CN103059024B - Functionalized ion liquid and application thereof - Google Patents
Functionalized ion liquid and application thereof Download PDFInfo
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- CN103059024B CN103059024B CN201210530884.2A CN201210530884A CN103059024B CN 103059024 B CN103059024 B CN 103059024B CN 201210530884 A CN201210530884 A CN 201210530884A CN 103059024 B CN103059024 B CN 103059024B
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- ion liquid
- functionalized ion
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Abstract
The invention discloses a functionalized ion liquid, which has a chemical structure of a general formula (I) shown in the description, wherein, R1 is -H, R2 is -H, and R3 is -CH3; a chemical structural formula of the negative ion is shown in the description, the ion liquid is used for absorbing sulfur dioxide in waste gas. The temperature of the absorbed waste gas is 5-35 DEG C, the partial pressure of sulfur dioxide in the waste gas is 0.001-0.1MPa, the detention time of the waste gas in the ion liquid is 2-20 min, and the desorption temperature is 70-160 DEG C. Compared with the traditional technology of depriving sulfur dioxide in waste gas, the application is of high efficiency and high selectivity for absorption and free of sea water in absorption process without generating wastes after absorption, and can be regenerated through heating.
Description
Technical field
The present invention relates to technical field of chemistry, specifically a kind of ionic liquid of sulfur dioxide absorption and application thereof.
Background technology
Sulfur dioxide gas is the principal pollutant of air, and in recent years, although China takes reduction of discharging policy, China every year on average acid gas emissions amount is still more, on the impact of the damaging property of physical environment that we depend on for existence.At present ripe for removing of acid waste gas, the means of large-scale application mainly can still take absorption agent or the sorbent material of alkalescence, and it is converted into more stable compound, therefore all not reproducible use.Common absorption process has limestone-gypsum method, sour method, magnesium oxide method, activated coke method etc., its assimilated efficiency is general lower, poor selectivity, although wherein improve desulfuration efficiency as desulfurization method of limestone-gypsum technology most widely used in desulfurization process for flue gases, but the liquid and waste slag produced amount produced in sweetening process is large, needs special disposal or utilizes these by products.State Intellectual Property Office of the People's Republic of China website discloses a kind of method utilizing seawater to carry out scrubbing CO_2, add the flyash of 6 ~ 15% weight percents in the seawater, stir 10 ~ 60 minutes, leave standstill to the abundant sedimentation of flyash, get supernatant liquor as absorption liquid; Absorption liquid and flue gas carry out reverse contact mass transfer in absorption tower, and flue gas enters from tower top emptying at the bottom of tower, and absorption liquid sprays downwards from tower top, discharge at the bottom of tower with after flue gas mass transfer, and the liquid-gas ratio of absorption liquid and flue gas is 5 ~ 20L/Nm
3; The absorption liquid that absorption tower is discharged mixes with the ratio of 0.6:1 ~ 1.5:1 with seawater, and discharges after air aeration and neutralizing treatment.But the method obviously has the one side of its significant limitation, first vast hinterland can be used without seawater, and secondly, the saturated sulfurous gas of flyash and Absorption by Sea Water is difficult to process.
State Intellectual Property Office of the People's Republic of China website also discloses a kind of method of sulfur dioxide absorption, adopt sodium sulphite as absorption agent, absorption liquid obtains byproduct five water Sulfothiorine through filtration, evaporation, decolouring, crystallization, separation.Although the method solves hydrogen sulfide absorption problem, bring the process problem of solid waste after absorbing.
Summary of the invention
The technical problem to be solved in the present invention is, overcomes the deficiencies in the prior art, provides one to be applied to sulfur dioxide absorption, assimilated efficiency is high, absorption process does not need seawater, absorb after do not produce refuse and through heating and reproducible functionalized ion liquid.
Technical scheme of the present invention is:
A kind of functionalized ion liquid, structural formula is as shown in the formula shown in (I):
Y
-
（I）
R in formula
1=-H, R
2=-H, R
3=-CH
3;
Y is selected from fluoroform sulfonamide anions, shown in the following formula II of structural formula:
(Ⅱ)
Or ethynyl cyanamide negatively charged ion, shown in the following formula III of structural formula:
(Ⅲ)。
The purposes of described functionalized ion liquid is for absorbing sulfur dioxide in exhaust gas.
The spent air temperture that described functionalized ion liquid absorbs is 5 ~ 35 DEG C.
The dividing potential drop of the SO 2 in waste gas that described functionalized ion liquid absorbs is 0.001 ~ 0.1MPa.
Described functionalized ion liquid is in sulfurous gas absorption process, the residence time of sulfurous gas in ionic liquid is adjusted by adjustment gas flow rate, the residence time is short does not reach assimilation effect, overstand can waste soak time, and assimilation effect does not have and rises appreciably, the therefore suitable residence time is 2 ~ 20 minutes.
Described functionalized ion liquid can reach desorb by heating after saturated to sulfurous gas absorption, thus reach the object of recycling, the low desorption effect of temperature is poor, and temperature height desorption effect is good but can waste energy, and therefore suitable desorption temperature is 70 ~ 160 DEG C.
Described functionalized ion liquid, in desorption process, can pass into nitrogen to make ionic liquid homogeneous heating in ionic liquid, accelerates the process of ionic liquid regeneration.
Functionalized ion liquid shown in structural formula (I) can be adopted and synthesize with the following method:
(1) 2-methyl-6,9-dihydro purine-6-amine is carried out amido protecting reaction;
(2) step (1) carries out halogenating reaction 20-30 hour by under gained reactant 60-80 DEG C of condition;
(3) by 60-80 DEG C of hydrolysis 2-4 hour under step (2) gained reactant;
(4) by step (3) gained reactant at 50-90 DEG C of reduction vaporization 0.5-10 hour, remove etoh solvent, water and hydrolysate acetic acid;
(5) step (4) products therefrom at room temperature being crossed anionite-exchange resin, is then that solvent and fluoroform sulfonamide or ethynyl cyanamide salt are reacted and prepared ionic liquid with ethanol;
(6) by the ionic liquid of step (5) gained 60-90 DEG C of reduction vaporization 0.5-10 hour in Rotary Evaporators, the water in ethanol and solution is removed; Finally dry 12-24 hour in 60-90 DEG C, drying under reduced pressure case.
Compared with prior art, beneficial effect of the present invention is:
The volatility of ionic liquid is extremely low, makes ionic liquid in absorption process, compares the advantage that usual way has two aspects:
1, the saturated vapor pressure of ionic liquid is extremely low not volatile, and absorption and desorption process losses is few;
2, functionalized ion liquid of the present invention is high to sulfurous gas assimilated efficiency, desorb is reached by simply heating, and reusable after desorb, do not produce refuse after absorption, solve the problem of the refuse process after absorption, do not need seawater to be applicable to each department and promote the use of.
Embodiment
Below by concrete case study on implementation, the invention will be further described.
Described waste gas is with sulfurous gas and nitrogen simulation, and the residence time of described absorption process is adjusted by adjustment gas flow rate, and method of calculation are: the residence time=scrubbing bottle volume/exhaust gas flow.Described ionic liquid absorption is saturated refers to that the scrubbing bottle that ionic liquid is housed continues to pass into waste gas, and weight no longer increases.The concentration of the sulfurous gas absorbed in ionic liquid adopts GB HJ/T56-2000 to detect.
The present invention is applied to the functionalized ion liquid that sulfurous gas absorbs, and its preparation process is:
(1) 1mol2-methyl-6,9-dihydro purine-6-amine, 3mol diacetyl oxide and 4mol ethanol will be added in reaction flask, be heated to backflow under room temperature and carry out amido protecting reaction in 12 hours;
(2) step (1) by gained reactant under 80 DEG C of agitation conditions with monobromethane generation substitution reaction 20 hours;
(3) add 2mol water in step (2) gained reactant, at 60 DEG C, be hydrolyzed 2 hours;
(4) by step (3) gained reactant at 60 DEG C of evaporation under reduced pressure removed ethanol, hydrolysate acetic acid and water;
(5) step (4) products therefrom is at room temperature crossed anionite-exchange resin [DOWEX MONOSPHERE 550A (OH)] and prepare intermediate product alkali ionic liquid, again by the alkali ionic liquid of gained and fluoroform sulfonamide sodium salts A in molar ratio for 1:2 react prepare required ionic liquid (its reaction conditions in etoh solvent, stirring at room temperature 24 hours, be obtained by reacting functionalized ion liquid 1 with fluoroform sulfonamide sodium salts A, its structural formula is
, lower same;
Ionic liquid 2 prepares for step (5) intermediate product alkali ionic liquid and ethynyl cyanamide sodium salt react, and processing condition congenerous ionic liquid 1, its structural formula is
, lower same, above-mentioned desired raw material is all bought from Sigma-Aldrich chemical reagents corporation.
(6) the 60 DEG C of decompressions in Rotary Evaporators of the ionic liquid of step (5) gained are steamed second alcohol and water; Last in 60 DEG C, drying under reduced pressure case dry 24 hours.
Embodiment 1 ~ 5:
Under 20 DEG C of conditions, by the waste gas of different sulfur dioxide partial by be equipped with under 1mol functionalized ion liquid 1(with) scrubbing bottle, the residence time of adjustment absorption process is 10 minutes, absorbs after 10 minutes, and mensuration ionic liquid absorption amount, measurement result is in table 1.
Table 1:
| Embodiment | Sulfur dioxide partial (MPa) | Absorbed dose (SO 2/ ionic liquid) |
| 1 | 0.02 | 3.0 |
| 2 | 0.04 | 3.4 |
| 3 | 0.06 | 3.8 |
| 4 | 0.08 | 4.6 |
| 5 | 0.10 | 5.5 |
Absorbed dose refers to the amount of substance of the sulfurous gas that ionic liquid absorbs and the ratio of ionic liquid amount of substance, lower same.
Embodiment 6 ~ 10:
Under 20 DEG C of conditions, the simulated exhaust of different sulfur dioxide partial passed into and 1mol ionic liquid 2 scrubbing bottle is housed, the residence time of adjustment absorption process is 8 minutes, and absorb after 15 minutes, measurement result is as follows:
| Embodiment | Sulfur dioxide partial (MPa) | Absorbed dose (SO 2/ ionic liquid) |
| 6 | 0.02 | 2.3 |
| 7 | 0.04 | 2.6 |
| 8 | 0.06 | 3.1 |
| 9 | 0.08 | 3.8 |
| 10 | 0.10 | 4.6 |
Embodiment 11 ~ 14:
Be that the simulated exhaust of 0.06MPa passes into 1mol functionalized ion liquid 1 by differing temps, sulfur dioxide partial, the residence time of adjustment absorption process is 15 minutes, and absorb after 10 minutes, measurement result is in table 2.
Table 2:
| Embodiment | Temperature (DEG C) | Absorbed dose (SO 2/ ionic liquid) |
| 11 | 10 | 3.8 |
| 12 | 20 | 3.0 |
| 13 | 30 | 2.2 |
| 14 | 35 | 1.8 |
Embodiment 15 ~ 20
By 20 DEG C, sulfur dioxide partial is that the simulated exhaust of 0.1MPa passes into 1mol functionalized ion liquid 1 respectively, the residence time of absorption process is 10 minutes, absorb saturated after, pass through raised temperature, pass into the nitrogen of 1 liter/min to reach desorb, desorption time 30 minutes, then sulfur dioxide residual quantity in measurement function ionic liquid 1, experimental result is in table 3.
Table 3:
| Embodiment | Raised temperature (DEG C) | Residual quantity (SO 2/ ionic liquid) |
| 15 | 70 | 0.03 |
| 16 | 80 | 0.01 |
| 17 | 90 | 0.002 |
| 18 | 100 | Do not detect |
| 19 | 110 | Do not detect |
| 20 | 125 | Do not detect |
Note: sulfur dioxide residual quantity refers to the ratio of sulfurous gas amount of substance that ionic liquid absorbs and ionic liquid amount of substance.
Embodiment 20 ~ 29:
By 215 DEG C, sulfur dioxide partial is that the waste gas of 0.1MPa passes into the scrubbing bottle that 1 mole of functionalized ion liquid 1 is housed, absorb to saturated, then (desorption temperature 80 DEG C, the nitrogen of 1 liter/min is passed into its desorb, desorption time 30 minutes), and then repeat to absorb to saturated with condition to it, the absorbed dose of measurement function ionic liquid 1 pair of sulfurous gas, repetitive operation 9 times, experimental result is in table 4.
Table 4:
| Embodiment | Absorbed dose (SO 2/ ionic liquid) |
| 20 | 5.5 |
| 21 | 5.6 |
| 22 | 5.5 |
| 23 | 5.5 |
| 24 | 5.4 |
| 25 | 5.6 |
| 26 | 5.4 |
| 27 | 5.5 |
| 28 | 5.5 |
| 29 | 5.6 |
By above-mentioned experimental result, visible ionic liquid has efficient assimilation effect absorbed dose to sulfurous gas and reaches the 5-6 of ionic liquid amount of substance doubly, and repeat performance is good, reuses 10 times, absorptive character have no obvious reduction, have prospect capable of being industrialized.
Claims (7)
1. a functionalized ion liquid, structural formula is as shown in the formula shown in (I):
R in formula
1=-H, R
2=-H, R
3=-CH
3;
Y is selected from fluoroform sulfonamide anions, shown in the following formula II of structural formula:
Or ethynyl cyanamide negatively charged ion, shown in the following formula III of structural formula:
2. a purposes for functionalized ion liquid according to claim 1, is characterized in that: for absorbing sulfur dioxide in exhaust gas.
3. the purposes of functionalized ion liquid according to claim 2, is characterized in that: the spent air temperture absorbed is 5 ~ 35 DEG C.
4. the purposes of functionalized ion liquid according to claim 2, is characterized in that: the dividing potential drop of the sulfurous gas in the waste gas absorbed is 0.02 ~ 0.1MPa.
5. the purposes of functionalized ion liquid according to claim 2, is characterized in that: adjust the residence time of sulfurous gas in ionic liquid by adjustment gas flow rate in absorption process, the residence time is 2 ~ 20 minutes.
6. the purposes of functionalized ion liquid according to claim 2, is characterized in that: after saturated to sulfurous gas absorption, reach desorb by heating, desorption temperature is 70 ~ 160 DEG C.
7. the purposes of functionalized ion liquid according to claim 6, is characterized in that: in desorption process, in ionic liquid, passes into nitrogen.
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103623678A (en) * | 2013-12-04 | 2014-03-12 | 宁波赛茵特科技服务有限公司 | Acid gas collecting medium |
| CN103638778A (en) * | 2013-12-04 | 2014-03-19 | 宁波赛茵特科技服务有限公司 | Sulfur dioxide gas collection medium |
| CN103816788A (en) * | 2014-02-14 | 2014-05-28 | 山东紫晶光电新材料有限公司 | Gas purifying technology utilizing double-dielectric barrier discharge plasma |
| CN103816789A (en) * | 2014-02-14 | 2014-05-28 | 山东紫晶光电新材料有限公司 | Alkaline denitration absorbent |
| CN103816783A (en) * | 2014-02-14 | 2014-05-28 | 山东紫晶光电新材料有限公司 | Desulfurization and denitration technology utilizing double-dielectric barrier discharge plasma |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102531991A (en) * | 2011-12-23 | 2012-07-04 | 中国科学院过程工程研究所 | Novel multi-amino functionalized ionic liquid and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102531991A (en) * | 2011-12-23 | 2012-07-04 | 中国科学院过程工程研究所 | Novel multi-amino functionalized ionic liquid and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| A fast and highly efficient protocol for Michael addition of N-heterocycles to a,b-unsaturated compound using basic ionic liquid [bmIm]OH as catalyst and green solvent;Jian-Ming Xu et al;《Tetrahedron》;20061130;第63卷;986-990 * |
| 离子液体在有机合成中的应用研究进展;应安国等;《有机化学》;20081231;第28卷(第12期);2081-2094 * |
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