CN102794082B - Mixed solvent for trapping carbon dioxide - Google Patents
Mixed solvent for trapping carbon dioxide Download PDFInfo
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- CN102794082B CN102794082B CN201210262268.3A CN201210262268A CN102794082B CN 102794082 B CN102794082 B CN 102794082B CN 201210262268 A CN201210262268 A CN 201210262268A CN 102794082 B CN102794082 B CN 102794082B
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Abstract
The invention relates to a mixed solvent for trapping carbon dioxide, and belongs to the technical field of separating gas by an adsorption effect. The mixed solvent for trapping the carbon dioxide is prepared by compounding and mixing organic alkali and alcohol amine ionic liquid, wherein the molar ratio of the organic alkali to the alcohol amine ionic liquid is (1: 1)-(3: 1). By compounding the organic alkali with high boiling point and the alcohol amine ionic liquid, the mixed solvent improves the absorptive capacity for the carbon dioxide gas, and reduces the consumption of the solvent in a using process; and the mixed solvent has the advantages of being simple to prepare, high in absorptive capacity and capable of being recycled.
Description
Technical field
The present invention relates to a kind of mixed solvent of capturing carbon dioxide, belong to by separating gases by adsorption technical field.
Background technology
In recent years, along with widely using of the fossil fuel such as coal, oil and natural gas, the discharge capacity of carbon dioxide is increased year by year, exacerbates greenhouse effects, compromise ecological environment, therefore control the discharge of carbon dioxide and capturing carbon dioxide and cause and pay close attention to widely.Meanwhile, carbon dioxide is also a kind of important carbon resource, can be converted into important industrial chemicals and intermediate.Therefore, the trapping of research carbon dioxide, fixing and transform tool and be of great significance, and become the common hot issue paid close attention in the whole world.
Solvent (liquid) absorption process is a kind of isolation technics widely using capturing carbon dioxide at present the most.Lyosoption is different, and the capacity of capturing carbon dioxide also can change thereupon.At present, industrial the most frequently used carbon dioxide absorption solvent is aqueous alkanolamine, have with low cost, absorb the advantages such as fast.But this type of lyosoption is volatile, corrosivity strong, absorption rate is slow, meanwhile, needs to add certain activator to improve the performance (201110093748.7) of aqueous alkanolamine capturing carbon dioxide.
Ionic liquid has good stability, steam forces down and the advantage such as designability, is widely used in trapping or dissolved carbon dioxide in recent years.Now there are some researches show, the ability of normal alkyl imidazole ion liquid capturing carbon dioxide is at ambient pressure more weak, with Physical Absorption take as the leading factor (
nature,399,28,1999).Although the imidazole type ion liquid of the amino functional developed thereafter increases in the ability of capturing carbon dioxide, under normal pressure every mole of ionic liquid Absorbable rod be about 0.5mol carbon dioxide (
j. Am. Chem. Soc.,124,926,2004), but its viscosity can increase along with the increase of carbon dioxide absorption amount, and finally affects absorption and the desorption of carbon dioxide.Recently, Wang etc. prepare a series of with alkyl quaternary phosphine be cation, the substituted phenol novel ion liquid that is anion, and achieve mole capturing carbon dioxide gas such as normal temperature and pressure (
chem. Eur. J.,18,2153,2012).Due to the raw material of this type of ionic liquid and preparation cost costly, and preparation process relative complex, therefore is also not suitable for carrying out large-scale promotion in industrial processes at present.Therefore, develop a kind of good stability, adsorption capacity is large, carbon dioxide absorption solvent that price is low, have great importance.
Summary of the invention
The first object of the present invention is to provide a kind of green mixed solvent of simple, capturing carbon dioxide that good stability, adsorption capacity are high.
Realize the technical scheme that the present invention first object takes as follows:
A mixed solvent for capturing carbon dioxide, is mixed through composite by organic base and alcohol amine ion liquid, and the mol ratio of organic base and alcohol amine ion liquid is 1:1-3:1.
Described organic base is 1,8-diazacyclo [5,4,0] 11 carbon-7-alkene (DBU), 1,5-diazabicyclo [4,3,0]-5-alkene in the ninth of the ten Heavenly Stems (DBN) or 7-methyl isophthalic acid, 5,7-tri-azabicyclic [4,4,0]-5-alkene in the last of the ten Heavenly stems (MTBD).
Described alcohol amine ion liquid is the one of monoethanolamine formic acid (HMEAF), diethanol amine formic acid (HDEAF), monoethanolamine acetic acid (HMEAA), diethanol amine acetic acid (HDEAA), triethanolamine acetic acid (HTEAA), monoethanolamine lactic acid (HMEAL), diethanol amine lactic acid (HDEAL) and triethanolamine lactic acid (HTEAL) etc.
Described organic base and alcohol amine ion liquid composite after, stir 3 ~ 6 hours at normal temperatures, mix, obtain the mixed solvent of capturing carbon dioxide of the present invention.
The mixed solvent that the second object of the present invention is to provide above-mentioned capturing carbon dioxide is applied to the method for capturing carbon dioxide.
Described mixed solvent can be applicable to pure carbon dioxide, also can be applicable to the trapping of the carbon dioxide in the mists such as air, flue gas, waste gas, by adsorption and desorption process, at the temperature, pressure of certain adsorption and desorption, carbon dioxide is trapped.
Described adsorptive pressure is 0.01 ~ 0.1MPa, and adsorption temp is 20 ~ 50 DEG C.
Described desorption temperature is 80 ~ 100 DEG C, and desorption pressure is normal pressure.
Wherein, normal temperature refers to 20-25 DEG C, and normal pressure is standard atmospheric pressure.In the present invention, alcohol amine ion liquid is obtained by mole neutralization reactions such as hydramine (monoethanolamine, diethanol amine or triethanolamine) and corresponding sour (formic acid, acetic acid or lactic acid) carry out, and concrete preparation method is as follows:
The monoethanolamine of 0.2mol is dissolved in 20mL ethanol, at normal temperatures, slowly drip the ethanolic solution (volume of ethanol is about 20mL) containing 0.2mol glacial acetic acid while stirring, dropwise, continue reaction 2 ~ 4 hours, revolve and steam removing ethanol, activated carbon decolorizing, vacuum drying obtains monoethanolamine acetic acid ion liquid (HMEAA), and the preparation method of other alcohol amine ion liquids related in the present invention is by this method.
Compare with alcohol amine ion liquid with traditional aqueous alkanolamine, normal alkyl imidazole ion liquid, the mixed solvent of capturing carbon dioxide of the present invention has following beneficial effect:
(1) using high boiling organic base and the composite mixed solvent obtained of alcohol amine ion liquid as absorbent, avoid volatilization and the loss of solvent in desorption process;
(2) organic base and alcohol amine ion liquid is composite, reduces the viscosity of alcohol amine ion liquid on the one hand, is conducive to the carrying out of desorption process; On the other hand, mixed solution is compared with single component, add the absorptive capacity of the carbon dioxide of alcohol amine ion liquid, when 1,8-diazacyclo [5,4,0] 11 carbon-7-alkene (DBU): during triethanolamine acetic acid (HTEAA)=3:1, the capacity of its absorbing carbon dioxide can reach 1.5 moles/mole mixed solutions.
Detailed description of the invention
The present invention, by following examples, is specifically described and illustrates.
The preparation of alcohol amine ion liquid: alcohol amine ion liquid is by hydramine (monoethanolamine, diethanol amine or triethanolamine) and corresponding acid (formic acid, acetic acid or lactic acid) to carry out etc. that mole neutralization reaction obtains, concrete preparation method is: be dissolved in by the monoethanolamine of 0.2mol in 20mL ethanol, at normal temperatures, slowly drip the ethanolic solution (volume of ethanol is about 20mL) containing 0.2mol glacial acetic acid while stirring, dropwise, continue reaction 2 ~ 4 hours, revolve and steam removing ethanol, activated carbon decolorizing, vacuum drying obtains monoethanolamine acetic acid ion liquid (HMEAA), the preparation method of other alcohol amine ion liquids related in the present invention is by this method.
The preparation of the mixed solvent of capturing carbon dioxide: mix composite by equimolar ratio with alcohol amine ion liquid by organic base, under air-proof condition, under normal temperature, stirs 3-6 hour, prepares the mixed solvent of capturing carbon dioxide.Wherein, the mol ratio of organic base and alcohol amine ion liquid is specially: organic base (DBU, DBN or MTBD) is 1:1 with the mol ratio of ethanolamine ion liquid (HMEAF, HMEAA or HMEAL), mixing time 3 hours under normal temperature; Organic base (DBU, DBN or MTBD) is 2:1 with the mol ratio of diethanol amine ionic liquid (HDEAF, HDEAA or HDEAL), under normal temperature, and mixing time 5 hours; Organic base (DBU, DBN or MTBD) is 3:1 with the mol ratio of triethanolamine-ion liquid (HTEAA or HTEAL), under normal temperature, and mixing time 6 hours.
Embodiment 1-12
Be about 1cm at diameter, volume is in the vial of about 5mL, respectively by such as aforesaid way organic base and alcohol amine ion liquid mix according to different ratios, magnetic agitation, controlling adsorption temp is 30 DEG C, then slowly pass into carbon dioxide, control carbon dioxide flow is 50mL/min, and adsorptive pressure is 0.1MPa, be adsorbed to saturated after weigh, the result of capturing carbon dioxide is as shown in table 1.
The effect of the mixed solvent capturing carbon dioxide of table 1 different component ratio
In the present invention, mol/mol IL represents the amount of substance of the carbon dioxide that every mole of ionic liquid or organic base absorb.
Comparative example 13-23
Be about 1cm at diameter, volume is in the vial of about 5mL, controlling adsorption temp is 30 DEG C, carbon dioxide adsorption pressure is 0.1MPa, carbon dioxide flow is 50mL/min, test the performance of pure alcohol amine ion liquid or organic base capturing carbon dioxide respectively, the result of capturing carbon dioxide is as shown in table 2.
The result of table 2 alcohol amine ion liquid and organic base capturing carbon dioxide
Embodiment 24
By carbon dioxide absorption in embodiment 1-12 to saturated mixed solvent magnetic agitation, and slowly pass into High Purity Nitrogen, wherein High Purity Nitrogen flow is 50mL/mim, the pressure of High Purity Nitrogen is 0.1MPa, controlling desorption temperature is 80 DEG C, desorption time is 0.5 hours, and weighing results shows, the carbon dioxide absorbed in mixed solvent desorption completely.
Result shows, under identical adsorption conditions, adopts mixed solution of the present invention, absorbing carbon dioxide capacity is far away higher than single alcohol ammonium ion liquid or organic base, and desorption only needs 0.5 hours, and desorption rate is also very fast, decrease the loss of solvent, can be recycled.
Claims (4)
1. a mixed solvent for capturing carbon dioxide, is characterized in that: formed through composite by organic base and alcohol amine ion liquid, and described organic base is 1,8-diazacyclo [5,4,0] 11 carbon-7-alkene, 1,5-diazabicyclo [4,3,0]-5-alkene in the ninth of the ten Heavenly Stems, 7-methyl isophthalic acid, any one in 5,7-tri-azabicyclic [4,4,0]-5-alkene in the last of the ten Heavenly stems, described alcohol amine ion liquid is monoethanolamine formic acid, diethanol amine formic acid, monoethanolamine acetic acid, diethanol amine acetic acid, triethanolamine acetic acid, monoethanolamine lactic acid, diethanol amine lactic acid, any one in triethanolamine lactic acid, organic base and monoethanolamine formic acid, the mol ratio of monoethanolamine acetic acid or monoethanolamine lactic acid is 1:1, organic base and diethanol amine formic acid, the mol ratio of diethanol amine acetic acid or diethanol amine lactic acid is 2:1, the mol ratio of organic base and triethanolamine acetic acid or triethanolamine lactic acid is 3:1, above-mentioned organic base and alcohol amine ion liquid composite after, stir 3 ~ 6 hours at normal temperatures, mix, obtain the mixed solvent of capturing carbon dioxide,
Described mixed solvent is applied to the trapping of the carbon dioxide in pure carbon dioxide, air, flue gas, waste gas: organic base and alcohol amine ion liquid are mixed according to different ratios respectively, magnetic agitation, controlling adsorption temp is 30 DEG C, then carbon dioxide is passed into, control carbon dioxide flow is 50mL/min, adsorptive pressure is 0.1MPa, and be adsorbed to saturated, carbon dioxide adsorption is complete; Again by the mixed solvent magnetic agitation after absorption, and pass into High Purity Nitrogen, High Purity Nitrogen flow is 50mL/mim, and the pressure of High Purity Nitrogen is 0.1MPa, and controlling desorption temperature is 80 DEG C, and desorption time is 0.5 hour, and carbon dioxide desorption is complete.
2. the mixed solvent of a kind of capturing carbon dioxide as claimed in claim 1, it is characterized in that: respectively by 1,8-diazacyclo [5,4,0] 11 carbon-7-alkene and monoethanolamine acetic acid ion liquid mix according to the mol ratio of 1:1, magnetic agitation, controlling adsorption temp is 30 DEG C, and then pass into carbon dioxide, control carbon dioxide flow is 50mL/min, adsorptive pressure is 0.1MPa, be adsorbed to saturated after weigh; Again by mixed solvent magnetic agitation, and pass into High Purity Nitrogen, High Purity Nitrogen flow is 50mL/mim, and the pressure of High Purity Nitrogen is 0.1MPa, and controlling desorption temperature is 80 DEG C, and desorption time is 0.5 hour, and carbon dioxide desorption is complete.
3. the mixed solvent of a kind of capturing carbon dioxide as claimed in claim 1, it is characterized in that: respectively by 1,8-diazacyclo [5,4,0] 11 carbon-7-alkene and diethanol amine acetic acid ion liquid mix according to the mol ratio of 2:1, magnetic agitation, controlling adsorption temp is 30 DEG C, and then pass into carbon dioxide, control carbon dioxide flow is 50mL/min, adsorptive pressure is 0.1MPa, be adsorbed to saturated after weigh; Again by mixed solvent magnetic agitation, and pass into High Purity Nitrogen, High Purity Nitrogen flow is 50mL/mim, and the pressure of High Purity Nitrogen is 0.1MPa, and controlling desorption temperature is 80 DEG C, and desorption time is 0.5 hour, and carbon dioxide desorption is complete.
4. the mixed solvent of a kind of capturing carbon dioxide as claimed in claim 1, it is characterized in that: respectively by 1,8-diazacyclo [5,4,0] 11 carbon-7-alkene and triethanolamine acetic acid ion liquid mix according to the mol ratio of 3:1, magnetic agitation, controlling adsorption temp is 30 DEG C, and then pass into carbon dioxide, control carbon dioxide flow is 50mL/min, adsorptive pressure is 0.1MPa, be adsorbed to saturated after weigh; Again by mixed solvent magnetic agitation, and pass into High Purity Nitrogen, High Purity Nitrogen flow is 50mL/mim, and the pressure of High Purity Nitrogen is 0.1MPa, and controlling desorption temperature is 80 DEG C, and desorption time is 0.5 hour, and carbon dioxide desorption is complete.
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| CN103418226B (en) * | 2013-08-20 | 2015-09-16 | 昆明理工大学 | A kind of preparation method of absorbent |
| CN104829427B (en) * | 2014-12-25 | 2016-11-02 | 青岛科技大学 | The recovery process of ethanol and device thereof in a kind of sodium alginate pneumatic conveying drying tail gas |
| CN108993125B (en) * | 2018-10-12 | 2021-04-13 | 安徽工业大学 | Eutectic solvent for removing carbon dioxide in air and flue gas |
| CN115364623A (en) * | 2022-06-08 | 2022-11-22 | 郑州大学 | Efficient CO capture 2 The renewable ionic liquid compound solvent |
| CN115228247B (en) * | 2022-08-15 | 2023-08-22 | 北京石大油源科技开发有限公司 | Technological method and process suitable for capturing high-concentration carbon dioxide |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101804292A (en) * | 2010-03-25 | 2010-08-18 | 南京大学 | Special MDEA formula solution activated by functional ion liquid for CO2 gas absorption separation |
| WO2012033973A1 (en) * | 2010-09-09 | 2012-03-15 | Exxonmobil Research And Engineering Company | Ionic liquids for removal of carbon dioxide |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101804292A (en) * | 2010-03-25 | 2010-08-18 | 南京大学 | Special MDEA formula solution activated by functional ion liquid for CO2 gas absorption separation |
| WO2012033973A1 (en) * | 2010-09-09 | 2012-03-15 | Exxonmobil Research And Engineering Company | Ionic liquids for removal of carbon dioxide |
Non-Patent Citations (1)
| Title |
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| "Solubilities of CO2 in hydroxyl ammonium ionic liquids at elevated pressures";Xiaoliang Yuan et al;《Fluid Phase Equilibria》;20070203;第257卷;摘要,第2-4节 * |
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