; 2-Ethyl-1-hexylamine; 2-Fluorophenethylamine; 3-Fluorophenethylamine; 3,5-Difluorobenzylamine; N-methylbenzylamine; 3-fluoro-N-methylbenzylamine; 4-fluoro-N-methylbenzylamine; imidazole; benzimidazole; N-methylimidazole; 1-trifluoroacetylimidazole; 1,2,3-triazole; 1,2,4-triazole; or a mixture thereof.

2. 10. The solvent system of claim 1, wherein the nitrogen base comprises N-methylbenzylamine.

3. 10. The solvent system of claim 1, wherein the organic diluent comprises polyethylene glycol dibutyl ether.

4. 4. The solvent system of claim 3, wherein the organic diluent is selected from the group consisting of diethylene glycol dibutyl ether, triethylene glycol dibutyl ether, tetraethylene glycol dibutyl ether, or mixtures thereof.

5. 10. The solvent system of claim 1, wherein the concentration of the chemical absorption component ranges from 10 to 20% by weight of the total system.

6. 10. The solvent system of claim 1, wherein the physical absorption component is present in a concentration ranging from 40 to 95% by weight of the total system.

7. 7. The solvent system of claim 6, wherein the concentration of the physical absorption component ranges from 50 to 90% by weight of the total system.

8. 8. The solvent system of claim 7, wherein the concentration of the physical absorption component ranges from 70 to 90% by weight of the total system.

9. The solvent system of claim 1 , wherein the system further comprises water.

10. 10. The solvent system of claim 9, wherein the water is present at a concentration ranging from 1 to 10% by weight of the total system.

11. The ingredients are: 1 to 20 wt. % of a chemical absorbing component; 70 to 98 weight percent of a physical absorption component; 1 to 10% by weight of water; 10. The solvent system of claim 9, wherein the solvent system is present in a concentration of

12. The acid gas is carbon dioxide (CO 2 ), carbonyl sulfide (COS), carbon disulfide (CS 2 ), sulfur oxide (SO x 10. The solvent system of claim 1, comprising:

13. 10. The solvent system of claim 1 having a dynamic viscosity in the range of 1 to 30 mPas at a temperature of 10 to 60°C.

14. 10. The solvent system of claim 1 having a vapor pressure at 20°C in the range of 0.02 to 0.03 mbar.

15. 10. The solvent system of claim 1 having a boiling point in the range of 180 to 250°C.

16. 1. A method for removing acid gases from a gas stream, the method comprising: introducing a non-aqueous solvent system comprising a physical absorption component and a chemical absorption component into an absorption vessel operating at a pressure above atmospheric pressure; introducing a gas stream comprising an acid gas into the absorption vessel such that the gas stream passes in fluid contact with the non-aqueous solvent system; wherein the organic diluent comprises a polyethylene glycol dialkyl ether and the non-aqueous solvent system is the solvent system of claim 1. A method for removing acid gases from a gas stream.

17. 17. The method of claim 16, wherein the absorption vessel operates at a pressure of from 2 to 60 bar.

18. 18. The method of claim 17, wherein the absorption vessel operates at a pressure of 10 to 30 bar.

19. 17. The method of claim 16, wherein at least 90% by weight of the acid gas is removed from the gas stream.

20. 20. The method of claim 19, wherein at least 95% by weight of the acid gas is removed from the gas stream.

21. 17. The method of claim 16, wherein 30 to 95 wt. % of the acid gas is removed from the gas stream.

22. 17. The method of claim 16, wherein the gas stream has an initial concentration of acid gases when introduced into the absorption vessel and a reduced concentration of acid gases after passing through the absorption vessel, wherein the reduced concentration of acid gases is between 750 ppm and 1500 ppm.

23. 17. The method of claim 16, wherein the gas stream has an initial concentration of acid gases when introduced into the absorption vessel and a reduced concentration of acid gases after passing through the absorption vessel, wherein the reduced concentration of acid gases is 1500 ppm or less.

24. The acid gas is carbon dioxide (CO 2 ), carbonyl sulfide (COS), carbon disulfide (CS 2 ), sulfur oxide (SO x 17. The method of claim 16, comprising:

25. The acid gas is CO 2 and S.O. x The method comprises: 2 and the SO x 25. The method of claim 24, further comprising separating the from each other so that each is in a separate stream.

26. 1. A method for reducing the amount of energy required for solvent regeneration of a non-aqueous solvent system (NASS) in an acid gas scrubbing process relative to the amount of energy required for solvent regeneration of a conventional aqueous solvent, comprising: removing acid gases from a process stream in an absorption vessel operating at a pressure above atmospheric pressure but less than 60 bar using the NASS of claim 1, thereby forming an acid gas-containing NASS; introducing the acid gas-containing NASS into a pressure relief vessel, wherein the pressure relief vessel is operated at a temperature and pressure, wherein the operating pressure of the pressure relief vessel is lower than the operating pressure of an absorption vessel, whereby the acid gases absorbed by the physical absorption component of the NASS are released from the acid gas-containing NASS upon introduction into the pressure relief vessel, and wherein the operating temperature of the pressure relief vessel is such that the acid gases absorbed by the chemical absorption component of the acid gas-containing NASS are released from the acid gas-containing NASS, thereby providing regenerated NASS that is free of acid gases and can be reused in a gas scrubbing process; wherein the energy used to provide the regenerated NASS is reduced compared to the energy used to provide a regenerated form of aqueous solvent in an acid gas scrubbing process; A method for reducing the amount of energy required for solvent regeneration of a non-aqueous solvent system (NASS) in an acid gas scrubbing process.

27. 27. The method of claim 26, wherein the proportion of acid gases absorbed by the physisorptive component of the NASS is greater than the proportion of acid gases absorbed by the chemisorptive component of the NASS.

28. 28. The method of claim 27, wherein the ratio of acid gases absorbed by the physical sorption component to the acid gases absorbed by the chemical component ranges from 1.5:1 to 30:

1.

29. 29. The method of claim 28, wherein the ratio is selected from 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1 and 10:

1.

30. The acid gas is carbon dioxide (CO 2 ), carbonyl sulfide (COS), carbon disulfide (CS 2 ), sulfur oxide (SO x 27. The method of claim 26, comprising:

31. 27. The method of claim 26, wherein the absorption vessel is operated at a pressure of from 2 to 60 bar.

32. 32. The method of claim 31, wherein the absorption vessel is operated at a pressure of 10 to 30 bar.

33. 27. The method of claim 26, wherein the chemical absorption component comprises N-methylbenzylamine.

34. 27. The solvent system of claim 26, wherein the physically absorbing component comprises polyethylene glycol dibutyl ether.

Citation Information

Patent Citations

  • Hybrid absorption liquid, gas separation and refining method, and apparatus for the same

    JP2011230056A

  • Method for separating and recovering mixed gas component, and device therefor

    JP2011251220A

  • Renewable solvent mixture for acid-gas separation

    JP2013538125A

  • Moisture control in non-hydrogen acid gas removal systems

    JP2017506150A

  • Regenerable solvent mixtures for acid-gas separation

    US20130164200A1