CN109529555A - Eutectic solvent based on aprotic organic and the method using its efficient absorption sulfur dioxide - Google Patents
Eutectic solvent based on aprotic organic and the method using its efficient absorption sulfur dioxide Download PDFInfo
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- CN109529555A CN109529555A CN201811547461.5A CN201811547461A CN109529555A CN 109529555 A CN109529555 A CN 109529555A CN 201811547461 A CN201811547461 A CN 201811547461A CN 109529555 A CN109529555 A CN 109529555A
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- eutectic solvent
- solvent system
- absorption
- eutectic
- succinonitrile
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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
-
- 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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- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Treating Waste Gases (AREA)
- Gas Separation By Absorption (AREA)
Abstract
The present invention provides a kind of eutectic solvent system based on aprotic organic, is made of imidazole salts and aprotic organic succinonitrile (SN).The imidazole salts and the molar ratio of the succinonitrile are 1:1~8.The present invention also provides a kind of absorption/trapping SO2Method, include the following steps: by the eutectic solvent system with containing SO2Gas contact absorb.Eutectic solvent system of the present invention is to SO2Absorptive capacity with higher, recycling effect is good, is able to achieve to SO2Efficient reversible absorption.
Description
Technical field
The invention belongs to gas separation fields, and in particular to a kind of eutectic solvent and utilization based on aprotic organic
The method of its efficient absorption sulfur dioxide.
Background technique
Sulfur dioxide (SO2), it as a kind of main atmosphere pollution, will lead to acid rain, acid mist, seriously endanger ecology
The health of environment and people.SO2It is mainly derived from the combustion of the fossil fuels such as coal in industrial processes, petroleum, natural gas
It burns.Currently, industrially controlling SO in flue gas2The method of discharge mainly has the flue gas desulfurization techniques such as dry method, semidry method, wet process.
Wherein, what industrial application was most is the limestone-gypsum method flue gas desulfurization technology in wet process.This method is with higher de-
Sulphur efficiency.But limestone-gypsum method is there is also many deficiencies, such as sweetening process a large amount of solid by-product gypsum production
Raw, absorbent cannot reuse, the waste of water etc..In addition, when carrying out desulfurization using limestone-gypsum method, sweetening process meeting
Generate CO2, the discharge of greenhouse gases is increased, if dealing with improperly, and will cause the secondary pollution to environment.Therefore, exploitation and
Study new and effective, environmentally friendly control SO2The method of discharge, is also very important.
In recent years, ionic liquid is due to its unique property, such as extremely low vapour pressure, wider liquid journey, good heat
Stability, property are easy adjusting etc., receive the extensive concern of people.Ionic liquid just because of these unique properties,
It has been used for SO2Absorption and separation field.Currently, researcher's design and synthesis have gone out many kinds for absorbing SO2Ionic liquid
Body.Wherein, the functionalized ion liquids such as oxazolyl class, amino are to SO2With preferable assimilation effect.But imidazoles, amino
The synthesis step of the functionalized ion liquids such as class is comparatively laborious, results in their higher production costs, limits them in work
Use during industry.
Recently, eutectic solvent also be used to absorb SO as a kind of novel solvent2Process.Eutectic solvent also has
The property of similar ionic liquid, such as lower vapour pressure, property are easy adjusting etc..But compared with ionic liquid, eutectic
The preparation process of solvent is very simple.By the way that suitably two or more material mixing, heating, cooling can be arrived
Required eutectic solvent.Currently, the formation of most of eutectic solvents is realized by the hydrogen bond action between ingredient.Often
It include the hydrogen bond donors such as alcohols, carboxylic acids, amides and quaternary ammonium salt, season phosphine for synthesizing the substance of eutectic solvent
The hydrogen bond receptors such as salt, imidazole salts.Eutectic solvent obtains in fields such as organic synthesis, material preparation, catalysis reaction, extraction and separation
It is widely applied.In SO2Absorption and separation field, eutectic solvent also obtained the extensive research of people.Choline chloride
Class (Green Chem., 2013,15,2261；Ind.Eng.Chem.Res., 2015,54,8019), imidazole salt (ACS
Sustainable.Eng.,2017,5,4382；Energy Fuels, 2018,32,10737), betaines
Eutectic solvents such as (J.Hazard.Mater., 2017,324,457) show preferable SO2Assimilation effect.It is low at these
In congruent melting solvent, hydrogen bond donor is all proton type organic.Due to SO2Content in flue gas is very low, how to improve
Eutectic solvent is to low concentration SO2Absorptive capacity and people need a problem solving.
Summary of the invention
An object of the present invention is to provide a kind of eutectic solvent system based on aprotic organic.
Eutectic solvent system provided by the present invention based on aprotic organic, by imidazole salts and aprotic organic
Succinonitrile (SN) composition.
In the eutectic solvent system, the molar ratio of the imidazole salts and the succinonitrile can be 1:1~8, specifically may be used
For 1:1,1:2,1:4,1:1~4 or 1:1~6.
In the eutectic solvent system, the imidazole salts can be 1- methyl -3- ethyl imidazol(e) villaumite ([Emim] [Cl])
And/or 1- methyl -3- ethyl imidazol(e) hexafluorophosphate ([Emim] [PF6]), structural formula is shown below:
The present invention also provides a kind of methods for preparing above-mentioned eutectic solvent system.
Described method includes following steps: the imidazole salts being mixed with the succinonitrile, system is heated to and all becomes
Liquid, be cooled to room temperature to get.
In the method, the temperature of the heating can be 70~90 DEG C, concretely 80 DEG C.
The eutectic solvent system is in efficient absorption/trapping SO2In application also belong to protection scope of the present invention.
It is a further object of the present invention to provide a kind of absorption/trapping SO2Method.
Absorption provided by the present invention/trapping SO2Method, include the following steps: by the eutectic solvent system with
Containing SO2Gas contact absorb.
The method of above-mentioned sulfur dioxide absorption specifically comprises the following steps: that the gas slowly containing sulfur dioxide is made to be passed through Sheng
In the container for having the eutectic solvent system, pressure and temperature is controlled, is weighed in absorption process, until the quality of container
No longer change.
In the method, the pressure for contacting absorption gas in absorption process can be 0.0001~0.10MPa, concretely
0.10MPa, absorbing temperature can be 20~60 DEG C, concretely 20 DEG C.
The method can also further comprise: the eutectic solvent system for absorbing sulfur dioxide being heated, is desorbed out two
Sulfur oxide gas recycles the step of eutectic solvent system.
Wherein, the temperature of the desorption can be 70~90 DEG C.
The invention has the following advantages that
Eutectic solvent system of the present invention is to SO2Absorptive capacity with higher, recycling effect is good, energy
It realizes to SO2Efficient reversible absorption.
Specific embodiment
The present invention will be described below by way of specific embodiments, but the present invention is not limited thereto.
Experimental method used in following embodiments is conventional method unless otherwise specified；Institute in following embodiments
Reagent, material etc., are commercially available unless otherwise specified.
Embodiment 1 efficiently traps SO2Eutectic solvent system preparation
Efficiently trapping SO is prepared respectively by following methods2Eutectic solvent system, it is specific as follows:
1) 1- methyl -3- ethyl imidazol(e) villaumite and succinonitrile (SN) are heated according to the ratio that molar ratio is 1:1 at 80 DEG C
Stirring, until all becoming liquid to mixed system, then cools to room temperature, can be obtained eutectic solvent, be denoted as [Emim]
[Cl]-SN(1:1)。
2) 1- methyl -3- ethyl imidazol(e) villaumite and succinonitrile (SN) are heated according to the ratio that molar ratio is 1:2 at 80 DEG C
Stirring, until all becoming liquid to mixed system, then cools to room temperature, can be obtained eutectic solvent, be denoted as [Emim]
[Cl]-SN(1:2)。
3) 1- methyl -3- ethyl imidazol(e) villaumite and succinonitrile (SN) are heated according to the ratio that molar ratio is 1:4 at 80 DEG C
Stirring, until all becoming liquid to mixed system, then cools to room temperature, can be obtained eutectic solvent, be denoted as [Emim]
[Cl]-SN(1:4)。
4) by 1- methyl -3- ethyl imidazol(e) hexafluorophosphate and succinonitrile (SN) according to the ratio that molar ratio is 1:1 80
DEG C heating stirring then cools to room temperature until all becoming liquid to mixed system, can be obtained eutectic solvent, is denoted as
[Emim][PF6]-SN(1:1)。
Embodiment 2,
In the teat glass that internal diameter is 10mm, it is separately added into the eutectic solvent of the preparation of the about 1.0g embodiment of the present invention 1
[Emim] [Cl]-SN (1:1), is then slowly introducing SO2Gas, flow 50mL/min, absorption gas pressure are 0.1MPa, control
Temperature processed is 20 DEG C, is weighed in absorption process by electronic analytical balance, and certain interval of time weighs the matter of teat glass
Amount is until no longer change.Every gram of solvent absorption SO is calculated21.13 gram.
Embodiment 3,
In the teat glass that internal diameter is 10mm, it is separately added into the eutectic solvent of the preparation of the about 1.0g embodiment of the present invention 1
[Emim] [Cl]-SN (1:2), is then slowly introducing SO2Gas, flow 50mL/min, absorption gas pressure are 0.1MPa, control
Temperature processed is 20 DEG C, is weighed in absorption process by electronic analytical balance, and certain interval of time weighs the matter of teat glass
Amount is until no longer change.Every gram of solvent absorption SO is calculated20.96 gram.
Embodiment 4,
In the teat glass that internal diameter is 10mm, it is separately added into the eutectic solvent of the preparation of the about 1.0g embodiment of the present invention 1
[Emim] [Cl]-SN (1:4), is then slowly introducing SO2Gas, flow 50mL/min, absorption gas pressure are 0.1MPa, control
Temperature processed is 20 DEG C, is weighed in absorption process by electronic analytical balance, and certain interval of time weighs the matter of teat glass
Amount is until no longer change.Every gram of solvent absorption SO is calculated20.79 gram.
Embodiment 5,
In the teat glass that internal diameter is 10mm, it is separately added into the eutectic solvent of the preparation of the about 1.0g embodiment of the present invention 1
[Emim][PF6]-SN (1:1), then it is slowly introducing SO2Gas, flow 50mL/min, absorption gas pressure are 0.1MPa, control
Temperature processed is 20 DEG C, is weighed in absorption process by electronic analytical balance, and certain interval of time weighs the matter of teat glass
Amount is until no longer change.Every gram of solvent absorption SO is calculated20.36 gram.
Embodiment 6,
Internal diameter be 10mm teat glass in, be added the about 1.0g embodiment of the present invention 1 in 1) synthesized by eutectic it is molten
Agent [Emim] [Cl]-SN (1:1), then passes to pure SO2Gas, gas flow 50mL/min, temperature are 20 DEG C, and pressure is
0.1MPa, separated in time weighs the weight of teat glass until quality no longer changes, and about 20min reaches absorption equilibrium.It inhales
After receipts, it is passed through N2, flow 50mL/min, desorption temperature is 80 DEG C, desorbs about 80min, and eutectic solvent absorbs exhausted
Most of (about 98%) SO2It desorbs completely.According to above-mentioned steps, cyclic absorption is desorbed 5 times, and eutectic solvent is to SO2Suction
Receipts amount kept stable.Concrete outcome such as following table (table 1).
1 eutectic solvent of table [Emim] [Cl]-SN (1:1), five cyclic absorption SO2Experimental result
Embodiment 7,
Internal diameter be 10mm teat glass in, be added the about 1.0g embodiment of the present invention 1 in 2) synthesized by eutectic it is molten
Agent [Emim] [Cl]-SN (1:2), then passes to pure SO2Gas, gas flow 50mL/min, temperature are 20 DEG C, and pressure is
0.1MPa, separated in time weighs the weight of teat glass until quality no longer changes, and about 20min reaches absorption equilibrium.It inhales
After receipts, it is passed through N2, flow 50mL/min, desorption temperature is 80 DEG C, about 70min is desorbed, what which absorbed
SO2It desorbs completely.According to above-mentioned steps, cyclic absorption is desorbed 5 times, and eutectic solvent is to SO2Uptake keep steady substantially
It is fixed.Concrete outcome such as following table (table 2).
2 eutectic solvent of table [Emim] [Cl]-SN (1:2), five cyclic absorption SO2Experimental result
Embodiment 8,
Internal diameter be 10mm teat glass in, be added the about 1.0g embodiment of the present invention 1 in 3) synthesized by eutectic it is molten
Agent [Emim] [Cl]-SN (1:4), then passes to pure SO2Gas, gas flow 50mL/min, temperature are 20 DEG C, and pressure is
0.1MPa, separated in time weighs the weight of teat glass until quality no longer changes, and about 20min reaches absorption equilibrium.It inhales
After receipts, it is passed through N2, flow 50mL/min, desorption temperature is 70 DEG C, about 60min is desorbed, what which absorbed
SO2It desorbs completely.According to above-mentioned steps, cyclic absorption is desorbed 5 times, and eutectic solvent is to SO2Uptake keep stablize.
Concrete outcome such as following table (table 3).
3 eutectic solvent of table [Emim] [Cl]-SN (1:4), five cyclic absorption SO2Experimental result
Embodiment 9,
Internal diameter be 10mm teat glass in, be added the about 1.0g embodiment of the present invention 1 in 1) prepared by eutectic it is molten
Agent [Emim] [Cl]-SN (1:1), then passes to SO2Content is the SO of 2000ppm2And N2Gaseous mixture, gas flow 50mL/
Min, temperature are 20 DEG C, and separated in time weighs the weight of teat glass until no longer changing.Every gram of absorbent is calculated
Absorb SO20.12 gram.
Claims (10)
1. a kind of eutectic solvent system, is made of imidazole salts and aprotic organic succinonitrile.
2. eutectic solvent system according to claim 1, it is characterised in that: described in the eutectic solvent system
Imidazole salts and the molar ratio of the succinonitrile are 1:1~8.
3. eutectic solvent system according to claim 1 or 2, it is characterised in that: in the eutectic solvent system, institute
Stating imidazole salts is 1- methyl -3- ethyl imidazol(e) villaumite and/or 1- methyl -3- ethyl imidazol(e) hexafluorophosphate.
4. a kind of method for preparing eutectic solvent system of any of claims 1-3, includes the following steps: institute
State imidazole salts to mix with the succinonitrile, be heated to system and all become liquid, be cooled to room temperature to get.
5. according to the method described in claim 4, it is characterized by: the temperature of the heating is 70~90 DEG C in the method.
6. eutectic solvent system of any of claims 1-3 is in efficient absorption/trapping SO2In application.
7. a kind of absorption/trapping SO2Method, include the following steps: eutectic of any of claims 1-3 is molten
Agent system with contain SO2Gas contact absorb.
8. according to the method described in claim 7, it is characterized by: contacting in the method and absorbing gas in absorption process
Pressure is 0.0001~0.10MPa, and absorbing temperature is 20~60 DEG C.
9. method according to claim 7 or 8, it is characterised in that: the method, which may further comprise:, will absorb dioxy
The eutectic solvent system heating for changing sulphur, is desorbed out the operation of sulfur dioxide gas recycling eutectic solvent system.
10. according to the method described in claim 9, it is characterized by: the temperature of the desorption is 70~90 DEG C.
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| CN201811547461.5A CN109529555B (en) | 2018-12-18 | 2018-12-18 | Eutectic solvent based on aprotic organic matter and method for efficiently absorbing sulfur dioxide by using eutectic solvent |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN113082960A (en) * | 2021-04-09 | 2021-07-09 | 辽宁科技大学 | Eutectic solvent for wide temperature window flue gas desulfurization and production and regeneration method thereof |
| CN113171671A (en) * | 2020-04-10 | 2021-07-27 | 盐城师范学院 | Eutectic solvent with amphiprotic molecular function design and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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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2018
- 2018-12-18 CN CN201811547461.5A patent/CN109529555B/en active Active
Patent Citations (1)
| 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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| DEZHONG YANG等: "Efficient Absorption of SO2 by EmimCl-EG Deep Eutectic Solvents", 《ACS SUSTAINABLE CHEM. ENG》 * |
| 吴桐等: "低共熔溶剂在化工分离过程中的应用及研究进展", 《山东化工》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN113082960A (en) * | 2021-04-09 | 2021-07-09 | 辽宁科技大学 | Eutectic solvent for wide temperature window flue gas desulfurization and production and regeneration method 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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