CN109529555B - Eutectic solvent based on aprotic organic matter and method for efficiently absorbing sulfur dioxide by using eutectic solvent - Google Patents
Eutectic solvent based on aprotic organic matter and method for efficiently absorbing sulfur dioxide by using eutectic solvent Download PDFInfo
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- CN109529555B CN109529555B CN201811547461.5A CN201811547461A CN109529555B CN 109529555 B CN109529555 B CN 109529555B CN 201811547461 A CN201811547461 A CN 201811547461A CN 109529555 B CN109529555 B CN 109529555B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
- B01D53/18—Absorbing units; Liquid distributors therefor
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
- B01D53/1456—Removing acid components
- B01D53/1481—Removing sulfur dioxide or sulfur trioxide
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
- B01D53/1493—Selection of liquid materials for use as absorbents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
- B01D2252/20—Organic absorbents
- B01D2252/205—Other organic compounds not covered by B01D2252/00 - B01D2252/20494
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Abstract
The invention provides a eutectic solvent system based on an aprotic organic matter, which consists of imidazole salt and aprotic organic matter Succinonitrile (SN). The molar ratio of the imidazole salt to the succinonitrile is 1: 1-8. The invention also provides a method for absorbing/trapping SO2The method comprises the following steps: mixing the eutectic solvent system with SO2The gas is contacted and absorbed, and then the product is obtained. Eutectic solvent system adopted by the invention for SO2Has higher absorption capacity and good recycling effect, and can realize SO2Efficient reversible absorption.
Description
Technical Field
The invention belongs to the field of gas separation, and particularly relates to an aprotic organic eutectic solvent and a method for efficiently absorbing sulfur dioxide by using the same.
Background
Sulfur dioxide (SO)2) As a main atmospheric pollutant, the acid rain and the acid mist can be caused, and the ecological environment and the body health of people are seriously harmed. SO (SO)2Mainly comes from the combustion of fossil fuels such as coal, petroleum, natural gas and the like in the industrial production process. Currently, industrial control of SO in flue gas2The emission method mainly comprises the flue gas desulfurization technologies such as a dry method, a semi-dry method and a wet method. Among them, the limestone-gypsum method flue gas desulfurization technique in the wet process is most industrially applied. The method has high desulfurization efficiency. However, the limestone-gypsum method also has many disadvantages, such as the generation of a large amount of solid by-product gypsum in the desulfurization process, the inability to reuse the absorbent, the waste of water, and the like. In addition, when desulfurization is performed by the limestone-gypsum method, CO is generated during desulfurization2The emission of greenhouse gases is increased, and if the greenhouse gases are not treated properly, secondary pollution to the environment is caused. Therefore, development and research of novel, efficient, environmentally friendly, controlled SO2A method of discharging is also highly necessary.
In recent years, ionic liquids have attracted much attention due to their unique properties, such as extremely low vapor pressure, wide liquid path, good thermal stability, easy property adjustment, and the like. Ionic liquids have also been used for SO due to these unique properties2The field of absorption and separation. At present, researchers have designed and synthesized a wide variety of applicationsAbsorption of SO2The ionic liquid of (1). Wherein, the pair of SO by functionalized ionic liquid such as azole group, amino group and the like2Has better absorption effect. However, the synthesis steps of functional ionic liquids such as imidazoles and amino-based liquids are complicated, which results in high production cost and limits the use of the functional ionic liquids in industrial processes.
Recently, eutectic solvents have also been used to absorb SO as a new class of solvents2And (6) carrying out the process. Eutectic solvents also have properties similar to ionic liquids, such as lower vapor pressure, easily adjustable properties, and the like. However, the preparation process of the eutectic solvent is very simple compared to the ionic liquid. Mixing two or more proper substances, heating and cooling to obtain the required eutectic solvent. Currently, most eutectic solvent formation is achieved through hydrogen bonding between the components. Commonly used substances for synthesizing the eutectic solvent comprise hydrogen bond donors such as alcohols, carboxylic acids and amides, and hydrogen bond acceptors such as quaternary ammonium salt, quaternary phosphonium salt and imidazolium salt. The eutectic solvent is widely applied to the fields of organic synthesis, material preparation, catalytic reaction, extraction separation and the like. In SO2The eutectic solvent has also been widely studied in the absorption and separation field of the present invention. Eutectic solvents such as chlocholine (Green chem.,2013,15, 2261; ind. eng. chem. res.,2015,54,8019), imidazole salts (acssutainable. eng.,2017,5, 4382; Energy Fuels,2018,32,10737), betaine (j. hazard. mater.,2017,324,457) show better SO2And (4) absorption effect. In these eutectic solvents, the hydrogen bond donor is a protic organic species. Due to SO2The content of the eutectic solvent in the flue gas is very low, and how to improve the eutectic solvent to low-concentration SO2Is also a problem that one needs to solve.
Disclosure of Invention
One of the purposes of the invention is to provide a eutectic solvent system based on aprotic organic matters.
The eutectic solvent system based on the aprotic organic matter consists of imidazole salt and aprotic organic matter Succinonitrile (SN).
In the eutectic solvent system, the molar ratio of the imidazole salt to the succinonitrile can be 1: 1-8, specifically 1:1, 1:2, 1:4, 1: 1-4 or 1: 1-6.
In the eutectic solvent system, the imidazole salt can be 1-methyl-3-ethylimidazole chloride ([ Emim [ ])][Cl]) And/or 1-methyl-3-ethylimidazole hexafluorophosphate ([ Emim [ ]][PF6]) The structural formula is shown as the following formula:
the invention also provides a method for preparing the eutectic solvent system.
The method comprises the following steps: and mixing the imidazole salt and the succinonitrile, heating until the system is completely changed into liquid, and cooling to room temperature to obtain the product.
In the method, the heating temperature can be 70-90 ℃, and specifically can be 80 ℃.
The eutectic solvent system can absorb/capture SO with high efficiency2Also belongs to the protection scope of the invention.
It is another object of the present invention to provide an absorption/capture of SO2The method of (1).
The invention provides SO absorption/capture2The method comprises the following steps: mixing the eutectic solvent system with SO2The gas is contacted and absorbed, and then the product is obtained.
The method for absorbing the sulfur dioxide comprises the following steps: and (3) slowly introducing the gas containing sulfur dioxide into a container containing the eutectic solvent system, controlling the pressure and the temperature, and weighing in the absorption process until the mass of the container is not changed any more.
In the method, the pressure of the absorption gas in the contact absorption process can be 0.0001-0.10 MPa, specifically 0.10MPa, and the absorption temperature can be 20-60 ℃, specifically 20 ℃.
The method may further comprise: heating the eutectic solvent system absorbing the sulfur dioxide, desorbing the sulfur dioxide gas and recovering the eutectic solvent system.
Wherein the desorption temperature can be 70-90 ℃.
The invention has the following advantages:
eutectic solvent system adopted by the invention for SO2Has higher absorption capacity and good recycling effect, and can realize SO2Efficient reversible absorption.
Detailed Description
The present invention will be described below with reference to specific examples, but the present invention is not limited thereto.
The experimental methods used in the following examples are all conventional methods unless otherwise specified; reagents, materials and the like used in the following examples are commercially available unless otherwise specified.
Example 1 high efficiency capture of SO2Preparation of the eutectic solvent system
The high-efficiency trapped SO is prepared by the following method respectively2The eutectic solvent system is as follows:
1) heating and stirring 1-methyl-3-ethylimidazole chloride and Succinonitrile (SN) at a molar ratio of 1:1 at 80 ℃ until the mixed system is completely changed into liquid, and then cooling to room temperature to obtain a eutectic solvent, namely [ Emim ] [ Cl ] -SN (1: 1).
2) Heating and stirring 1-methyl-3-ethylimidazole chloride and Succinonitrile (SN) at a molar ratio of 1:2 at 80 ℃ until the mixed system is completely changed into liquid, and then cooling to room temperature to obtain a eutectic solvent, namely [ Emim ] [ Cl ] -SN (1: 2).
3) Heating and stirring 1-methyl-3-ethylimidazole chloride and Succinonitrile (SN) according to the molar ratio of 1:4 at 80 ℃ until the mixed system is completely changed into liquid, and then cooling to room temperature to obtain a eutectic solvent, namely [ Emim ] [ Cl ] -SN (1: 4).
4) Heating and stirring 1-methyl-3-ethylimidazole hexafluorophosphate and Succinonitrile (SN) according to the molar ratio of 1:1 at 80 ℃ until the mixed system is completely changed into liquid, and then cooling to room temperature to obtain the eutectic solventIs denoted as [ Emim][PF6]-SN(1:1)。
Examples 2,
About 1.0g of the eutectic solvent [ Emim ] prepared in example 1 of the present invention was added to each glass test tube having an inner diameter of 10mm][Cl]-SN (1:1) followed by slow SO injection2The flow of gas is 50mL/min, the pressure of absorbed gas is 0.1MPa, the temperature is controlled to be 20 ℃, the glass test tube is weighed by an electronic analytical balance in the absorption process, and the mass of the glass test tube is weighed at intervals until the mass is not changed any more. Calculating to obtain the SO absorbed by each gram of solvent21.13 g.
Examples 3,
About 1.0g of the eutectic solvent [ Emim ] prepared in example 1 of the present invention was added to each glass test tube having an inner diameter of 10mm][Cl]-SN (1:2) followed by slow SO injection2The flow of gas is 50mL/min, the pressure of absorbed gas is 0.1MPa, the temperature is controlled to be 20 ℃, the glass test tube is weighed by an electronic analytical balance in the absorption process, and the mass of the glass test tube is weighed at intervals until the mass is not changed any more. Calculating to obtain the SO absorbed by each gram of solvent20.96 g.
Examples 4,
About 1.0g of the eutectic solvent [ Emim ] prepared in example 1 of the present invention was added to each glass test tube having an inner diameter of 10mm][Cl]-SN (1:4) followed by slow SO injection2The flow of gas is 50mL/min, the pressure of absorbed gas is 0.1MPa, the temperature is controlled to be 20 ℃, the glass test tube is weighed by an electronic analytical balance in the absorption process, and the mass of the glass test tube is weighed at intervals until the mass is not changed any more. Calculating to obtain the SO absorbed by each gram of solvent20.79 g.
Examples 5,
About 1.0g of the eutectic solvent [ Emim ] prepared in example 1 of the present invention was added to each glass test tube having an inner diameter of 10mm][PF6]-SN (1:1) followed by slow SO injection2The flow of gas is 50mL/min, the pressure of absorbed gas is 0.1MPa, the temperature is controlled to be 20 ℃, the glass test tube is weighed by an electronic analytical balance in the absorption process, and the mass of the glass test tube is weighed at intervals until the mass is not changed any more. Calculating to obtain the SO absorbed by each gram of solvent20.36 g.
Examples 6,
About 1.0g of the eutectic solvent [ Emim ] synthesized in example 1) of the present invention was added to a glass test tube having an inner diameter of 10mm][Cl]SN (1:1), then pure SO2The gas flow is 50mL/min, the temperature is 20 ℃, the pressure is 0.1MPa, the weight of the glass test tube is weighed at certain time intervals until the mass does not change any more, and the absorption balance is achieved within about 20 min. After the absorption is finished, N is introduced2The flow rate is 50mL/min, the desorption temperature is 80 ℃, the desorption time is about 80min, and the most part (about 98%) of SO absorbed by the eutectic solvent2Completely desorbed. Absorbing and desorbing for 5 times in a circulating way according to the steps, and enabling the eutectic solvent to react with SO2The absorption amount of (a) is kept substantially constant. The specific results are shown in the following table (table 1).
TABLE 1 eutectic solvents [ Emim][Cl]Five cycles of SO absorption by SN (1:1)2Experimental results of (2)
Example 7,
About 1.0g of the eutectic solvent [ Emim ] synthesized in example 1) of the present invention in the amount of 2) was charged in a glass test tube having an inner diameter of 10mm][Cl]SN (1:2), then pure SO2The gas flow is 50mL/min, the temperature is 20 ℃, the pressure is 0.1MPa, the weight of the glass test tube is weighed at certain time intervals until the mass does not change any more, and the absorption balance is achieved within about 20 min. After the absorption is finished, N is introduced2The flow rate is 50mL/min, the desorption temperature is 80 ℃, the desorption time is about 70min, and SO absorbed by the eutectic solvent2Completely desorbed. Absorbing and desorbing for 5 times in a circulating way according to the steps, and enabling the eutectic solvent to react with SO2The absorption amount of (a) is kept substantially constant. The specific results are shown in the following table (Table 2).
TABLE 2 eutectic solvents [ Emim][Cl]Five cycles of SO absorption by SN (1:2)2Experimental results of (2)
Example 8,
About 1.0g of the eutectic solvent [ Emim ] synthesized in 3) of example 1 of the present invention was added to a glass test tube having an inner diameter of 10mm][Cl]SN (1:4), then pure SO2The gas flow is 50mL/min, the temperature is 20 ℃, the pressure is 0.1MPa, the weight of the glass test tube is weighed at certain time intervals until the mass does not change any more, and the absorption balance is achieved within about 20 min. After the absorption is finished, N is introduced2The flow rate is 50mL/min, the desorption temperature is 70 ℃, the desorption time is about 60min, and SO absorbed by the eutectic solvent2Completely desorbed. Absorbing and desorbing for 5 times in a circulating way according to the steps, and enabling the eutectic solvent to react with SO2The absorption amount of (a) is kept stable. The specific results are shown in the following table (Table 3).
TABLE 3 eutectic solvents [ Emim][Cl]Five cycles of SO absorption by SN (1:4)2Experimental results of (2)
Examples 9,
About 1.0g of the eutectic solvent [ Emim ] prepared in example 1) of the present invention was added to a glass test tube having an inner diameter of 10mm][Cl]-SN (1:1) and then SO2SO content of 2000ppm2And N2The gas flow of the mixed gas is 50mL/min, the temperature is 20 ℃, and the weight of the glass test tube is weighed at certain intervals until the weight is not changed. Calculating to obtain the SO absorbed by each gram of absorbent20.12 g.
Claims (10)
1. A eutectic solvent system is composed of imidazole salt and non-proton organic matter succinonitrile.
2. The eutectic solvent system of claim 1, characterized in that: in the eutectic solvent system, the molar ratio of the imidazole salt to the succinonitrile is 1: 1-8.
3. The eutectic solvent system according to claim 1 or 2, characterized in that: in the eutectic solvent system, the imidazole salt is 1-methyl-3-ethylimidazole chloride salt and/or 1-methyl-3-ethylimidazole hexafluorophosphate.
4. A method of preparing the eutectic solvent system of any one of claims 1 to 3, comprising the steps of: and mixing the imidazole salt and the succinonitrile, heating until the system is completely changed into liquid, and cooling to room temperature to obtain the product.
5. The method of claim 4, wherein: in the method, the heating temperature is 70-90 ℃.
6. High efficiency SO absorption/capture by eutectic solvent system as claimed in any one of claims 1 to 32The use of (1).
7. Absorbing/trapping SO2The method comprises the following steps: reacting the eutectic solvent system of any one of claims 1 to 3 with SO2The gas is contacted and absorbed, and then the product is obtained.
8. The method of claim 7, wherein: in the method, the pressure of the absorption gas in the contact absorption process is 0.0001-0.10 MPa, and the absorption temperature is 20-60 ℃.
9. The method according to claim 7 or 8, characterized in that: the method still further comprises: heating the eutectic solvent system absorbing sulfur dioxide, desorbing sulfur dioxide gas and recovering the eutectic solvent system.
10. The method of claim 9, wherein: the desorption temperature is 70-90 ℃.
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| CN110448996A (en) * | 2019-08-21 | 2019-11-15 | 浙江工业大学 | A method of being based on Emim [Cl] eutectic solvent capture sulfur dioxide |
| CN113171671A (en) * | 2020-04-10 | 2021-07-27 | 盐城师范学院 | Eutectic solvent with amphiprotic molecular function design and application thereof |
| CN113082960B (en) * | 2021-04-09 | 2022-05-20 | 辽宁科技大学 | Eutectic solvent for wide temperature window flue gas desulfurization and production and regeneration method thereof |
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| CN103143234A (en) * | 2013-02-19 | 2013-06-12 | 浙江大学 | Method for trapping sulfur dioxide through nitrile group-containing anionic functionalized ionic liquid |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103143234A (en) * | 2013-02-19 | 2013-06-12 | 浙江大学 | Method for trapping sulfur dioxide through nitrile group-containing anionic functionalized ionic liquid |
Non-Patent Citations (2)
| Title |
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| Efficient Absorption of SO2 by EmimCl-EG Deep Eutectic Solvents;Dezhong Yang等;《ACS Sustainable Chem. Eng》;20171231;第6382-6386页 * |
| 低共熔溶剂在化工分离过程中的应用及研究进展;吴桐等;《山东化工》;20141231;第66-69页 * |
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