CN105498451B - For absorbing SO2Double imidazole ion liquid binary systems of ether and preparation method thereof and application method - Google Patents
For absorbing SO2Double imidazole ion liquid binary systems of ether and preparation method thereof and application method Download PDFInfo
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- CN105498451B CN105498451B CN201510833404.3A CN201510833404A CN105498451B CN 105498451 B CN105498451 B CN 105498451B CN 201510833404 A CN201510833404 A CN 201510833404A CN 105498451 B CN105498451 B CN 105498451B
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 title claims abstract description 175
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 title claims abstract description 155
- 239000007788 liquid Substances 0.000 title claims abstract description 92
- 229910002056 binary alloy Inorganic materials 0.000 title claims abstract description 49
- 238000000034 method Methods 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000002904 solvent Substances 0.000 claims abstract description 28
- 238000010521 absorption reaction Methods 0.000 claims abstract description 23
- 238000003795 desorption Methods 0.000 claims abstract description 12
- -1 imidazole ion Chemical class 0.000 claims description 109
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 49
- 238000006243 chemical reaction Methods 0.000 claims description 31
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 26
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 23
- 230000015572 biosynthetic process Effects 0.000 claims description 16
- 238000003786 synthesis reaction Methods 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 12
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 10
- 150000002460 imidazoles Chemical class 0.000 claims description 10
- 238000002390 rotary evaporation Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- JLGLQAWTXXGVEM-UHFFFAOYSA-N triethylene glycol monomethyl ether Chemical compound COCCOCCOCCO JLGLQAWTXXGVEM-UHFFFAOYSA-N 0.000 claims description 7
- 150000001450 anions Chemical class 0.000 claims description 6
- 239000011230 binding agent Substances 0.000 claims description 6
- 239000007795 chemical reaction product Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000005349 anion exchange Methods 0.000 claims description 5
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 5
- QARBMVPHQWIHKH-UHFFFAOYSA-N methanesulfonyl chloride Chemical compound CS(Cl)(=O)=O QARBMVPHQWIHKH-UHFFFAOYSA-N 0.000 claims description 5
- 238000005554 pickling Methods 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 4
- 230000008020 evaporation Effects 0.000 claims description 4
- 239000000376 reactant Substances 0.000 claims description 4
- 238000010025 steaming Methods 0.000 claims description 4
- 238000005292 vacuum distillation Methods 0.000 claims description 4
- SGRHVVLXEBNBDV-UHFFFAOYSA-N 1,6-dibromohexane Chemical compound BrCCCCCCBr SGRHVVLXEBNBDV-UHFFFAOYSA-N 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- SIXOAUAWLZKQKX-UHFFFAOYSA-N carbonic acid;prop-1-ene Chemical compound CC=C.OC(O)=O SIXOAUAWLZKQKX-UHFFFAOYSA-N 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 3
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- 125000000129 anionic group Chemical group 0.000 claims description 2
- 125000003963 dichloro group Chemical group Cl* 0.000 claims description 2
- 239000003085 diluting agent Substances 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims 2
- 239000002250 absorbent Substances 0.000 abstract description 12
- 230000008569 process Effects 0.000 abstract description 6
- 230000002745 absorbent Effects 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 5
- 238000012546 transfer Methods 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 230000002349 favourable effect Effects 0.000 abstract description 3
- 239000002608 ionic liquid Substances 0.000 description 32
- 239000007789 gas Substances 0.000 description 6
- XIYHKUFUMFHKHJ-UHFFFAOYSA-N 1-methylsulfonyloxybutyl methanesulfonate Chemical compound CCCC(OS(C)(=O)=O)OS(C)(=O)=O XIYHKUFUMFHKHJ-UHFFFAOYSA-N 0.000 description 5
- 125000001033 ether group Chemical group 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000001273 butane Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- 239000003546 flue gas Substances 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 125000002883 imidazolyl group Chemical group 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000006477 desulfuration reaction Methods 0.000 description 2
- 230000023556 desulfurization Effects 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 230000001965 increasing effect Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- ZPFKRQXYKULZKP-UHFFFAOYSA-N butylidene Chemical group [CH2+]CC[CH-] ZPFKRQXYKULZKP-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- JISVIRFOSOKJIU-UHFFFAOYSA-N hexylidene Chemical group [CH2+]CCCC[CH-] JISVIRFOSOKJIU-UHFFFAOYSA-N 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000001473 noxious effect Effects 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 150000004040 pyrrolidinones Chemical class 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229950004288 tosilate Drugs 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- Gas Separation By Absorption (AREA)
Abstract
It is used to absorb SO the present invention relates to one kind2The double imidazole ion liquid binary systems of ether, by the double imidazole ion liquids of ether and solvent (0.1~10) by weight ratio:1 is constituted.The double imidazole ion liquid binary systems of the ether of acquisition, for absorbing SO2, with mass transfer is fast, absorption efficiency is high, the advantage that easy desorption, reusable edible, use cost are low, in sweetening process non-secondary pollution, environmental protection is a kind of removing SO with good prospects for commercial application2High-efficiency absorbent.The preparation method technique of the present invention is simple, and preparation process stability is high, favorable repeatability.
Description
Technical field
It is used to absorb SO the present invention relates to a kind of ionic liquid binary system, more particularly to one kind2The double imidazoles of ether from
Sub- liquid dihydric system, while the invention further relates to the preparation method of the double imidazole ion liquid binary systems of the ether and user
Method.
Background technology
With developing rapidly for China's economy, the demand to the energy is continuously increased, in fuel such as coal, oil, natural gases
Combustion process causes to contain SO2A large amount of discharges of waste gas, SO2The acid rain of formation brings serious harm to the health of the mankind, to warp
Ji brings immeasurable loss, has had a strong impact in social environment and economic fast development, therefore removing flue gas
SO2It is very urgent.
Flue gas desulfurization technique traditional at present is broadly divided into wet method, dry method and semi-dry desulphurization according to the state of absorbent,
Alkaline absorbent or adsorbent is mainly used to remove SO2, non-renewable or regeneration is transformed into by chemical reaction
Difficult sulfide or sulphur, this processing method is by SO2Pollution to air is converted into noxious waste pollution, causes secondary dirt
Dye, also results in the serious loss of Sulphur ressource.In recent years, ionic liquid is because it is high, dissolvable almost without vapour pressure, stability
The good characteristics such as sour gas, reusable edible, and utilize the SO discharged in ionic liquid regenerative process2It can recycle
Advantage, ionic liquid is had broad application prospects for flue gas desulfurization.It is modifiable that ionic liquid is that one kind can be designed
Material, design meet demand object ion liquid be typically research difficult point, and to make ionic liquid have or strengthen
Feature in conventional ionic liquid structure, it is necessary to be embedded in functional groups, but embedded prepare of functional groups is often present
Difficulty.And ionic liquid due to viscosity it is big, cause the problems such as sweetening process consumption is big, cost is high, to have impact on it in industry
On popularization and application.
The content of the invention
To solve the deficiencies in the prior art, the invention provides the use of a kind of absorptive capacity height, reusable edible
In absorption SO2The double imidazole ion liquid binary systems of ether.
To achieve the above object, it is of the invention to be used to absorb SO2The double imidazole ion liquid binary systems of ether, by ether
Double imidazole ion liquids and solvent (0.1~10) by weight ratio:1 is constituted, and the structure of the double imidazole ion liquids of the ether is such as
Under：
Wherein RmRepresentative structure isGroup；
Representative structure isOrIn a kind of anion base
Group；
M is that 1~3, y is 4,6；
The solvent is a kind of solvent in water, dimethyl sulfoxide (DMSO), 1-METHYLPYRROLIDONE or propene carbonate.
The effect of imidazole ring is more ether chains for introducing and containing ether (- O-) in ionic liquid structure, and each ether is
One and SO2The avtive spot of molecular action, the avtive spot catches SO by electrostatic force2Molecule, and imidazole ring from
Can increase in structure with regulation activity site, enhancing ionic liquid to SO2Adsorption capacity.The double imidazol ions of the ether of the present invention
Liquid is double-core ionic liquid, not only because of its symmetrical double glyoxaline structure, enhances the stability of ionic liquid；Also Yin Qiyang from
Ether constitutes the spatial distribution and space length for absorbing site, promoted to SO in the distributed architecture at two ends in minor structure2After absorption
Stability；And because of the voidage increase between ionic liquid molecules caused by its specific molecular structure, can accommodate more
SO2Small molecule has been entered in ionic liquid so as to SO2Absorbent properties increase, compared to containing equal amount absorption site
Feature ether list imidazole ion liquid, absorptive capacity is higher；In addition, improving ionic liquid to SO2Absorbent properties exist
Restricted problem on, i.e., because ionic liquid is to SO2Absorption occupied an leading position with electrostatic force, but with the upside of cation
The increase electrostatic force of carbon number can weaken in chain substituent, therefore increase SO by increasing ether chain length2Active sites
Point can reduce the electrostatic force of ionic liquid on the contrary, cause to SO2Absorbent properties limited, and double imidazol ions of ether
Liquid makes carbochain be distributed in both sides by symmetrical structure, restricted problem is effectively solved.But there is viscosity in ionic liquid
Big defect, to solve this problem, the double imidazole ion liquids of ether and solvent are constituted diploid by the present invention with appropriate proportioning
System, by the viscosity of the addition greatly double imidazole ion liquids of reduction ether of solvent, increases contact area, mass transfer enhancement improves
Absorption process, reduces the consumption of ionic liquid on the premise of uptake is not reduced, and reduces use cost.The ether of acquisition is double
Imidazole ion liquid binary system, with the advantage that mass transfer is fast, absorption efficiency is high, use cost is low, due to SO2Absorption category
In Physical Absorption, easily desorption, also with reusable edible, energy consumption be low, environmental protection advantage.
As the restriction to aforesaid way, the weight proportion of the double imidazole ion liquids of the ether and solvent for (0.3~
5):1。
As the restriction to aforesaid way, the double imidazol ions of ether described in the structure of the double imidazole ion liquids of the ether
M is 2~3 in the structure of liquid；Y is 6.
Ether structure can be ethylene glycol monomethyl ether base, two in the cationic structural of the double imidazole ion liquids of the ether of the present invention
Ethylene glycol monomethyl ether base or triethylene glycol methyl ether base, its structural formula is respectively：
-CH2-CH2-O-CH3、
Ionic liquid is for SO during using m as 2 or 32Absorbent properties it is optimal.
It is that y values can be 4 or 6 to connect the C atom numbers contained by the chain hydrocarbon of two imidazole rings, and its structure is respectively：
During using y as 6, ionic liquid is for SO2Absorbent properties it is optimal.
Meanwhile, it is of the invention to be used to absorb SO2The double imidazole ion liquid binary systems of ether preparation method, including with
Lower step：
Step 1: the double imidazole ion liquids of synthesis ether, are carried out according to the following steps：
A, the double imidazoles alkane of synthesis：
A1, by imidazoles and sodium hydroxide in molar ratio 1:1 consumption mixing, adds solvent dimethyl sulfoxide (DMSO), controls temperature
At 60~65 DEG C, stirring reaction treats that sodium hydroxide is completely dissolved and obtains yellow solution；
A2, two bromoalkanes are added dropwise into yellow solution, 4~5h of stirring reaction, the dibromo alkane at 60~65 DEG C of temperature
Hydrocarbon is Isosorbide-5-Nitrae-dibromobutane or 1,6- dibromo-hexane, and the mol ratio of two bromoalkanes and imidazoles is 1:2；
A3, the reaction product for obtaining step a2 carry out purification processes, obtain double imidazoles alkane；
B, synthesis RmYlmethyl sulphonic acid ester：
B1, using one kind in ethylene glycol monomethyl ether, diethylene glycol dimethyl ether or triethylene glycol methyl ether as raw material and methylsufonyl chloride
In molar ratio 1:1 consumption carries out dropwise reaction：By by the methylsufonyl chloride of diluent dchloromethane, it is added drop-wise to by solvent
Dichloromethane, acid binding agent triethylamine are mixed with one kind in raw material ethylene glycol monomethyl ether, diethylene glycol dimethyl ether or triethylene glycol methyl ether
Solution system, controlling reaction temperature is below 10 DEG C, completion of dropping, continues stirring reaction 1~2h；
B2, the reactant for obtaining step b1 are carried out after rotary evaporation, washing, drying process successively, then vacuum distillation,
90~100 DEG C of collection steaming things, as RmYlmethyl sulphonic acid ester；
C, the double imidazole ion liquids of synthesis ether：
By double imidazoles alkane and RmYlmethyl sulphonic acid ester in molar ratio 1:2 consumption mixing, at 70~75 DEG C of temperature, is stirred
20~24h of reaction is mixed, the double imidazole ion liquids of ether that anion is pyrovinic acid root are obtained, then pass through anion exchange reaction
Obtain the double imidazol ion liquid of ether that anion is respectively p-methyl benzenesulfonic acid root, tetrafluoroborate, hexafluoro-phosphate radical or nitrate anion
Body；
Step 2: preparing the double imidazole ion liquid binary systems of ether：
The double imidazole ion liquids of ether and the solvent (0.1~10) by weight ratio that step one is obtained:1 mixing, stirring
Uniformly, obtain being used to absorb SO2The double imidazole ion liquid binary systems of ether, the solvent is water, dimethyl sulfoxide (DMSO), N- first
Any of base pyrrolidones or propene carbonate solvent.
Each reaction equation of the double imidazole ion liquid preparation process of ether is as follows：
The synthesis of double imidazoles alkane：
RmThe synthesis of ylmethyl sulphonic acid ester：
The synthesis of the double imidazole ion liquids of ether：
The preparation of the double glyoxaline ion liquid binary systems of ether, is carried out in two steps, and first synthesizes the double imidazol ion liquid of ether
Body, then ionic liquid and solvent are mixed and made into binary system.In the preparation process of the double imidazole ion liquids of ether, first with miaow
Azoles, sodium hydroxide and two bromoalkanes synthesize a series of pairs of imidazoles alkane, wherein two bromoalkanes can be Isosorbide-5-Nitrae-dibromobutane or 1,
6- dibromo-hexanes；Then using one kind and methylsufonyl chloride in ethylene glycol monomethyl ether, diethylene glycol dimethyl ether or triethylene glycol methyl ether as
Raw material, dichloromethane is solvent, and triethylamine is acid binding agent, synthesizes a series of RmWith tiing up acid in ylmethyl sulphonic acid ester, course of reaction
Agent absorbs the acid of generation, promotes reaction mobile to forward direction；Finally with double imidazoles alkane and RmYlmethyl sulphonic acid ester reacts, and synthesizes ether
Double glyoxaline ion liquids of base, then by anion exchange reaction, by pyrovinic acid root respectively with p-methyl benzenesulfonic acid root, tetrafluoro
Borate, hexafluoro-phosphate radical or nitrate anion carry out anion exchange, generate the double imidazole ion liquids of ether of other anion.System
It is difficult point that ether group, which is symmetrically embedded in cationic structural, in Preparation Method, and it is crucial, Er Qiexu to design suitable intermediate
The synthesis thinking of Gonna breakthrough routine ether list imidazole ion liquid.The preparation method technique of the present invention is simple, and preparation process is stable
Property high, favorable repeatability.
As the restriction to aforesaid way, it is 1.5ml/min that the dropwise reaction of the step b1, which controls that flow velocity is added dropwise,.
Flow velocity is added dropwise by limiting, reaction rate is controlled, makes reaction temperature control below 10 DEG C, to ensure that reaction is smooth
Carry out, it is to avoid the generation of impurity.
As the restriction to aforesaid way, rotating evaporation temperature is 50 DEG C in the step b2.
As the restriction to aforesaid way, carrying out washing treatment is to dissolve the thing that is evaporated for selecting evaporation to obtain in the step b2
In dichloromethane, pickling, washing process are then carried out.
As the restriction to aforesaid way, drying process is added to the dichloromethane solution after washing in the step b2
Anhydrous magnesium sulfate is dried, then steams dichloromethane by rotary evaporation.
The obtained reactants of step b1 are sequentially passed through into rotary evaporation processing in step b2, pickling, washing process and dry
Dry processing, removes solvent, acid binding agent and other impurity, is easy to follow-up distillation to collect RmYlmethyl sulphonic acid ester.
Meanwhile, the present invention is as described above to be used to absorb SO2The double imidazole ion liquid binary systems of ether user
Method, including the use of the double imidazole ion liquid binary systems of ether to containing SO2The absorption step that is absorbed of gas, it is and right
Absorb SO2The desorption procedure that the double imidazole ion liquid binary systems of ether afterwards are desorbed, it is characterised in that：It is described to absorb step
Absorption temperature control in rapid is 25~60 DEG C.
It is used to absorb SO in the double imidazole ion liquid binary systems of ether2During, limit and absorb temperature, make diploid
It is the assimilation effect being optimal.
As the restriction to aforesaid way, the desorption temperature control in the desorption procedure is 100~140 DEG C.
In summary, using technical scheme, acquisition be used for absorb SO2The double imidazole ion liquids two of ether
First system, with mass transfer is fast, absorption efficiency is high, the advantage that easy desorption, reusable edible, use cost are low, sweetening process without
Secondary pollution, environmental protection is a kind of removing SO with good prospects for commercial application2High-efficiency absorbent.The system of the present invention
Preparation Method technique is simple, and preparation process stability is high, favorable repeatability.
Embodiment
Embodiment one
The present embodiment is related to one group and is used to absorb SO2The double imidazole ion liquid binary systems of ether, it is as shown in the table：
By taking the double imidazole ion liquid binary systems of the ether of embodiment 1.2 as an example, using following preparation method：
Step 1: synthesis ionic liquid pair-(3- ethylene glycol monomethyl ether base -1- imidazoles) butylidene dimethanesulfonate, by following
Step is carried out：
A, the double imidazoles butane of synthesis 1,4-：
A1,1mol (68g) imidazoles and 1mol (40g) sodium hydroxide added in flask, add 200ml solvents dimethyl sub-
Sulfone (DMSO), controls 65 DEG C of temperature, and stirring reaction treats that sodium hydroxide is completely dissolved and obtains yellow solution；
A2,0.5mol (108g) Isosorbide-5-Nitrae-dibromobutane is added dropwise into yellow solution, the stirring reaction 4h at 65 DEG C of temperature；
A3, step a2 reaction system is cooled to after room temperature and pours into reaction product in the beaker for filling ice cube, stirred
Until ice-out, then carries out suction filtration, washed with frozen water after filter cake, carry out 3 recrystallizations again to filter cake, be dried to obtain white
The double imidazoles butane crystal of 1,4-.It is in order to reduce the temperature of system, to make the double imidazoles alkane of product quick from body using ice cube stirring
Crystallized out in system, because being crystallized comparatively fast in system, have some impurity and be wrapped in crystal group, then one is entered to crystal with frozen water
Washing impurity-removing is walked, then recrystallizes purification.Isosorbide-5-Nitrae-bis- imidazoles butane crystal of white is dried to obtain, its structural formula is as follows：
Sealing, which is put into drier, to be saved backup；
B, synthesizing glycol methyl ether ylmethyl sulphonic acid ester：
B1,190mL methylene chlorides, 40mL ethylene glycol monomethyl ethers and 210mL acid binding agents triethylamine (TEA) sequentially added
In 1000mL four-hole boiling flask；39mL methylsufonyl chlorides and 40mL dichloromethane (diluting effect) are added into 100mL constant pressure additions
In funnel；Four-hole boiling flask is placed in ice-water bath, starts dropwise reaction, adjustment drop speed is 1.5ml/min, makes reaction temperature control
Below 10 DEG C, after completion of dropping, 1.5h stoppings are stirred for, is added dropwise in process system and occurs having Huang on white haze, four-hole boiling flask
White solid adheres to；
B2, comprise the following steps：
Evaporation：The consersion unit constituted with circulation vacuum pump and Rotary Evaporators subtracts to the obtained reactants of step b1
Rotary evaporation is pressed, the temperature of Rotary Evaporators is set to 50 DEG C, and methylene chloride and acid binding agent triethylamine are gradually steamed, and are treated not
Again after dropping liquid, continue rotary evaporation 20min；
Washing：It is evaporated thing about 100ml dichloromethane to dissolve, then carries out containing reaction product in suction filtration, filtrate, receive
Collect filtrate, discard filter cake triethylamine salt；Pickling 5 times is carried out to filtrate, hydrochloric acid and water volume ratio 1 is used:The mixing of (3~5) is molten
Liquid, removes the triethylamine remained in filtrate, separatory funnel upper strata is the hydrochloric acid solution for being dissolved with triethylamine salt, is discarded, and lower floor is
The dichloromethane solution of reaction product is dissolved with, is collected；Washing 5 times is carried out to dichloromethane solution, the salt of pickling residual is removed
Acid, until water layer is close to neutrality, separatory funnel upper strata is hydrochloric water layer, is discarded, and lower floor is the dichloro for dissolving reaction product
Dichloromethane, is collected；
Dry：Anhydrous MgSO is added to dichloromethane solution4Stand overnight, filter MgSO4, then carry out rotation steaming
Hair, steams dichloromethane；
Vacuum distillation：The material that rotary evaporation is left carries out vacuum distillation, and steaming thing, as ethylene glycol are collected at 98 DEG C
Methyl ether ylmethyl sulphonic acid ester, its structural formula is as follows：
Sealing, which is put into drier, to be saved backup；
C, double imidazole ion liquids pair-(3- ethylene glycol monomethyl ether base -1- imidazoles) the butylidene dimethanesulfonates of synthesis ether：
By the double imidazoles butane of 0.02mol1,4- and 0.04mol ethylene glycol monomethyl ether ylmethyls sulphonic acid ester add equipped with drying tube,
Thermometer is simultaneously equipped with the three-necked flask of rotor, and three-necked flask is put into the heat collecting type heated at constant temperature magnetic agitation for filling conduction oil
In device, oil bath heating to flask interior temperature of charge is 70 DEG C, continuously stirs 24h, and reaction, which is finished, obtains lurid sticky
Shape liquid, collects the liquid, is placed in vacuum drying chamber at 80 DEG C drying 6h, obtains being used to absorb SO2The double miaows of ether
Oxazolinium ion liquid pair-(3- ethylene glycol monomethyl ether base -1- imidazoles) butylidene dimethanesulfonate, its structural formula is as follows：
Sealing, which is put into drier, to be saved backup；
Step 2: preparing the double imidazole ion liquid binary systems of ether：
Double imidazole ion liquids pair-(3- ethylene glycol monomethyl ether base -1- imidazoles) butylidene diformazans of ether that step one is obtained
Sulfonate is with solvent dimethyl sulfoxide (DMSO) by weight 1:1 mixing, stirs, and obtains being used to absorb SO2The double imidazoles of ether from
Sub- liquid dihydric system.
Double-(3- ethylene glycol monomethyl ether base -1- imidazoles) butylidene dimethanesulfonate sample of acquisition is subjected to nucleus magnetic hydrogen spectrum point
Analysis, obtains nucleus magnetic hydrogen spectrum figure as shown in Figure 1.Nucleus magnetic hydrogen spectrum map analysis to Fig. 1 draws, the ratio in nuclear magnetic spectrum with it is theoretical
Value is close, and it is target product pair-(3- ethylene glycol monomethyl ether base -1- imidazoles) butylidene dimethanesulfonate to show the material.
The material and proportioning listed by upper table, using identical preparation method, prepare the double imidazole ion liquid binary of ether
System.When preparing ionic liquid, first synthetic anionic is the double imidazole ion liquids of ether of pyrovinic acid root, is then carried out cloudy
Ion-exchange reactions, by taking embodiment 1.7 as an example, anion exchange reaction equation is as follows：
Obtain the double imidazole ion liquids pair-tosilate of (triethylene glycol methyl ether base -1- imidazoles) hexylidene two of ether.
The material and proportioning listed by upper table, using identical preparation method, prepare the double imidazole ion liquids of other ethers
Binary system.
Embodiment two
The present embodiment is related to the double imidazole ion liquid binary systems of ether to SO2Absorbent properties evaluation.
Embodiment 2.1
The double imidazole ion liquid binary systems of ether that the present embodiment is related to embodiment one are used to absorb SO2When, absorb and hold
Amount is influenceed evaluation by temperature is absorbed.
Absorption experiment is：The double imidazole ion liquid binary systems of the ether of precise are fitted into absorption tube, with 20mL/
Min gas flow, is passed through containing SO2Gas, absorption pressure is 0.1MPa, and tail gas is passed through in sodium hydroxide solution, use
Weight method determines SO2Absorptive capacity in ionic liquid, absorption reaches after balance that calculating obtains SO2In the ionic liquid
Uptake, it is as a result as shown in the table：
| Binary system | Temperature (DEG C) | SO2Uptake (mg/g) | |
| Embodiment 2.1.1 | Embodiment 1.1 | 25 | 335.6 |
| Embodiment 2.1.2 | Embodiment 1.1 | 35 | 298.9 |
| Embodiment 2.1.3 | Embodiment 1.1 | 55 | 202.4 |
| Embodiment 2.1.4 | Embodiment 1.2 | 25 | 927.4 |
| Embodiment 2.1.5 | Embodiment 1.3 | 40 | 715.9 |
| Embodiment 2.1.6 | Embodiment 1.4 | 40 | 829.9 |
| Embodiment 2.1.7 | Embodiment 1.5 | 40 | 504.8 |
| Embodiment 2.1.8 | Embodiment 1.6 | 25 | 1212.3 |
| Embodiment 2.1.9 | Embodiment 1.7 | 50 | 501.6 |
| Embodiment 2.1.10 | Embodiment 1.8 | 50 | 600.7 |
| Embodiment 2.1.11 | Embodiment 1.9 | 50 | 96.1 |
From upper table result, the double imidazole ion liquid binary systems of ether of the invention are in SO2In terms of absorbent properties by
The quantity of ether in ionic liquid, the species of solvent, the weight proportion of ionic liquid and solvent and the influence for absorbing temperature.
As the growth of ionic liquid ether chain is the increase of ether number, to SO2Uptake increase；With ionic liquid and solvent weight
The increase of amount proportioning ratio, to SO2Uptake first increase and reduce afterwards；With the rise for absorbing temperature, to SO2Uptake drop
It is low.
Embodiment 2.2
The present embodiment is related to the double imidazole ion liquid binary systems of ether compared to the double imidazol ion liquid of exclusive use ether
Body is for absorbing SO2When superiority assessment.Absorption experiment operates be the same as Example 2.1, as a result as shown in the table：
From upper table result, the double imidazole ion liquid binary systems of ether of the invention and pure ionic liquid or solvent phase
Under comparing, mass transfer is fast, and absorption rate is high, and uptake is high.
Embodiment three
The double imidazole ion liquid binary systems of ether that the present embodiment is related to the present invention are absorbing SO2Using when circulation make
Use performance evaluation.
Recycling experiment is：The double glyoxaline ion liquid binary systems of the ether of the embodiment 1.1 of precise are fallen
Enter in absorption tube, under 25 DEG C of constant temperatures, be passed through with 20mL/min gas flow into the device equipped with the binary system
Pure SO2Gas, absorption pressure is 0.1MPa, is absorbed, after binary system reaches saturation, with 50mL/min flow to dress
Nitrogen is passed through in putting, it is 0.1MPa to control desorption pressures, it is 100 DEG C to control desorption temperature, is desorbed, whole process repeats five
Secondary carry out circulation experiment, SO is determined with weight method2Absorptive capacity in ionic liquid.
| Access times | SO2Uptake (mg/g) | |
| Embodiment 3.1 | 1st time | 335.6 |
| Embodiment 3.2 | 2nd time | 328.2 |
| Embodiment 3.3 | 3rd time | 343.4 |
| Embodiment 3.4 | The 4th | 341.6 |
| Embodiment 3.5 | The 5th | 338.1 |
From upper table result, the double imidazole ion liquid binary system stability of ether of the invention are high, and easily desorption can be more
Secondary to recycle, absorptive capacity is stable, can be used as a kind of economic, green efficient SO2Absorbent.
Claims (10)
1. one kind is used to absorb SO2The double imidazole ion liquid binary systems of ether, it is characterised in that the binary system is by ether
Double imidazole ion liquids and solvent (0.1~10) by weight ratio:1 is constituted, and the structure of the double imidazole ion liquids of the ether is such as
Under：
Wherein RmRepresentative structure isGroup；
Representative structure isIn a kind of anionic group；
M is that 1~3, y is 4,6；
The solvent is a kind of solvent in water, dimethyl sulfoxide (DMSO), 1-METHYLPYRROLIDONE or propene carbonate.
2. according to claim 1 be used to absorb SO2The double imidazole ion liquid binary systems of ether, it is characterised in that：Institute
The weight proportion for stating the double imidazole ion liquids of ether and solvent is (0.3~5):1.
3. according to claim 1 be used to absorb SO2The double imidazole ion liquid binary systems of ether, it is characterised in that：Institute
It is 2~3 to state m in the structure of the double imidazole ion liquids of ether；Y is 6.
4. one kind is used to absorb SO2The double imidazole ion liquid binary systems of ether preparation method, it is characterised in that this method
Comprise the following steps：
Step 1: the double imidazole ion liquids of synthesis ether, are carried out according to the following steps：
A, the double imidazoles alkane of synthesis：
A1, by imidazoles and sodium hydroxide in molar ratio 1:1 consumption mixing, adds solvent dimethyl sulfoxide (DMSO), control temperature is 60
~65 DEG C, stirring reaction treats that sodium hydroxide is completely dissolved and obtains yellow solution；
A2, two bromoalkanes are added dropwise into yellow solution, 4~5h of stirring reaction at 60~65 DEG C of temperature, two bromoalkane is
Isosorbide-5-Nitrae-dibromobutane or 1,6- dibromo-hexane, the mol ratio of two bromoalkanes and imidazoles is 1:2；
A3, the reaction product for obtaining step a2 carry out purification processes, obtain double imidazoles alkane；
B, synthesis RmYlmethyl sulphonic acid ester：
B1, using one kind in ethylene glycol monomethyl ether, diethylene glycol dimethyl ether or triethylene glycol methyl ether be raw material and methylsufonyl chloride massage
You compare 1:1 consumption carries out dropwise reaction：By by the methylsufonyl chloride of diluent dchloromethane, it is added drop-wise to by solvent dichloro
It is molten that methane, acid binding agent triethylamine are mixed with a kind of in raw material ethylene glycol monomethyl ether, diethylene glycol dimethyl ether or triethylene glycol methyl ether
Liquid system, controlling reaction temperature is below 10 DEG C, completion of dropping, continues 1~2h of stirring reaction；
B2, the reactant for obtaining step b1 are carried out after rotary evaporation, washing, drying process successively, then vacuum distillation, 90~
100 DEG C of collection steaming things, as RmYlmethyl sulphonic acid ester；
C, the double imidazole ion liquids of synthesis ether：
By double imidazoles alkane and RmYlmethyl sulphonic acid ester in molar ratio 1:2 consumption mixing, at 70~75 DEG C of temperature, stirring is anti-
20~24h is answered, the double imidazole ion liquids of ether that anion is pyrovinic acid root are obtained, then obtain by anion exchange reaction
Anion is respectively the double imidazole ion liquids of ether of p-methyl benzenesulfonic acid root, tetrafluoroborate, hexafluoro-phosphate radical or nitrate anion；
Step 2: preparing such as the double imidazole ion liquid binary systems of ether according to any one of claims 1 to 3：
The double imidazole ion liquids of ether that step one is obtained are mixed with solvent, are stirred, and obtain being used to absorb SO2Ether
Double imidazole ion liquid binary systems.
5. according to claim 4 be used to absorb SO2The double imidazole ion liquid binary systems of ether preparation method, its
It is characterised by：It is 1.5ml/min that the dropwise reaction of the step b1, which controls that flow velocity is added dropwise,.
6. according to claim 4 be used to absorb SO2The double imidazole ion liquid binary systems of ether preparation method, its
It is characterised by：Rotating evaporation temperature is 50 DEG C in the step b2.
7. according to claim 6 be used to absorb SO2The double imidazole ion liquid binary systems of ether preparation method, its
It is characterised by：Carrying out washing treatment is that the thing that is evaporated for obtaining rotary evaporation is dissolved in dichloromethane in the step b2, Ran Houjin
Row pickling, washing process.
8. according to claim 7 be used to absorb SO2The double imidazole ion liquid binary systems of ether preparation method, its
It is characterised by：Drying process is to add anhydrous magnesium sulfate to the dichloromethane solution after washing to be dried in the step b2,
Again dichloromethane is steamed by rotary evaporation.
9. a kind of being used for as any one of claim 1-3 absorbs SO2Ether double imidazole ion liquid binary systems
Application method, including the use of the double imidazole ion liquid binary systems of ether to containing SO2The absorption step that is absorbed of gas,
And to absorbing SO2The desorption procedure that the double imidazole ion liquid binary systems of ether afterwards are desorbed, it is characterised in that：It is described
Absorption temperature control in absorption step is 25~60 DEG C.
10. according to claim 9 be used to absorb SO2The double imidazole ion liquid binary systems of ether application method, its
It is characterised by：Desorption temperature control in the desorption procedure is 100~140 DEG C.
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