CN111821811B - Dication ionic liquid containing ether bond and nitrogen heterocycle and having physical and chemical absorption effects and method for trapping sulfur dioxide - Google Patents
Dication ionic liquid containing ether bond and nitrogen heterocycle and having physical and chemical absorption effects and method for trapping sulfur dioxide Download PDFInfo
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- CN111821811B CN111821811B CN201910319143.1A CN201910319143A CN111821811B CN 111821811 B CN111821811 B CN 111821811B CN 201910319143 A CN201910319143 A CN 201910319143A CN 111821811 B CN111821811 B CN 111821811B
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- 238000010521 absorption reaction Methods 0.000 title claims abstract description 53
- 239000002608 ionic liquid Substances 0.000 title claims abstract description 46
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 19
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 239000000126 substance Substances 0.000 title claims abstract description 14
- 230000000694 effects Effects 0.000 title description 9
- -1 bisimidazole cations Chemical class 0.000 claims abstract description 45
- 239000007789 gas Substances 0.000 claims abstract description 16
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 21
- 238000003795 desorption Methods 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 5
- 230000008929 regeneration Effects 0.000 claims description 5
- 238000011069 regeneration method Methods 0.000 claims description 5
- KAESVJOAVNADME-UHFFFAOYSA-N 1H-pyrrole Natural products C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 4
- 238000007664 blowing Methods 0.000 claims description 4
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N methylimidazole Natural products CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 239000012964 benzotriazole Substances 0.000 claims description 3
- 238000010926 purge Methods 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims 2
- 125000002091 cationic group Chemical group 0.000 claims 1
- 238000006477 desulfuration reaction Methods 0.000 abstract description 12
- 230000023556 desulfurization Effects 0.000 abstract description 12
- 239000003546 flue gas Substances 0.000 abstract description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 abstract description 3
- 125000000623 heterocyclic group Chemical group 0.000 abstract description 2
- 238000004064 recycling Methods 0.000 abstract description 2
- 229920001223 polyethylene glycol Polymers 0.000 abstract 2
- 239000002202 Polyethylene glycol Substances 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 17
- 239000000243 solution Substances 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 7
- AZUHIVLOSAPWDM-UHFFFAOYSA-N 2-(1h-imidazol-2-yl)-1h-imidazole Chemical compound C1=CNC(C=2NC=CN=2)=N1 AZUHIVLOSAPWDM-UHFFFAOYSA-N 0.000 description 6
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 6
- 239000003957 anion exchange resin Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 150000003536 tetrazoles Chemical class 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical compound C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229910052602 gypsum Inorganic materials 0.000 description 2
- 239000010440 gypsum Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000012086 standard solution Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- QWENRTYMTSOGBR-UHFFFAOYSA-N 1H-1,2,3-Triazole Chemical compound C=1C=NNN=1 QWENRTYMTSOGBR-UHFFFAOYSA-N 0.000 description 1
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- XGDRLCRGKUCBQL-UHFFFAOYSA-N 1h-imidazole-4,5-dicarbonitrile Chemical compound N#CC=1N=CNC=1C#N XGDRLCRGKUCBQL-UHFFFAOYSA-N 0.000 description 1
- LDWZDAMJGLOLGF-UHFFFAOYSA-N 1h-imidazole;hydrochloride Chemical compound Cl.C1=CNC=N1.C1=CNC=N1 LDWZDAMJGLOLGF-UHFFFAOYSA-N 0.000 description 1
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 description 1
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
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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
-
- 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
- B01D53/1425—Regeneration of liquid absorbents
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
- C07D207/32—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
- C07D207/323—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to the ring nitrogen atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/04—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D233/20—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with substituted hydrocarbon radicals, directly attached to ring carbon atoms
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
- C07D233/58—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring nitrogen atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
- C07D233/60—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms with hydrocarbon radicals, substituted by oxygen or sulfur atoms, attached to ring nitrogen atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/66—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D233/90—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D235/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings
- C07D235/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings condensed with carbocyclic rings or ring systems
- C07D235/04—Benzimidazoles; Hydrogenated benzimidazoles
- C07D235/06—Benzimidazoles; Hydrogenated benzimidazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached in position 2
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D249/04—1,2,3-Triazoles; Hydrogenated 1,2,3-triazoles
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/16—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms condensed with carbocyclic rings or ring systems
- C07D249/18—Benzotriazoles
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D257/00—Heterocyclic compounds containing rings having four nitrogen atoms as the only ring hetero atoms
- C07D257/02—Heterocyclic compounds containing rings having four nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D257/04—Five-membered rings
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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
- B01D2252/30—Ionic liquids and zwitter-ions
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- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
- Gas Separation By Absorption (AREA)
Abstract
The invention discloses a dication ionic liquid containing ether bond and nitrogen heterocycle and having physical and chemical absorption functions and a method for trapping sulfur dioxide, and dicationThe sub-ionic liquid consists of polyethylene glycol functionalized bisimidazole cations and non-proton type nitrogen-containing heterocyclic ring anions, integrates the physical absorption function of PEG-linked biscations and the chemical absorption function of the nitrogen-containing heterocyclic ring dianions, and is applied to SO2Trapping of gases, especially ultra-low concentrations of SO in flue gases2Gas capture, rapid absorption, high absorption rate, stable recycling performance and the like, and can be used for flue gas desulfurization and low-concentration SO2The gas absorption has better application prospect.
Description
Technical Field
The invention belongs to the technical field of gas separation and purification, and particularly relates to a novel dicationic ionic liquid containing ether bonds and nitrogen heterocycles, a preparation method thereof and a method for trapping SO2The method of (1).
Background
With the rapid development of social economy, the SO in the coal-fired flue gas is strictly implemented2The ultralow emission is effective in suppressing SO2An important means of contamination. Flue gas desulfurization techniques can be classified into three major categories, wet, dry and semi-dry, according to the desulfurization method and the form of the desulfurization product. The wet desulfurization technology is the most mature and widely applied method at present, about 90% of coal-fired flue gas desulfurization treatment adopts a limestone-gypsum method in wet desulfurization, the desulfurization efficiency of the method can reach 99% at most, but the method has the defects of huge equipment, high initial investment and operation and maintenance cost, low additional value of desulfurization by-product gypsum, easy secondary pollution and the like, and is contrary to the principle of sustainable development. The dry and semi-dry desulfurization technology has the advantages of simple process, small floor area, low investment, low water consumption and the like, but the desulfurization efficiency is only 70-80%, the method is suitable for the condition of low sulfur content of the fire coal, and the application range is limited to a certain extent.
Based on the problems of the traditional desulfurization technology, researchers try to find a novel absorbent with excellent performance to realize SO in flue gas2The efficient reversible removal solution of (1). The ionic liquid has the advantages of low vapor pressure, good thermal stability, wide liquid process temperature, strong gas dissolving capacity, good controllability and the like. Among them, Dicationic Ionic Liquids (DILs) have more flexible regulation performance and good thermal stability. However, most of the ionic liquids reported in the literature at present are prepared by physically adsorbing SO with higher concentration2Has good absorption effect but can absorb low-concentration SO2The absorption effect of (2) is poor. Chemical adsorption can realize low-concentration SO2The ionic liquid has the defects of poor recycling performance, poor stability and the like, so that the ionic liquid needs to be fully designed to develop a method for preparing the ionic liquidCan not only keep low concentration SO2Has higher absorption capacity and is convenient for desorption and has the functions of physical absorption and chemical absorption.
Disclosure of Invention
The invention aims to overcome the defect that the existing ionic liquid can not react with low-concentration SO2The disadvantage of low absorption capacity, provides a novel dicationic ionic liquid containing ether bond and nitrogen heterocycle, a preparation method thereof and a method for trapping SO2The method of (1).
The technical purpose of the invention is realized by the following technical scheme.
A novel dicationic ionic liquid containing ether bonds and nitrogen heterocycles, which consists of PEG functionalized bisimidazole cations and non-proton type nitrogen-containing heterocycle anions, wherein:
the structural formula of the PEG functionalized bisimidazole cation is as follows
R is H or one of alkyl of C1-C10; n is an integer of 1 to 4
The non-proton type nitrogen-containing heterocyclic anion is pyrrole ion, pyrazole ion, imidazole ion, 1,2, 3-triazole ion, 1,2, 4-triazole ion, tetrazole ion, 2-phenylimidazole ion, benzimidazole ion, benzotriazole ion, 4, 5-dicyanoimidazole ion, 4-trifluoromethane imidazole ion or 4-methylimidazole ion, and is specifically shown in the following table.
The invention relates to the kind of anions
A method for preparing novel dicationic ionic liquid containing ether bond and nitrogen heterocycle comprises the following steps of treating PEG-linked bisimidazole chloride and aprotic nitrogen-containing heterocyclic compound by strong-base anion exchange resin, wherein the weight ratio of the PEG-linked bisimidazole chloride to the aprotic nitrogen-containing heterocyclic compound is 1: (2-2.5) at room temperature to obtain an ionic liquid.
In the technical scheme, the molar ratio of the PEG-connected bisimidazole chloride to the aprotic nitrogen-containing heterocyclic compound is 1: (2-2.4), preferably 1: (2.2-2.4), the molar ratio of the PEG functionalized bisimidazole cation to the non-proton type nitrogen-containing heterocyclic anion in the ionic liquid is 1: (2-2.4), preferably 1: 2.
in the technical scheme, the strong-base anion exchange resin is 717 type strong-base anion exchange resin, and the PEG-linked bisimidazole chloride and the strong-base anion exchange resin are treated to exchange chloride ions by hydroxide radicals.
In the technical scheme, ethanol is selected as a reaction atmosphere, namely, the PEG-connected bisimidazole chloride is dissolved (or uniformly dispersed) in the ethanol, ion exchange is carried out through strong-base anion exchange resin, and then the exchanged solution is reacted with an ethanol solution in which the aprotic nitrogen-containing heterocyclic compound is dissolved (or uniformly dispersed).
In the technical scheme, the room temperature is 20-25 ℃, and the stirring reaction is carried out for 6-24 hours, preferably 10-20 hours; after the reaction, the ionic liquid is obtained after the reaction system is subjected to rotary evaporation, washing and vacuum drying.
In the above technical scheme, the PEG-linked bis-imidazole chloride is
R is H or one of alkyl of C1-C10; n is an integer and 1. ltoreq. n.ltoreq.4, i.e.substances corresponding to PEG-functionalized bisimidazole cations having two chloride ions, such as 1,1'- (3,6, 9-trioxaundecane-1, 11-diyl) bis (3-methyl-1H-imidazol-1-yl) dichloride, 1' - (3,6, 9-trioxaundecane-1, 11-diyl) bis (3-ethyl-1H-imidazol-1-yl) dichloride, 1'- (3,6, 9-trioxaundecane-1, 11-diyl) bis (3-propyl-1H-imidazol-1-yl) dichloride or 1,1' - (3,6, 9-trioxaundecane-1, 11-diyl) bis (3-butyl-1H-imidazol-1-yl) dichloride.
In the technical scheme, the aprotic nitrogen-containing heterocyclic compound is pyrrole, pyrazole, imidazole, 1,2, 3-triazole, 1,2, 4-triazole, tetrazole, 2-phenylimidazole, benzimidazole, benzotriazole, 4, 5-dicyanoimidazole, 4-trifluoromethane imidazole or 4-methylimidazole, namely a substance corresponding to the aprotic nitrogen-containing heterocyclic anion on the table above, and the N atom does not lose proton.
The application of the novel dicationic ionic liquid in sulfur dioxide absorption is suitable for SO in different states2Efficient reversible absorption. The novel method for absorbing sulfur dioxide by using dicationic ionic liquid has the advantages that the absorption temperature is controlled within the range of 20-120 ℃, the absorption pressure is controlled within the range of 1-20 atm, and the absorption time is controlled within 10-600 min; the SO can be desorbed by heating or blowing under vacuum2The regeneration of the ionic liquid is realized, and the high-purity N is selected as the purge gas2The gas flow is controlled to be 60-120 mL/min, the desorption temperature is controlled to be 50-150 ℃, the desorption pressure is controlled to be-1 atm, and the desorption time is 10-200 min.
Preferably, the absorption temperature is 20-80 ℃, the absorption pressure is 5-10 atm, and the absorption time is 30-60 min; desorbing SO by heating or blowing under vacuum2The regeneration of the ionic liquid is realized, the gas flow is controlled to be 80-100 mL/min, the desorption temperature is controlled to be 80-120 ℃, the desorption pressure is controlled to be-1 atm, and the desorption time is 30-60 min.
Compared with the ionic liquid reported in the literature, the novel dicationic ionic liquid containing ether bonds and nitrogen heterocycles has the following characteristics: (1) the bisimidazoles are adopted as dications, SO that the bisimidazoles have good thermal stability and lower saturated vapor pressure, and are beneficial to SO at high temperature2Absorption of (2); (2) the dication is connected by ether bond, has good space freedom degree, low viscosity and convenient SO2The diffusion in the ionic liquid improves the absorption efficiency; (3) the introduction of the non-proton nitrogen-containing heterocyclic ring in the anion is avoidedAbsorption of SO by ionic liquids2Formation of post-hydrogen bond network, and reduction of ionic liquid-SO2The viscosity of the system; (4) n atom and SO with stronger electronegativity in aprotic nitrogen-containing heterocycle2The strong acting force between S atoms in the middle ensures that the ionic liquid acts on SO2The absorption capacity of (A) is up to 2.733mol SO at 20 ℃ and 2000ppm2Mol DIL (mass absorption of 0.360 gSO)2DIL)/g), at the highest level at present; (5) SO is generated by heating and nitrogen purging2And desorbing from the ionic liquid to realize the regeneration and utilization of the ionic liquid.
Detailed Description
The present invention is described in detail by the following examples, but is not limited to the following examples, and all the technologies realized based on the above contents of the present invention belong to the technical scope of the present invention.
Example 1
The embodiment relates to a preparation process of a series of dicationic ionic liquids containing ether bonds and nitrogen heterocycles, and a specific preparation method taking 1,1' - (3,6, 9-trioxaundecane-1, 11-diyl) bis (3-ethyl-1H-imidazol-1-yl) tetrazole as an example is as follows:
(1) a717 type strongly basic anion exchange resin was pretreated with 1mol/L hydrochloric acid solution, and then 8 times the resin volume of 1mol/L NaOH solution was passed through the resin column at a rate of 10 mL/min. The excess NaOH was eluted with deionized water until the effluent was neutral.
(2) 19.60g of 1,1' - (3,6, 9-trioxaundecane-1, 11-diyl) bis (3-ethyl-1H-imidazol-1-yl) dichloride was dissolved in 100mL of absolute ethanol, and the dissolved liquid sample was passed through the column of the treated resin at a flow rate of 10mL/min until no Cl was detected in the effluent liquid-The collected liquid was made up to 500mL of standard solution with ethanol. The above solution was titrated with 0.1mol/L NaOH as a standard solution and the concentration of hydroxyl in the solution was calculated to be about 0.18 mol/L.
(3) Dissolving 7.78g of tetrazole in 100mL of absolute ethyl alcohol, dropwise adding the dissolved solution into ethyl ester of 1,1' - (3,6, 9-trioxaundecane-1, 11-diyl) bis (3-ethyl-1H-imidazole-1-yl) hydroxideAlcohol solution, and stirring the reaction solution at room temperature for 24 hours. And then removing water and ethanol by using a rotary evaporator to obtain a crude product, washing the crude product by using 3X 20mL of anhydrous ether, drying the crude product in a vacuum drying oven at the temperature of 80 ℃, and drying for 48 hours to obtain a refined sample of 1,1' - (3,6, 9-trioxaundecane-1, 11-diyl) bis (3-ethyl-1H-imidazole-1-yl) tetrazole. The nuclear magnetic resonance hydrogen spectrum data are as follows:1H NMR(400MHz,DMSO-d6) δ 1.42(t, J ═ 7.3Hz,3H),3.47(dt, J ═ 6.5, 2.8Hz,2H), 3.50-3.57 (m,2H),3.78(t, J ═ 5.0Hz,2H),4.23(q, J ═ 7.3Hz,2H),4.37(t, J ═ 5.0Hz,2H),7.79(t, J ═ 1.8Hz,1H),7.87(t, J ═ 1.8Hz,1H),8.43(s,1H),9.33(d, J ═ 1.6Hz, 1H). The infrared data is (4000--1)3392,3142,3099,2981,2874,1565,1447,1351,1167, 1118,838,759,704,652。
Example 2
In analogy to example 1,1' - (3,6, 9-trioxaundecane-1, 11-diyl) bis (3-ethyl-1H-imidazol-1-yl) 1,2, 4-triazole was prepared by replacing 7.78g of tetrazole in step (3) with 7.67g of 1,2, 4-triazole and by otherwise performing the same procedure as in example 1. The nuclear magnetic resonance hydrogen spectrum data are as follows:1H NMR(400MHz,DMSO-d6) δ 1.41(t, J ═ 7.3Hz,3H), 3.43-3.57 (m,4H),3.77(t, J ═ 5.0Hz,2H),4.22(q, J ═ 7.3Hz,2H),4.36(t, J ═ 5.0Hz,2H), 7.72-7.81 (m,3H),7.85(t, J ═ 1.7Hz,1H),8.33(s,1H),9.40(t, J ═ 1.6Hz, 1H). The infrared data is (4000--1)3141,3085,1667,1565,1479,1351,1247,1167,1145, 1026,970,857,759,684,653。
Example 3
In analogy to example 1,1' - (3,6, 9-trioxaundecane-1, 11-diyl) bis (3-ethyl-1H-imidazol-1-yl) imidazole was prepared by replacing 7.78g of tetrazole in step (3) with 7.56g of imidazole and the other operations were identical to example 1. The nuclear magnetic resonance hydrogen spectrum data are as follows:1H NMR(400MHz,DMSO-d6) δ 1.41(t, J ═ 7.3Hz,3H), 3.41-3.52 (m,2H), 3.47-3.59 (m,2H), 3.72-3.81 (m,2H),4.21(q, J ═ 7.3Hz,2H),4.35(t, J ═ 4.9Hz,2H),6.94(d, J ═ 1.0Hz,3H),7.52(s,2H),7.78(d, J ═ 2.0Hz,1H),7.84(d, J ═ 2.0Hz, 1H). The infrared data is (4000-400 cm)-1)3106,2914,1662,1564,1451,1350,1323,1300,1167, 1095,1065,926,832,758,667,623。
The preparation of other dicationic ionic liquids containing ether bond and nitrogen heterocycle is similar to the preparation method of the examples 1,2 and 3, namely selecting the corresponding PEG-linked bisimidazole chloride and the aprotic nitrogen-containing heterocyclic compound for reaction.
Example 4
1.17g of the ionic liquid obtained in example 1 was placed in an absorption flask having an inner diameter of 10mm and a volume of 10mL, and SO was introduced thereinto2Gas with gas flow rate of 80mL/min, absorption temperature of 20 ℃, SO2The pressure is 0.1 MPa. The mass of the absorption bottle is weighed at regular intervals until the mass does not change any more, and the absorption balance is reached in about 10 min. SO finally obtained2Absorption capacity of 6.958 molSO2/mol DIL。
Examples 5 to 9
Similar to example 4, the ionic liquid species was varied, and the SO obtained2The absorption effect is shown in the following table.
Different nitrogen heterocyclic ring dicationic ionic liquid pairs SO2Absorption effect of
Examples 10 to 21
Analogously to example 4, the absorption temperature and SO were varied2The gas partial pressure is that 1,1' - (3,6, 9-trioxaundecane-1, 11-diyl) bis (3-ethyl-1H-imidazol-1-yl) imidazole is used as an absorbent to absorb SO2The gas absorption effect is shown in the following table.
SO under different absorption conditions2Absorption effect
Example 22
2.23g of ionic liquid 1,1' - (3,6, 9-trioxaundecane-1, 11-diyl) bis (3-ethyl-1H-imidazol-1-yl) tetrazole saturated for absorbing sulfur dioxide was added into an absorption bottle having an inner diameter of 10mm and a volume of 10 mL. Introducing high-purity nitrogen, controlling the gas flow to be 100mL/min, controlling the absorption temperature to be 100 ℃, and controlling the desorption time to be 60 min. Measurement of SO by weighing2The desorption rate of (2) was 100%.
Examples 23 to 29
Similarly to example 22, the kind of ionic liquid, desorption time and desorption temperature were changed, and the desorption effect was as shown in the following table.
SO under different desorption conditions2Effect of desorption
The preparation of the ionic liquid can be realized by adjusting parameters according to the content of the invention, and the ionic liquid shows basically consistent performance with the invention, namely shows efficient reversible absorption performance for sulfur dioxide. The invention has been described in an illustrative manner, and it is to be understood that any simple variations, modifications or other equivalent changes which can be made by one skilled in the art without departing from the spirit of the invention fall within the scope of the invention.
Claims (6)
1. A dicationic ionic liquid containing ether bonds and nitrogen heterocycles and having physical and chemical absorption functions is characterized by consisting of PEG functionalized bisimidazole cations and non-proton type nitrogen-containing heterocycle anions, wherein:
the structural formula of the PEG functionalized bisimidazole cation is as follows
R is H or one of alkyl of C1-C10; n is an integer, and n is more than or equal to 1 and less than or equal to 4;
the non-proton type nitrogen-containing heterocyclic anion is one of pyrrole ions, pyrazole ions, imidazole ions, 1,2, 3-triazole ions, 1,2, 4-triazole ions, tetrazole ions, 2-phenylimidazole ions, benzimidazole ions, benzotriazole ions, 4, 5-dicyanoimidazole ions, 4-trifluoromethane imidazole ions or 4-methylimidazole ions.
2. The dicationic ionic liquid containing ether bond and nitrogen heterocycle with physical and chemical absorption function as claimed in claim 1, wherein R is one of C3-C8 alkyl.
3. The dicationic ionic liquid containing ether bonds and nitrogen heterocycles and having physical and chemical absorption functions as claimed in claim 1 or 2, wherein the molar ratio of the PEG functionalized bisimidazole cations to the non-proton nitrogen-containing heterocycle anions in the ionic liquid is 1 (2-2.4).
4. Use of the dicationic ionic liquid containing ether bond and nitrogen heterocycle with physical and chemical absorption in sulfur dioxide absorption according to any one of claims 1 to 3.
5. The method for absorbing sulfur dioxide by using the dicationic ionic liquid containing ether bond and nitrogen heterocycle and having physical and chemical absorption functions as claimed in any one of claims 1 to 3, wherein the absorption temperature is controlled within the range of 20 to 120 ℃, the absorption pressure is controlled within the range of 1 to 20atm, the absorption time is controlled within 10 to 600min, and SO is desorbed by heating or blowing under vacuum2The regeneration of the ionic liquid is realized, and the high-purity N is selected as the purge gas2The gas flow is controlled to be 60-120 mL/min, the desorption temperature is controlled to be 50-150 ℃, the desorption pressure is controlled to be-1 atm, and the desorption time is 10-200 min.
6. The method of claim 5, wherein the physical and chemical absorption of the compound is achieved by a compound containing an ether bond and a nitrogen heterocycleThe method for absorbing sulfur dioxide by using cationic ionic liquid is characterized in that the absorption temperature is 20-80 ℃, the absorption pressure is 5-10 atm, the absorption time is 30-60 min, and SO is desorbed by a mode of blowing under a heating or vacuum condition2The regeneration of the ionic liquid is realized, the gas flow is controlled to be 80-100 mL/min, the desorption temperature is controlled to be 80-120 ℃, the desorption pressure is controlled to be-1 atm, and the desorption time is 30-60 min.
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