CN104923036A - Method for catching sulfur dioxide by adopting halogenated carboxylic acid ion liquid - Google Patents
Method for catching sulfur dioxide by adopting halogenated carboxylic acid ion liquid Download PDFInfo
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- CN104923036A CN104923036A CN201510308506.3A CN201510308506A CN104923036A CN 104923036 A CN104923036 A CN 104923036A CN 201510308506 A CN201510308506 A CN 201510308506A CN 104923036 A CN104923036 A CN 104923036A
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Abstract
The invention discloses a method for catching sulfur dioxide by adopting a halogenated carboxylic acid ion liquid. According to the halogenated carboxylic acid ion liquid, halogen is introduced onto carboxylic acid negative ions of a functionalized ionic liquid, the absorbing capacity of sulfur dioxide is improved by utilization of the action of halogen reinforced onto the negative ions and sulfur dioxide, and the electron absorption property of the halogen on the negative ions is utilized to improve the desorption property of carboxylic acid ion liquid, so that efficient reversible absorption of the sulfur dioxide can be realized.
Description
Technical field
The invention belongs to sulfur dioxide absorption techniques field, be specifically related to a kind of method adopting halogenated carboxylic acid radical ion liquid trap sulfur dioxide.
Background technology
In recent years, along with the fast development of economic society, the sulfur dioxide that coal combustion discharges makes atmospheric environment continuous worsening, acid rain harm aggravation, human survival and ecological environment are had a strong impact on, thus cause the extensive concern of science and industrial quarters both at home and abroad, for this reason, people's an urgent demand controls and reduces the discharge of sulfur dioxide gas.Therefore, new material and the new technology of developing efficiently reversible, economic environmental protection have great importance for sulfur dioxide absorption gas.
At present, the traditional handicraft sulfur dioxide absorption gases such as lime stone, ammonia, organic solvent are utilized to have the advantages such as cost is low, infiltration rate is fast, uptake is large, but the problems such as this type of absorbent exists, and solvent is volatile, corrosivity strong, generate a large amount of low-grade accessory substance, absorbent not easily regenerates, do not meet the principle of sustainable development.
Due to ionic liquid there is good stability, volatility is low, gas dissolution capacity is strong and the advantage such as designability, the industrial absorbent for sulfur dioxide gas provides good alternative.Many researchers adopt experiment and the theory and method research physical solubility of sulfur dioxide gas in different ionic liquid.Such as, Huang etc. determine the performance of the guanidine radicals ionic liquid absorption sulfur dioxide gas containing tetrafluoroborate, bis trifluoromethyl sulfimide root, show that every mole of ionic liquid physical efficiency absorbs 1-2 mole of sulfur dioxide gas at ambient pressure, but under reduced pressure uptake very little (Chem. Commun. 2006,4027).Another kind method adopts the ionic liquid of anionic functional to carry out the chemical absorbing of sulfur dioxide gas, as Han etc. adopts guanidine radicals lactic acid ion liquid to carry out sulfur dioxide absorption gas first, every mole of ionic liquid can absorb sulfur dioxide gas (the Angew. Chem. of 1.7 moles at ambient pressure, Int. Ed. 2004,2415).Recently, azoles base season phosphine type ionic liquid is applied in the chemical absorbing of sulfur dioxide gas by Wang etc., obtains good assimilation effect (J. Am. Chem. Soc. 2011,11916).
But, utilize in the method for anionic functional ionic liquid absorption sulfur dioxide various at present, ubiquity uptake be high not enough, absorb that enthalpy is high, the not easily problem such as desorption, cycle performance difference, have impact on its commercial Application.Therefore, it may be necessary the structural design of anionic functional ionic liquid, both improved the uptake of ionic liquid to sulfur dioxide, reduce again and absorb enthalpy, improve the desorption performance of ionic liquid, thus realize high power capacity and the low energy consumption absorption of sulfur dioxide.
Summary of the invention
The technical problem that the present invention solves there is provided a kind of method adopting halogenated carboxylic acid radical ion liquid trap sulfur dioxide, by introducing halogen on the anion of carboxylic acid functional ionic liquid, the halogen utilizing anion to strengthen and sulfur dioxide are used for improving the uptake of sulfur dioxide, and utilize the electron-withdrawing desorption performance improving ionic liquid of halogen on anion, thus realize the efficient reversible absorption of sulfur dioxide.
The present invention adopts following technical scheme for solving the problems of the technologies described above, a kind of method adopting halogenated carboxylic acid radical ion liquid trap sulfur dioxide, it is characterized in that: with halogenated carboxylic acid radical ion liquid for absorbent is in order to sulfur dioxide absorption gas, in absorption process, absorption gas pressure is 0.001-0.1MPa, absorption temperature is 20-80 DEG C, soak time is 0.5-5h, in desorption process, desorption temperature is 60-120 DEG C, desorption time is 0.5-1.5h, the functionalized ion liquid that described halogenated carboxylic acid radical ion liquid is is anion with the halogenated carboxylic acid compound of deprotonation, and wherein halogenated carboxylic acid compound is bromoacetic acid, fluoroacetic acid, 2-chloro-butyric acid, 2-bromine isovaleric acid, 4-bromocaproic acid, 6-bromocaproic acid, 6-chlorine caproic acid or 10-bromine capric acid, cation is myristyl three hexyl phosphine ion, propyl group three hexyl phosphine ion, butyl three hexyl phosphine ion, ethyl tributylphosphine ion, tetrabutyl phosphine ion, ethylmethylimidazolium ion, butyl methyl imidazol ion or ethyl tributyl ammonium ion.
Halogenated carboxylic acid radical ion liquid of the present invention is preferably myristyl three hexyl phosphine 6-bromocaproic acid.
Halogenated carboxylic acid radical ion liquid of the present invention is tetraalkylphosphonium hydroxide phosphine, dialkyl group hydroxide imidazoles or the tetra-alkyl ammonium hydroxide and halogenated carboxylic acid compound that are formed through anion exchange reaction by tetra-alkyl-phosphonium halide phosphine, dialkyl imidazole halogen salt or quaternary alkylammonium halides, at normal temperatures and pressures by waiting mole neutralization reaction 6-24h to obtain.
Halogenated carboxylic acid radical ion liquid of the present invention and traditional lime stone, ammonia, organic solvent, conventional ionic liquid are compared with other functionalized ion liquid and are had the following advantages: (1) adopts the non-amine type functionalized ion liquid of high stability to be absorbent, avoid loss and the volatilization of system solvent before and after sulfur dioxide absorption gas, obviously accelerate the speed of reaction; (2) owing to introducing the halogen with action site on anion, the halogen utilizing anion to strengthen and the effect of sulfur dioxide gas, make its uptake significantly improve; (3) due to the electron attraction of halogen, disperseed the electric charge on anion, reduced the absorption enthalpy of sulfur dioxide gas, made the easy desorption of the sulfur dioxide gas of absorption.
Detailed description of the invention
Be described in further details foregoing of the present invention by the following examples, but this should be interpreted as that the scope of the above-mentioned theme of the present invention is only limitted to following embodiment, all technology realized based on foregoing of the present invention all belong to scope of the present invention.
Embodiment 1
Choose different types of tetra-alkyl-phosphonium halide phosphine, dialkyl imidazole halogen salt or quaternary alkylammonium halides respectively and form tetraalkylphosphonium hydroxide phosphine, dialkyl group hydroxide imidazoles or tetra-alkyl ammonium hydroxide through anion exchange reaction, the hydroxide of formation is reacted 6-24h different types of halogenated carboxylic acid radical ion liquid namely obtained as shown in table 1 with different types of halogenated carboxylic acid compound according to the ratio that mol ratio is 1:1 respectively at normal temperatures and pressures.
Be in the 5mL glass container of 1cm at internal diameter, add different types of halogenated carboxylic acid radical ion liquid of the above-mentioned preparation of 0.002mol respectively, then slowly sulfur dioxide gas is passed into, flow is 40mL/min, absorption gas pressure is 0.1MPa, and control temperature is 20 DEG C, and soak time is that 0.5h carries out sulfur dioxide absorption, weighed by electronic analytical balance in absorption process, the absorption result of sulfur dioxide gas is as shown in table 1.
The impact that table 1 different types of halogenated carboxylic acid radical ion liquid absorbs sulfur dioxide gas
Wherein mol/mol IL represents the amount of substance (on as follows) of the sulfur dioxide gas that every mole of ionic liquid absorbs.
Embodiment 2
Be in the 5mL glass container of 1cm, add 0.002mol myristyl three hexyl phosphine 6-bromocaproic acid respectively at internal diameter, then slowly sulfur dioxide gas is passed into, flow is 40mL/min, the absorption that different absorption gas pressures, absorption temperature and soak time carry out sulfur dioxide gas is set respectively, weighed by electronic analytical balance in absorption process, the absorption result of sulfur dioxide gas is as shown in table 2.
The different acceptance condition of table 2 is on the impact of myristyl three hexyl phosphine 4-bromocaproic acid sulfur dioxide absorption gas
Compared with table 1, associative list 2 can be found out, absorb the difference of temperature and absorption gas pressure, the uptake of sulfur dioxide gas then has significant change, absorption temperature is higher or absorption gas pressure is lower, the amount of described halogenated carboxylic acid radical ion liquid absorption sulfur dioxide gas is lower, and absorption temperature is lower or absorption gas pressure is higher, and the amount of halogenated carboxylic acid radical ion liquid absorption sulfur dioxide gas is higher.
Embodiment 3
Slowly nitrogen is passed in the myristyl three hexyl phosphine 6-bromocaproic acid of sulfur dioxide absorption gas, flow is 40mL/min, pressure is 0.1MPa, controlling desorption temperature is 120 DEG C, desorption time is 0.5h, and electronic analytical balance is weighed and shown to utilize the sulfur dioxide gas desorption completely of halogenated carboxylic acid radical ion liquid absorption.
Taking variety classes with electronic analytical balance the halogenated carboxylic acid radical ion liquid of sulfur dioxide absorption gas has joined internal diameter is respectively in the 5mL glass container of 1cm, then slowly nitrogen is passed into, flow is 40mL/min, pressure is 0.1MPa, control different desorption temperatures and desorption time, its desorption the results are shown in Table 3.
Table 3 different types of halogenated carboxylic acid radical ion liquid is on the impact of sulfur dioxide gas desorption
Embodiment 4
In order to investigate the Reversible Cycle of halogenated carboxylic acid radical ion liquid in capture sulfur dioxide gas process, sulfur dioxide and nitrogen is alternately passed in myristyl three hexyl phosphine 6-bromocaproic acid ionic liquid, gas flow is 40mL/min, pressure is 0.1MPa, the adsorption and desorption time is 0.5h, controlling adsorption temp is 20 DEG C, controlling desorption temperature is 120 DEG C, carry out 30 circulations, electronic analytical balance sulfur dioxide uptake scope of weighing is 4.30 ~ 4.40 mol/mol IL, uptake does not obviously decline, show that halogenated carboxylic acid radical ion liquid has good Reversible Cycle.
More than show and describe general principle of the present invention, principal character and advantage, without departing from the spirit and scope of the present invention, the present invention also has various changes and modifications, and these changes and improvements all fall into claimed scope of the present invention.
Claims (4)
1. one kind adopts the method for halogenated carboxylic acid radical ion liquid trap sulfur dioxide, it is characterized in that: with halogenated carboxylic acid radical ion liquid for absorbent is in order to sulfur dioxide absorption gas, in absorption process, absorption gas pressure is 0.001-0.1MPa, absorption temperature is 20-80 DEG C, soak time is 0.5-5h, in desorption process, desorption temperature is 60-120 DEG C, desorption time is 0.5-1.5h, the functionalized ion liquid that described halogenated carboxylic acid radical ion liquid is is anion with the halogenated carboxylic acid compound of deprotonation, wherein halogenated carboxylic acid compound is bromoacetic acid, fluoroacetic acid, 2-chloro-butyric acid, 2-bromine isovaleric acid, 4-bromocaproic acid, 6-bromocaproic acid, 6-chlorine caproic acid or 10-bromine capric acid, cation is myristyl three hexyl phosphine ion, propyl group three hexyl phosphine ion, butyl three hexyl phosphine ion, ethyl tributylphosphine ion, tetrabutyl phosphine ion, ethylmethylimidazolium ion, butyl methyl imidazol ion or ethyl tributyl ammonium ion.
2. the method for employing halogenated carboxylic acid radical ion liquid trap sulfur dioxide according to claim 1, is characterized in that: described halogenated carboxylic acid radical ion liquid is myristyl three hexyl phosphine 6-bromocaproic acid.
3. the method for employing halogenated carboxylic acid radical ion liquid trap sulfur dioxide according to claim 1 and 2, it is characterized in that: with myristyl three hexyl phosphine 6-bromocaproic acid for absorbent is in order to sulfur dioxide absorption gas, in absorption process, absorption gas pressure is 0.1MPa, absorbing temperature is 20 DEG C, soak time is 0.5h, the amount of substance of the sulfur dioxide gas that every mole of myristyl three hexyl phosphine 6-bromocaproic acid absorbs is 4.34mol, in desorption process, desorption temperature is 120 DEG C, desorption time is 0.5h, the complete desorption of sulfur dioxide that myristyl three hexyl phosphine 6-bromocaproic acid absorbs.
4. the method for employing halogenated carboxylic acid radical ion liquid trap sulfur dioxide according to claim 1, it is characterized in that: described halogenated carboxylic acid radical ion liquid is tetraalkylphosphonium hydroxide phosphine, dialkyl group hydroxide imidazoles or the tetra-alkyl ammonium hydroxide and halogenated carboxylic acid compound that are formed through anion exchange reaction by tetra-alkyl-phosphonium halide phosphine, dialkyl imidazole halogen salt or quaternary alkylammonium halides, at normal temperatures and pressures by waiting mole neutralization reaction 6-24h to obtain.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105944509A (en) * | 2016-06-27 | 2016-09-21 | 河南师范大学 | Method for capturing sulfur dioxide by using aldehyde-group-containing anion functionalized ionic liquid |
| CN107200787A (en) * | 2017-05-23 | 2017-09-26 | 四川大学 | A kind of imidazoles alginate ionic liquid and its synthetic method |
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| JP2003093835A (en) * | 2001-09-27 | 2003-04-02 | Hitachi Ltd | Regeneration method for gas absorbing liquid and regeneration system for gas absorbing liquid |
| CN102430319A (en) * | 2011-11-09 | 2012-05-02 | 浙江大学 | Method for catching carbon dioxide by adopting alcohol amine type ion liquid |
| CN103127815A (en) * | 2013-02-19 | 2013-06-05 | 浙江大学 | Method of improving trapping performance of sulfur dioxide through halide sulfur function |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003093835A (en) * | 2001-09-27 | 2003-04-02 | Hitachi Ltd | Regeneration method for gas absorbing liquid and regeneration system for gas absorbing liquid |
| CN102430319A (en) * | 2011-11-09 | 2012-05-02 | 浙江大学 | Method for catching carbon dioxide by adopting alcohol amine type ion liquid |
| CN103127815A (en) * | 2013-02-19 | 2013-06-05 | 浙江大学 | Method of improving trapping performance of sulfur dioxide through halide sulfur function |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105944509A (en) * | 2016-06-27 | 2016-09-21 | 河南师范大学 | Method for capturing sulfur dioxide by using aldehyde-group-containing anion functionalized ionic liquid |
| CN107200787A (en) * | 2017-05-23 | 2017-09-26 | 四川大学 | A kind of imidazoles alginate ionic liquid and its synthetic method |
| CN107200787B (en) * | 2017-05-23 | 2019-08-13 | 四川大学 | A kind of imidazoles alginate ionic liquid and its synthetic method |
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