CN102335545B - Dehumidifying agent for air dehumidification, method and device for air dehumidification - Google Patents

Dehumidifying agent for air dehumidification, method and device for air dehumidification Download PDF

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CN102335545B
CN102335545B CN 201010237558 CN201010237558A CN102335545B CN 102335545 B CN102335545 B CN 102335545B CN 201010237558 CN201010237558 CN 201010237558 CN 201010237558 A CN201010237558 A CN 201010237558A CN 102335545 B CN102335545 B CN 102335545B
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ionic liquid
air
solution
cation
regenerator
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CN102335545A (en
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田长青
罗伊默
邵双全
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Technical Institute of Physics and Chemistry of CAS
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Technical Institute of Physics and Chemistry of CAS
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Abstract

The invention discloses a dehumidifying agent for air dehumidification, which is an ionic liquid solution formed by dissolving an ionic liquid with a melting point close to room temperature or lower than room temperature, which is composed of organic positive ions and inorganic negative ions, in water. And further discloses a method and a device for dehumidifying air by using the dehumidifying agent. Compared with the traditional salt solution (aqueous solutions of lithium bromide, lithium chloride, calcium chloride and the like), the invention has the following advantages: 1) the ionic liquid solution is in a liquid state at normal temperature, is mutually soluble with water, cannot be crystallized in operation, and ensures the reliable operation of the system; 2) the water vapor partial pressure of the ionic liquid solution is similar to or lower than that of the traditional dehumidifying salt solution, so that the dehumidifying efficiency is high; 3) the ionic liquid solution has no corrosion to metal equipment such as steel and the like, and the equipment has low cost and long service life; 4) has non-volatility and reduces the pollution to the environment, etc.

Description

Be used for the dehumidizer of air dewetting, the method and apparatus of air dewetting
Technical field
The present invention relates to a kind of dehumidizer for air dewetting, and the method and apparatus that adopts this dehumidizer that air is dehumidified.
Background technology
Along with industrial expansion and growth in the living standard, dehumidifying obtains gradually people's attention and has produced multiple dehumanization method, comprises air themperature is reduced to below dew-point temperature the dehumidification by condensation method that moisture is separated out; Pressurization raises the steam partial pressure of air, the pressurization that steam is separated out; Solid or fluent material that use has wet-out property directly contact with air, realize the dehumidifying of air.Be used widely because the liquid dehumidifying material has the following advantages: (1) is easy to realize isothermal dehumidifying, and irreversible loss is little, and the thermodynamics sophistication is high; (2) can use more low-grade heat energy as drive energy; (3) without larger moving component, simple in structure, be easy to miniaturization; (4) can remove the nuisances such as airborne dust, bacterium, improve air quality.
For liquid dehumidifying commonly used, the performance of dehumidification solution is the key factor that affects liquid dehumidifying air-conditioning system.Desired dehumidizer characteristic has: under identical temperature, concentration, the dehumidizer superficial vapor is pressed lower; Dehumidizer has larger solubility for airborne moisture, can improve like this absorptivity and reduce the consumption of solution dehumidification agent; Dehumidizer does not absorb or absorbs very little when moisture in air is had stronger absorbability substantially to other components in mist, otherwise can not effectively realize separating; Low viscosity to reduce the conveying power consumption of pump, reduces heat transmission resistance; Higher boiling, high condensation heat and the heat of dilution, low-freezing; The dehumidizer stable in properties, low volatility, low-corrosiveness, avirulence; Cheap, easily obtain.
The hygroscopicity solution such as calcium chloride, lithium chloride and lithium bromide are often used as dehumidizer, but the inherent defect of its existence comprises easy crystallization, have corrosivity and contaminated environment etc.
Summary of the invention
Purpose of the present invention at first be to provide a kind of non-volatile, with water dissolve each other non-crystallizable, to the dehumidizer that is used for air dewetting of the metal non-corrosiveness such as iron and steel, high thermal stability, liquid journey wider range, nontoxic odorless, environmentally safe.
Another object of the present invention is to provide a kind of method that adopts above-mentioned dehumidizer that air is dehumidified.
Further aim of the present invention is to provide the device for said method.
In order to achieve the above object, technical scheme of the present invention is as follows:
A kind of dehumidizer for air dewetting, the fusing point that consists of for organic cation and inorganic anion is near room temperature or lower than the ionic liquid solution of the water-soluble rear formation of ionic liquid of room temperature.It is working media that the solution dehumidification technology adopts the ionic liquid solution with humidity conditioning function, utilize moisture absorption and the moisture releasing characteristic of solution that air humidity is controlled, ionic liquid solution and airborne steam partial pressure are poor is the driving gesture of both carrying out moisture transmission.The steam partial pressure of ionic liquid solution used in the present invention is similar or have than its lower steam partial pressure with dehumidifying salting liquid (as lithium bromide, lithium chloride and calcium chloride etc.) at present commonly used.That but the ionic liquid solution that the present invention uses has is non-volatile, with water dissolve each other non-crystallizable, to the characteristics of the metal non-corrosiveness such as iron and steel, high thermal stability, liquid journey wider range (for-40~300 ℃), nontoxic odorless, environmentally safe, therefore use it for dehumidifying, can effectively solve customary salt solution due to the problem with contaminated environment that volatility causes and the high problem of equipment cost that customary salt solution causes more greatly metal protection.
Above-mentioned dehumidizer, wherein said organic cation can be any organic cation with good wet-out property, any one in preferred quaternary ammonium cation, quaternary phosphine cation, glyoxaline cation, pyridylium, thiazole cation, triazole cation, pyrrolin cation, thiazoline cation, guanidine cation, BTA cation and derivative thereof.
Above-mentioned dehumidizer, wherein said inorganic anion can be any inorganic anions with good wet-out property, preferred [BF 4] -, [CF 3SO 3] -, [CH 3COO] -, [CF 3COO] -, [C 3F 7COO] -, [(CF 3S O 2) 2N] -, [(CH 3) 2PO 4] -, [C 3F 7COO] -, [C 4F 9S O 3] -[(C 2F 5SO 2) N] -[(CF 3SO 2) 3C] -In any one.
Above-mentioned dehumidizer, wherein said ionic liquid most preferably is: 1-butyl-3-methyl imidazolium tetrafluoroborate ([BMIM] BF 4), 1-ethyl-3-methylimidazole tetrafluoroborate ([EMIM] BF 4), 1,3-methylimidazole dimethyl phosphate salt ([MMIM] [(CH 3) 2PO 4]), two (trifluoromethyl sulfonyl) imines ([EMIM] [(CF of 1-ethyl-3-methylimidazole quinoline 3SO 2) 2N]), two (trifluoromethyl sulfonyl) imines ([BMIM] [(CF of 1-butyl-3-methylimidazole quinoline 3SO 2) 2N]), 1,3-methylimidazole dimethyl phosphate ([MMIM] [(CH 3) 2PO 4]), 1-butyl-3-methylimidazole diethyl phosphate ([BMIM] [(CH 3) 2PO 4]), 1-ethyl-3-methylimidazole diethyl phosphate ([EMIM] [(CH 3) 2PO 4]), 1-propyl group-3-methyl imidazolium tetrafluoroborate ([C 3MIM] BF 4).
A kind of air dehumidification method, it adopts above-mentioned dehumidizer that air is dehumidified.Concrete grammar can for, adopt the dehumidizer of high concentration contact with air, absorb the solution that moisture becomes low concentration from air, air becomes the lower dry air of humidity after passing through and dehumidifying; The solution circulation that is regenerated as high concentration after the solution of described low concentration evaporates moisture uses.
The air dehumidifier that is used for said method, comprise air dehumidifier, solution pump, solution regenerator, connect in proper order a dehumidifying regeneration cycle by solution line, be provided with the dehumidizer of high concentration in described air dehumidifier, described dehumidizer is the fusing point that consists of of organic cation and inorganic anion near room temperature or lower than the molten salt system that is in a liquid state of the water-soluble rear formation of ionic liquid of room temperature.
Said apparatus, wherein said air dehumidifier are heat insulation-type dehumidifier or internally cooled dehumidifier.In the air dehumidifier of heat insulation-type, when the ionic liquid solution of high concentration absorbed airborne moisture, the vapour-set latent heat of vaporization of meeting releasing water made the temperature of air and ionic liquid solution all raise, and the irreversible loss of moisture absorption process increases.Therefore adopt the air dehumidifier of internally cooled, cooling to moisture absorption process by external source, the isothermal dehumidifying process be can realize, thereby irreversible loss, raising dehumidification rate reduced.The cold water that the low-temperature receiver of internally cooled dehumidifier can adopt cooling water, underground water or high evaporation temperature refrigeration (heat pump) unit that cooling tower produces to produce.For contact area, the raising mass-transfer efficiency that improves ionic liquid solution and air, fill filler in air dehumidifier, in air dehumidifier, filler used can be metal packing or organic filler or combined stuffing.Metal packing can improve heat transfer property when improving mass-transfer efficiency, help to realize isothermal dehumidifying; Organic filler stable performance, long service life; And can adopt the combined stuffing of metal packing and organic filler, to improve the performance and used life of filler.
Said apparatus, wherein said solution regenerator utilizes regenerator etc. for utilizing heat energy to make the apparatus of moisture evaporation as existing heat supply heat supply network regenerator, heat pump heat supply regenerator, solar regenerator, electrical heating regenerator or waste heat/used heat.Improve temperature and the surface water vapor pressure of ionic liquid solution by absorbing outside heat, make moisture wherein be evaporated, solution becomes concentrated solution, recovers wettability power.
Said apparatus can also be provided with the concentrated solution tank between solution regenerator and air dehumidifier.Utilize concentrated solution to carry out accumulation of energy.The solution accumulation of energy is chemical energy, and energy storage density is high, dissipation is few, can be in the situation that thermal source is discontinuous or take full advantage of low-grade energy and can guarantee Systems balanth operation.
Technique scheme has following advantage: by adopt fusing point that special organic cation and inorganic anion consist of near room temperature or lower than the ionic liquid solution of the water-soluble rear formation of ionic liquid of room temperature as dehumidizer, reached and removed effectively, fast the purpose of water in air steam, and 1) dehumidizer is liquid at normal temperatures, dissolve each other with water, being in operation not can crystallization, guarantees system's reliability service; 2) steam partial pressure of ionic liquid solution used is similar or have than its lower steam partial pressure with traditional dehumidifying salting liquid, thereby dehumidification rate is high; 3) without corrosion, equipment cost is low, the life-span is long to hardwares such as iron and steel for ionic liquid solution used; 4) ionic liquid solution used has again fixedness, has reduced the pollution to environment.
Description of drawings
Fig. 1 is the device schematic diagram of embodiment 1;
Fig. 2 is the device schematic diagram of embodiment 2;
Fig. 3 is the solar energy heating/regenerator schematic diagram in embodiment 2;
Fig. 4 is the device schematic diagram of embodiment 3;
Fig. 5 is the device schematic diagram of embodiment 5.
The specific embodiment
Below in conjunction with drawings and Examples, the specific embodiment of the present invention is described in further detail.Following examples are used for explanation the present invention, but are not used for limiting the scope of the invention.
Embodiment 1:
Adopt 1-butyl-3-methyl imidazolium tetrafluoroborate ([BMIM] [BF 4]) the aqueous solution be dehumidizer.
As shown in Figure 1, show according to a kind of air dehumidification method of the present invention and device.this dehumidification system comprises air dehumidifier 1, solution regenerator 2 and solution pump 3, the ionic liquid solution of high concentration enters from the d end ionic liquid solution that becomes low concentration air dehumidifier 1 after the airborne steam of absorption and flows out from a end, it enters solution regenerator 2 from the b end under the effect of solution pump 3 regenerates, the heat that part moisture in the ionic liquid solution of low concentration provides due to regeneration heating device evaporates from the k end and is discharged into environment, the ionic liquid solution of low concentration becomes the ionic liquid solution of high concentration, flow out solution regenerator 2 from the c end, enter next circulation, regenerating medium enters solution regenerator 2 from the e end and carries out flowing out from the f end after the caloic exchange with ionic liquid solution, highly humid air enters air dehumidifier 1 from i end and becomes low humid air after dehumidified and discharge from the j end, lowers the temperature and sends into air-conditioned room after processing, interior cold medium enters from the g end and flows out from the h end after air dehumidifier 1 absorbs the heat of transformation.
Embodiment 2:
Adopt 1-ethyl-3-methylimidazole tetrafluoroborate ([EMIM] [BF 4]) the aqueous solution be dehumidizer.
Fig. 2 shows according to another kind of air dehumidification method of the present invention and device.This system comprises air dehumidifier 1, solution regenerator 2, solar thermal collector 4, heat-collecting pump 5 and concentrated solution tank 6 and solution pump 3, and they carry out dehumidifying to air by the Driven by Solar Energy ionic liquid solution.
The solar energy great advantage is that it has matching in good season, and weather is warmmer, when humidity is larger, and the solar radiation condition is better, and available to add heat also larger; Be a kind of energy of discontinuity due to solar energy, affected by Changes in weather larger, for the operation that guarantees that the solar energy dehumidifier/air-conditioning system can continous-stable, accumulation of energy is a very crucial technology.When system heat sources was more abundant, regenerating by regenerator stored a certain amount of concentrated solution in the concentrated solution tank, discharges into dehumidifier and complete air dewetting when the system heat sources heat supply is not enough, has made up the defective of solar energy as the discontinuity of system heat sources.Simultaneously also can alleviate the contradiction on electric power peak, namely utilize trough-electricity that solution is regenerated, release energy when the peak, complete the air dewetting process.The employing of energy storage equipment can reduce solution system for the demand that continues thermal source, can reduce the design capacity of system simultaneously.
In diagram, solar thermal collector 4 provides heat for regeneration of waste liquor: regenerating medium carries out flowing out from the i end after energy exchange with the ionic liquid solution of low concentration in solution regenerator 2, enter solar thermal collector from the j end under the effect of heat-collecting pump, after absorbing solar radiant heat, temperature raises, flow out from the k end, then the h end from solution regenerator 2 enters, and further processes the ionic liquid solution of low concentration.
As Fig. 3, also can use solar energy heating/regenerator 9 to replace solar thermal collector 4 and solution regenerator 2.Solar energy heating/regenerator 9 has solar energy heating and two kinds of functions of regeneration simultaneously.This device utilizes outdoor air to carry out heat and mass with the ionic liquid solution of low concentration in solar energy heating/regenerator, thereby makes the concentrated regeneration of solution.
In diagram, concentrated solution tank 6, control valve 7 and by-passing valve 8 co-controlling moisture removal: when the ionic liquid solution of the high concentration that flows out from the c of solution regenerator 2 end when processing the required ionic liquid solution amount of highly humid air, can reduce the actual ionic liquid solution flows that enter the high concentration in air processor 1 by regulating by-passing valve 8, be stored in concentrated solution tank 6 ionic liquid solution of part high concentration standby; When the ionic liquid solution of the high concentration that flows out from the c of solution regenerator 2 end when processing the required ionic liquid solution amount of highly humid air, can increase the actual ionic liquid solution flows that enter the high concentration in air processor 1 by regulating control valve 7, be used for practical requirement.
Embodiment 3:
Adopting the aqueous solution of 1,3-methylimidazole dimethyl phosphate salt ([MMIM] [DMP]) is dehumidizer.
Fig. 4 shows according to another air dehumidification method of the present invention and device.This system comprises air dehumidifier 1, solution regenerator 2 (air cooled condenser of a refrigeration unit) and solution pump 3, the condensation heat that provides by the refrigeration unit condenser is regenerated to the ionic liquid solution of low concentration and (is sprayed the ionic liquid solution of low concentration outside this condenser coil, utilize the evaporative condenser principle, thereby recovering condensing heat reaches the regeneration of dehumidification solution).
In diagram, the air cooled condenser of one refrigeration unit provides regeneration of waste liquor heat: the ionic liquid solution of low concentration enters air cooled condenser 2 from the b end, absorptive condenser liberated heat therein, the f end from air cooled condenser 2 after the dry air that the evaporation of part moisture is entered from the e mouth absorbs is discharged; The cold-producing medium that flows out HTHP from compressor 10 flows into from the g mouth of air cooled condenser 2, discharges from the h mouth after discharging therein condensation heat, carries out reducing pressure by regulating flow in choke valve 11, enters evaporimeter 11 evaporation endothermics after becoming the low-temp low-pressure fluid; Medium is held from o and is entered evaporimeter, flows out from the p end after cooling, is used as other purposes as cold water etc. is provided.
Embodiment 4:
Dehumidizer is two (trifluoromethyl sulfonyl) imines ([EMIM] [(CF of 1-ethyl-3-methylimidazole quinoline 3SO 2) 2N]) the aqueous solution.
Fig. 5 shows according to another air dehumidification method of the present invention and device, and the present embodiment is the improvement to embodiment 3.This system comprises air dehumidifier 1, comprise solution regenerator 2 (air cooled condenser of a source pump), comprise interior device for cooling 12 (evaporimeter of a source pump) and solution pump 3, by the condensation heat that the source pump condenser provides, the ionic liquid solution of low concentration is regenerated, the ionic liquid solution of processing by high concentration by the source pump evaporimeter absorbs the heat of transformation that the water in air steam produces.The condenser of source pump such as example two provide the heating source of ionic liquid solution regeneration, also can provide the domestic hot-water simultaneously; In the evaporimeter of source pump, the cold-producing medium evaporation absorbs the heat of transformation, thereby realizes isothermal dehumidifying, improves the dehumidification rate of system, also can provide cold water simultaneously.
In diagram, the part refrigerant that the source pump evaporimeter produces is introduced in air dehumidifier 2 by pipeline, absorb the heat of transformation, keep dehumidification process and carry out under isothermal, improve the dehumidification rate of system.
Embodiment 5-9:
Wherein adopt respectively two (trifluoromethyl sulfonyl) imines ([BMIM] [(CF of 1-butyl-3-methylimidazole quinoline except dehumidizer 3SO 2) 2N]), 1,3-methylimidazole dimethyl phosphate ([MMIM] [(CH 3) 2PO 4]), 1-butyl-3-methylimidazole diethyl phosphate ([BMIM] [(CH 3) 2PO 4]), 1-ethyl-3-methylimidazole diethyl phosphate ([EMIM] [(CH 3) 2PO 4]), 1-propyl group-3-methyl imidazolium tetrafluoroborate ([C 3MIM] BF 4) the aqueous solution outside, all the other are all with embodiment 1.
The above is only the preferred embodiment of the present invention; should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the technology of the present invention principle; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.

Claims (8)

1. a dehumidizer that is used for air dewetting, is characterized in that, described dehumidizer is the fusing point that consists of of organic cation and inorganic anion near room temperature or lower than the ionic liquid solution of the water-soluble rear formation of ionic liquid of room temperature; Described organic cation comprises any one in quaternary ammonium cation, quaternary phosphine cation, glyoxaline cation, pyridylium, thiazole cation, triazole cation, pyrrolin cation, thiazoline cation, guanidine cation, BTA cation and derivative thereof; Described inorganic anion comprises [BF 4] -, [CF 3SO 3] -, [CH 3COO] -, [CF 3COO] -, [C 3F 7COO] -, [(CF 3SO 2) 2N] -, [(CH 3) 2PO 4] -, [C 3F 7COO] -, [C 4F 9SO 3] -, [(C 2F 5SO 2) N] -[(CF 3SO 2) 3C] -In any one.
2. dehumidizer as claimed in claim 1, it is characterized in that, described ionic liquid comprises 1-butyl-3-methyl imidazolium tetrafluoroborate, 1-ethyl-3-methylimidazole tetrafluoroborate, 1, 3-methylimidazole dimethyl phosphate salt, two (trifluoromethyl sulfonyl) imines of 1-ethyl-3-methylimidazole quinoline, two (trifluoromethyl sulfonyl) imines of 1-butyl-3-methylimidazole quinoline, 1, 3-methylimidazole dimethyl phosphate, 1-butyl-3-methylimidazole diethyl phosphate, any one in 1-ethyl-3-methylimidazole diethyl phosphate and 1-propyl group-3-methyl imidazolium tetrafluoroborate.
3. an air dehumidification method, is characterized in that, adopts the described dehumidizer of claim 1 or 2.
4. method as claimed in claim 3, is characterized in that, adopts the ionic liquid solution of high concentration to contact with air, absorbs the ionic liquid solution that moisture becomes low concentration from air, and air becomes the lower dry air of humidity after dehumidifying; The ionic liquid solution that is regenerated as high concentration after the ionic liquid solution of described low concentration evaporates moisture recycles.
5. be used for the air dehumidifier of claim 3 or 4 described methods, it is characterized in that, comprise air dehumidifier (1), solution pump (3), solution regenerator (2), connect in proper order a dehumidifying regeneration cycle by solution line, the dehumidizer that high concentration is arranged in described air dehumidifier (1), described dehumidizer are the fusing point that consists of of organic cation and inorganic anion near room temperature or lower than the ionic liquid solution of the water-soluble rear formation of ionic liquid of room temperature.
6. device as claimed in claim 5, is characterized in that, described air dehumidifier (1) is heat insulation-type dehumidifier or internally cooled dehumidifier.
7. device as claimed in claim 5, is characterized in that, described solution regenerator (2) is that heat supply heat supply network regenerator, heat pump heat supply regenerator, solar regenerator, electrical heating regenerator or waste heat/used heat utilize regenerator.
8. device as claimed in claim 5, is characterized in that, also is provided with concentrated solution tank (6) between solution regenerator (2) and air dehumidifier (1).
CN 201010237558 2010-07-22 2010-07-22 Dehumidifying agent for air dehumidification, method and device for air dehumidification Expired - Fee Related CN102335545B (en)

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