CN1820830A - Composite support liquid film and its preparing method - Google Patents
Composite support liquid film and its preparing method Download PDFInfo
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- CN1820830A CN1820830A CN 200610033076 CN200610033076A CN1820830A CN 1820830 A CN1820830 A CN 1820830A CN 200610033076 CN200610033076 CN 200610033076 CN 200610033076 A CN200610033076 A CN 200610033076A CN 1820830 A CN1820830 A CN 1820830A
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Abstract
The present invention discloses a kind of compositely supported liquid film and its preparation process. The compositely supported liquid film is a three-layered structure, including one middle porous support layer with liquid film phase of 20-45 % concentration LiCl solution possessing high hydroscopicity and low volatility; and two superthin film layers separately on two sides of hydrophobic polyvinylidene fluoride film to protect the liquid film. The compositely supported liquid film may be prepared through one of three processes, including adhering process, dry solution depositing process and wet solution depositing process. The compositely supported liquid film of the present invention and product may be applied widely in water treatment, fresh wind all heat recovering, energy saving air conditioner, chemical metallurgy and other fields.
Description
Technical field
The invention belongs to air dewetting and the wet recovery field of heat, be specifically related to a kind of be used to realize air dewetting and wet composite support liquid film that reclaims of heat and preparation method thereof.
Background technology
At present, because people more and more pay attention to the quality of room air, and seek a kind of wet removal process of air dewetting and heat that can make and carry out continuously, no etching problem need not switch movement-less part by valve, the system reliability height, easy care, energy consumption is little, low dehumidifying that waits of maintenance cost and the wet recovery method of heat.And this membrane method dehumidifying and heat are wet just reclaims and tradition dehumidifying and the wet recovery method of heat and compare institute and have advantage.
Traditional air dehumidification method comprises cooling method dehumidifying, solid absorbent dehumidifying and liquid desiccant dehumidifying.Cooling method dehumidifying is that humid air is cooled to below the dew-point temperature, removes from air after making airborne water vapor condensation.The cooling method dehumidifying can not reach very low dew point, and it need consume lot of energy and cool off air, makes water vapor condensation and takes away the heat that condensation produces.The solid absorbent dehumidifying is to utilize the method for some solid absorbent moisture absorption to dehumidify, as silica gel, aluminium oxide, calcium chloride etc. steam there is strong suction-operated, when humid air flows through these hygroscopic agents and piles up the packed bed that forms, airborne steam just is removed, and reaches the purpose of dehumidifying.The disadvantage of solid absorbent dehumidifying is these solid absorbent regeneration difficulties, and the moisture absorption dehydrating unit is generally all very complicated, and the volume ratio of equipment is huger, and cost is also high, and these reasons make their application be subjected to certain restriction.The liquid desiccant dehumidifying is to utilize some to have hygroscopic solution to absorb airborne moisture and reach the dehumidifying purpose.Liquid dehumidifying regeneration easily, shortcoming is to handle air directly to contact with liquid desiccant, causes that easily air carries hygroscopic agent secretly, further causes the corrosion of pipeline and equipment.
The wet recovery of the heat of air is actually the full recuperation of heat of new wind, promptly between new wind air channel and indoor exhaust wind air channel, a total-heat exchanger is installed, summer, outdoor new wind was often wet and hot, and indoor exhaust wind is done and is cool, new wind and air draft in total-heat exchanger behind heat-shift and the moisture novel wind energy reach the state that approaches room air, saved the fresh air dehumidification required load that freezes; Winter is new air-dry and cold, and indoor exhaust wind is warm and moistening, and through behind the total-heat exchanger, it is wet that new wind warms, and also reaches the state that approaches room air, saves the warming and humidifying power consumption, saves new wind load equally.Because new wind load will account for 20%～40% of air conditioner load, is very great so use the full recuperation of heat of new wind to the meaning of building energy conservation.There are some researches show, adopt the full recuperation of heat of new wind to add the cooling ceiling system, than the annual primary energy of saving of traditional all-air conditioning system more than 20%.After simple conventional fan coil system adds full heat regenerator, also can energy-conservation 9%.
Traditional wet recovery method of air heat comprises metal walled heat exchanger, heat pipe, recuperation of heat runner etc.Wherein metal walled heat exchanger and heat pipe can only reclaim sensible heat, can not reclaim latent heat, though the technology comparative maturity, energy reclaims limited in one's ability, that at present full heat recovery technology adopts in the world is complete hot runner (Energy wheel), also the someone to attempt adopting with paper be the heat exchanger of the medium of exchange.The advantage of these two kinds of technology is to reclaim sensible heat and a part of latent heat simultaneously, improved organic efficiency, still, the runner cost is very high, and contain moving component, poor reliability, new wind and air draft are mixed easily mutually, are that not only organic efficiency is low for the wet recover of heat of media and adopt paper, and mixing and leakage between new wind and the air draft take place easily, more fatal is that condensate water has destructiveness to paper when moving winter, and these shortcomings have all limited their development.
Along with the development of membrane technology, utilize film to carry out air dewetting and also day by day cause people's attention with the wet technology that reclaims of heat.Being used for air dewetting generally is hydrophilic film with the wet film that reclaims of heat, and the kind of film can be organic film, inoranic membrane and liquid film.
The patent No. of announcing on May 22nd, 2003 is that the US Patent specification of WO03041844 proposes to adopt moisture permeable membrane that air is dehumidified, this moisture permeable membrane has very high selection permeability, when the air that contains water vapour passes through this steam blanket in the mode of convection current or adverse current, water vapour will see through this film, realizes dehumidifying.The patent No. of announcing on April 6th, 1999 is that the Japanese patent specification of JP11090194 proposes to adopt polyetherimde films that air is dehumidified, it is a kind of hollow-fibre membrane that this PEI removes wet film, this hollow-fibre membrane is by polyethers, acid imide-PEI, acid imide mixes, the inner surface of this film is coated the layer of polyethylene pyrrolidones or is coated with one deck NMF, this film can suppress the formation in hole effectively, and can improve endurance, the dehumidifying that the Chinese utility model patent specification of the CN2245205Y that on January 15th, 1997 was announced proposes to adopt the heat exchange membrane heat exchanger to carry out air is reclaimed with hot wetting, the material of heat exchange membrane can adopt metal or nonmetallic materials (as plastic sheeting), but this heat exchanger can only reclaim the sensible heat part, can not carry out full recuperation of heat.
Because the diffusion coefficient (10 of solute in liquid
-6～10
-5Cm
2/ s) than the diffusion coefficient (＜10 in solid
-8Cm
2/ s) high several magnitude is so the infiltration rate by liquid film is far above solid film.Just because of this, air is dehumidified and wet recovery of heat has the advantage that inoranic membrane and organic film do not have with liquid film, fast as speed, the efficient height, cost is low, select effective, easy operating management etc.
Liquid film has two kinds of forms, and a kind of is emulsion liquid film, and with the surfactant stabilizing films, another kind is the liquid film of band supporting layer, is about to liquid film and is filled in the micropore macromolecular structure, and the latter is more stable than the former.Therefore, studying stable composite support liquid film and preparation method thereof has very important and practical meanings, still, utilizes liquid film to carry out air dewetting and yet there are no report with the wet technology that reclaims of heat.
Summary of the invention
The objective of the invention is to overcome the shortcomings and deficiencies of prior art, a kind of wet composite support liquid film that reclaims of air dewetting and heat that is used to realize is provided.
Another object of the present invention is to provide described three kinds of preparation methods that are used to realize air dewetting and the wet composite support liquid film that reclaims of heat.
Composite support liquid film of the present invention is the film with three-decker, and the centre is the porous supporting body layer, and both sides are ultra-thin cortex; The liquid film phase has been fixed in described porous supporting body layer the inside, and ultra-thin cortex is a polyvinylidene fluoride film; The thickness of described porous supporting body layer is 50～100 μ m, and the thickness of ultra-thin cortex is 10～20 μ m.
Described porous supporting body layer is the porous hydrophilic polymeric membrane, as: poly-CAM, nitrocellulose filter, carbonic acid cellulose membrane, cellulose mixture film, polysulfones or polyimide film etc.; Described liquid film is that mass fraction is 20%～45% LiCl solution mutually, has strong wettability power and difficult volatility; Described ultra-thin cortex is a polyvinylidene fluoride film, is a kind of hydrophobic film, and composite support liquid film is shielded.
Composite support liquid film of the present invention has three kinds of preparation methods, is respectively mull technique, dry method solution-deposition method and wet method solution-deposition method.
Adopt mull technique to prepare described composite support liquid film, its step is as follows:
Under (1) 20～30 ℃, the preparation mass fraction is 20%～45% LiCl solution in an airtight glass container, and stirs, and the LiCl solution of being prepared is the liquid film phase;
(2) be thickness that the porous hydrophilic polymeric membrane of 50～100 μ m carries out 1～3 hour vacuum degassing again, porous hydrophilic polymeric membrane after the degasification is immersed in the above-mentioned liquid film Xiangli that has prepared, take out and be placed on one after 15～30 hours with on the clean glassware of alcohol wash, unnecessary LiCl solution is with paper handkerchief wiping slowly on the porous hydrophilic polymeric membrane surface, and this process is the infiltration fixation procedure of porous supporting body layer to the liquid film phase;
Described porous hydrophilic polymeric membrane is poly-CAM, nitrocellulose filter, carbonic acid cellulose membrane, cellulose mixture film, polysulfones or polyimide film etc.;
(3) on two surfaces of the porous supporting body layer of having fixed the liquid film phase, smear polyvinyl chloride glue, and on a surface of the thick ultra-thin cortex of Kynoar of 10～20 μ m, smear above-mentioned polyvinyl chloride glue simultaneously, both sticking together tightly, this process is the bonding process then;
(4) at last the above-mentioned composite membrane that has bondd is placed on the ventilation of carrying out in the ventilating kitchen 15～30 hours, the composite membrane after the ventilation is finished film.
Adopt the dry method solution-deposition method to prepare described composite support liquid film, its step is as follows:
Under (1) 20～30 ℃, the preparation mass fraction is 20%～45% LiCl solution in an airtight glass container, and stirs, and this LiCl solution is the liquid film phase;
(2) be thickness that the porous hydrophilic polymeric membrane of 50～100 μ m carries out 1～3 hour vacuum degassing again, porous hydrophilic polymeric membrane after the degasification is immersed in the above-mentioned liquid film Xiangli that has prepared, take out and be placed on one after 15～30 hours with on the clean glassware of alcohol wash, unnecessary LiCl solution is with paper handkerchief wiping slowly on the porous hydrophilic polymeric membrane surface, and this process is the infiltration fixation procedure of porous supporting body layer to the liquid film phase;
Described porous hydrophilic polymeric membrane is poly-CAM, nitrocellulose filter, carbonic acid cellulose membrane, cellulose mixture film, polysulfones or polyimide film etc.;
(3) 1～3 gram Kynoar is dissolved in 20～50ml dimethyl sulfoxide (DMSO) or the dimethylacetylamide, adds 0.2～1.0 grams lithium chloride and do additive, and the back that stirs place 2～5 days stand-by, this process is the process for preparation of casting solution;
(4) casting solution that will prepare is coated to the above-mentioned both sides of having fixed the porous supporting body layer of liquid film phase, composite membrane after the coating places under 50～100 ℃ of temperature and evaporated 15～30 minutes, drying was 1～2 day under composite membrane after the evaporation placed 20～30 ℃ again, and dried composite membrane is finished film.
Adopt the wet method solution-deposition method to prepare described composite support liquid film, its step is as follows:
Under (1) 20～30 ℃, the preparation mass fraction is 20%～45% LiCl solution in an airtight glass container, and stirs, and this LiCl solution is the liquid film phase;
(2) be thickness that the porous hydrophilic polymeric membrane of 50～100 μ m carries out 1～3 hour vacuum degassing again, porous hydrophilic polymeric membrane after the degasification is immersed in the above-mentioned liquid film Xiangli that has prepared, take out and be placed on one after 15～30 hours with on the clean glassware of alcohol wash, unnecessary LiCl solution is with paper handkerchief wiping slowly on the porous hydrophilic polymeric membrane surface, and this process is the infiltration fixation procedure of porous supporting body layer to the liquid film phase;
Described porous hydrophilic polymeric membrane is poly-CAM, nitrocellulose filter, carbonic acid cellulose membrane, cellulose mixture film, polysulfones or polyimide film etc.;
(3) 5～7 gram Kynoar are dissolved in the dimethylacetylamide of 50ml 2～5%, add 0.2～1.0 grams lithium chloride and do additive, and the back placement slaking in 2～3 days that stirs, this process is the process for preparation of casting solution;
(4) be 20～30 ℃ in temperature then, humidity is under 40～80% the condition, the above-mentioned casting solution that has prepared to be coated to the above-mentioned both sides of having fixed the how empty support body layer of liquid film phase, and to volatilize 15～30 hours, and this process is the coating deposition process;
(5) applied deposition good composite membrane is put into the water of 40～80 ℃ of coagulating baths above-mentioned, with the film water rinse, the film after the rinsing is cold soaking 15～30 hours again, and the film behind the cold soaking is finished film.
The present invention compared with prior art has following beneficial effect:
(1) composite support liquid film of the present invention is because LiCl solution liquid film phase has been fixed in its porous supporting body layer the inside, test shows to this composite support liquid film, under the same experiment condition, the steam exchange efficiency of this composite support liquid film (newly, between the air draft) is higher by 23%～100% than the mixed cellulose hydrophilic membrane of the solid of the condition of equivalent thickness that does not contain the liquid film phase;
(2) the present invention adopts mull technique to prepare described composite support liquid film, and compared with prior art, this method has that technology is simple, easy to operate, equipment investment is few and advantage such as energy-conservation;
(3) the present invention adopts dry method or wet method solution-deposition method to prepare described composite support liquid film, compared with prior art, this method has that technology is simple, equipment cost is low, between different layers in conjunction with closely, and the cortex of the composite support liquid film of being made is ultra-thin, can reach 10 μ m thickness.
Description of drawings
Fig. 1 is the structural representation that is used to realize air dewetting and the wet composite support liquid film that reclaims of heat of the present invention;
Fig. 2 is the dehumidifying process figure of composite support liquid film shown in Figure 1.
Fig. 3 is the wet total-heat exchanger that reclaims of heat that contains composite support liquid film.
Among the figure: the ultra-thin cortex 3-of 1-porous supporting body layer 2-liquid film phase 4-air compressor 5-composite support liquid film assembly
The specific embodiment
The invention will be further described below in conjunction with accompanying drawing.
As shown in Figure 1, composite support liquid film of the present invention is the film with three-decker, and the centre is a porous supporting body layer 1, and both sides are ultra-thin cortex 2; Liquid film phase 3 has been fixed in porous supporting body layer 1 the inside, and ultra-thin cortex 2 is polyvinylidene fluoride films; The thickness of porous supporting body layer 1 is 50～100 μ m, and the thickness of ultra-thin cortex 2 is 10～20 μ m.
Porous supporting body layer 1 is the porous hydrophilic polymeric membrane, as: poly-CAM, nitrocellulose filter, carbonic acid cellulose membrane, cellulose mixture film, polysulfones or polyimide film etc.; Liquid film phase 3 is that mass fraction is 20%～45% LiCl solution, has strong wettability power and difficult volatility; Ultra-thin cortex 2 is polyvinylidene fluoride films, is a kind of hydrophobic film, and composite support liquid film is shielded.
As shown in Figure 2, the dehumidifying process of composite support liquid film of the present invention: unstripped gas at first enters air compressor 4 and compresses, unstripped gas after the compression enters composite support liquid film assembly 5 again, 5 li of composite support liquid film assemblies, after the steam permeable membrane in the unstripped gas, steam and remove moisture and discharge by the above and below of composite support liquid film assembly 5 respectively.
As shown in Figure 3, the wet total-heat exchanger that reclaims of heat that contains composite support liquid film of the present invention.Outdoor new wind and indoor exhaust wind enter this total-heat exchanger that contains composite support liquid film, in the total-heat exchanger the inside of containing composite support liquid film, outdoor new wind and indoor exhaust wind are carried out the exchange of heat and moisture, after the exchange more respectively in the inlet chamber and be discharged to outdoor.
When utilizing this composite support liquid film to dehumidify with the wet recovery of heat to air, can realize dehumidification rate more than 90%, the sensible heat organic efficiency is more than 0.9, and the latent heat organic efficiency is more than 0.85.
One, adopt mull technique to prepare composite support liquid film.
Under (1) 25 ℃, the preparation mass fraction is 30% LiCl solution in an airtight glass container, and stirs, and the LiCl solution of being prepared is described liquid film phase;
(2) be thickness that the porous hydrophilic polymeric membrane of 80 μ m carries out 2 hours vacuum degassing again, porous hydrophilic polymeric membrane after the degasification is immersed in the above-mentioned liquid film Xiangli that has prepared, take out and be placed on one after 15 hours with on the clean glassware of alcohol wash, unnecessary LiCl solution is with paper handkerchief wiping slowly on the porous hydrophilic polymeric membrane surface, and this process is the infiltration fixation procedure of porous supporting body layer to the liquid film phase;
Above-mentioned porous hydrophilic polymeric membrane is poly-CAM, nitrocellulose filter, carbonic acid cellulose membrane, cellulose mixture film, polysulfones or polyimide film;
(3) on two surfaces of the porous supporting body layer of having fixed the liquid film phase, brush polyvinyl chloride glue then, and on a surface of the thick ultra-thin cortex of Kynoar of 20 μ m, brush simultaneously and state polyvinyl chloride glue, both sticking together tightly, this process is the bonding process then;
(4) at last the above-mentioned composite membrane that has bondd is placed on the ventilation of carrying out in the ventilating kitchen 15 hours, the composite membrane after the ventilation is finished film.
Under (1) 30 ℃, the preparation mass fraction is 45% LiCl solution in an airtight glass container, and stirs, and the LiCl solution of being prepared is described liquid film phase;
(2) be thickness that the porous hydrophilic polymeric membrane of 100 μ m carries out 3 hours vacuum degassing again, porous hydrophilic polymeric membrane after the degasification is immersed in the above-mentioned liquid film Xiangli that has prepared, take out and be placed on one after 30 hours with on the clean glassware of alcohol wash, unnecessary LiCl solution is with paper handkerchief wiping slowly on the porous hydrophilic polymeric membrane surface, and this process is the infiltration fixation procedure of porous supporting body layer to the liquid film phase;
Above-mentioned porous hydrophilic polymeric membrane is poly-CAM, nitrocellulose filter, carbonic acid cellulose membrane, cellulose mixture film, polysulfones or polyimide film;
(3) on two surfaces of the porous supporting body layer of having fixed the liquid film phase, brush polyvinyl chloride glue then, and on a surface of the thick ultra-thin cortex of Kynoar of 10 μ m, brush simultaneously and state polyvinyl chloride glue, both sticking together tightly, this process is the bonding process then;
(4) at last the above-mentioned composite membrane that has bondd is placed on the ventilation of carrying out in the ventilating kitchen 30 hours, the composite membrane after the ventilation is finished film.
Under (1) 20 ℃, the preparation mass fraction is 20% LiCl solution in an airtight glass container, and stirs, and the LiCl solution of being prepared is described liquid film phase;
(2) be thickness that the porous hydrophilic polymeric membrane of 50 μ m carries out 1 hour vacuum degassing again, porous hydrophilic polymeric membrane after the degasification is immersed in the above-mentioned liquid film Xiangli that has prepared, take out and be placed on one after 25 hours with on the clean glassware of alcohol wash, unnecessary LiCl solution is with paper handkerchief wiping slowly on the porous hydrophilic polymeric membrane surface, and this process is the infiltration fixation procedure of porous supporting body layer to the liquid film phase;
Above-mentioned porous hydrophilic polymeric membrane is poly-CAM, nitrocellulose filter, carbonic acid cellulose membrane, cellulose mixture film, polysulfones or polyimide film;
(3) on two surfaces of the porous supporting body layer of having fixed the liquid film phase, brush polyvinyl chloride glue then, and on a surface of the thick ultra-thin cortex of Kynoar of 13 μ m, smear above-mentioned polyvinyl chloride glue simultaneously, both sticking together tightly, this process is the bonding process then;
(4) at last the above-mentioned composite membrane that has bondd is placed on the ventilation of carrying out in the ventilating kitchen 20 hours, the composite membrane after the ventilation is finished film.
Two, adopt the dry method solution-deposition method to prepare composite support liquid film.
Embodiment 4
Under (1) 25 ℃, the preparation mass fraction is 30% LiCl solution in an airtight glass container, and stirs, and this LiCl solution is the liquid film phase;
(2) be thickness that the porous hydrophilic polymeric membrane of 80 μ m carries out 2 hours vacuum degassing again, porous hydrophilic polymeric membrane after the degasification is immersed in the above-mentioned liquid film Xiangli that has prepared, take out and be placed on one after 15 hours with on the clean glassware of alcohol wash, unnecessary LiCl solution is with paper handkerchief wiping slowly on the porous hydrophilic polymeric membrane surface, and this process is the infiltration fixation procedure of porous supporting body layer to the liquid film phase;
Above-mentioned porous hydrophilic polymeric membrane is poly-CAM, nitrocellulose filter, carbonic acid cellulose membrane, cellulose mixture film, polysulfones or polyimide film;
(3) then 1 gram Kynoar is dissolved in 20ml dimethyl sulfoxide (DMSO) or the dimethylacetylamide, adds 0.2 grams lithium chloride and do additive, and the back that stirs place 2 days stand-by, this process is the process for preparation of casting solution;
(4) casting solution that will prepare at last is coated to the above-mentioned both sides of having fixed the porous supporting body layer of liquid film phase, composite membrane after the coating places under 50 ℃ of temperature and evaporated 15 minutes, drying was 1 day under composite membrane after the evaporation placed 20 ℃ again, and dried composite membrane is finished film.
Embodiment 5
Under (1) 30 ℃, the preparation mass fraction is 45% LiCl solution in an airtight glass container, and stirs, and this LiCl solution is the liquid film phase;
(2) be thickness that the porous hydrophilic polymeric membrane of 100 μ m carries out 3 hours vacuum degassing again, porous hydrophilic polymeric membrane after the degasification is immersed in the above-mentioned liquid film Xiangli that has prepared, take out and be placed on one after 30 hours with on the clean glassware of alcohol wash, unnecessary LiCl solution is with paper handkerchief wiping slowly on the porous hydrophilic polymeric membrane surface, and this process is the infiltration fixation procedure of porous supporting body layer to the liquid film phase;
Above-mentioned porous hydrophilic polymeric membrane is poly-CAM, nitrocellulose filter, carbonic acid cellulose membrane, cellulose mixture film, polysulfones or polyimide film;
(3) then 2 gram Kynoar are dissolved in 30ml dimethyl sulfoxide (DMSO) or the dimethylacetylamide, add 0.5 grams lithium chloride and do additive, and the back that stirs place 3 days stand-by, this process is the process for preparation of casting solution;
(4) casting solution that will prepare at last is coated to the above-mentioned both sides of having fixed the porous supporting body layer of liquid film phase, composite membrane after the coating places under 70 ℃ of temperature and evaporated 20 minutes, drying was 30 hours under composite membrane after the evaporation placed 25 ℃ again, and dried composite membrane is finished film.
Embodiment 6
Under (1) 20 ℃, the preparation mass fraction is 20% LiCl solution in an airtight glass container, and stirs, and this LiCl solution is the liquid film phase;
(2) be thickness that the porous hydrophilic polymeric membrane of 50 μ m carries out 1 hour vacuum degassing again, porous hydrophilic polymeric membrane after the degasification is immersed in the above-mentioned liquid film Xiangli that has prepared, take out and be placed on one after 25 hours with on the clean glassware of alcohol wash, unnecessary LiCl solution is with paper handkerchief wiping slowly on the porous hydrophilic polymeric membrane surface, and this process is the infiltration fixation procedure of porous supporting body layer to the liquid film phase;
Above-mentioned porous hydrophilic polymeric membrane is poly-CAM, nitrocellulose filter, carbonic acid cellulose membrane, cellulose mixture film, polysulfones or polyimide film;
(3) then 3 gram Kynoar are dissolved in 50ml dimethyl sulfoxide (DMSO) or the dimethylacetylamide, add 1.0 grams lithium chlorides and do additive, and the back that stirs place 5 days stand-by, this process is the process for preparation of casting solution;
(4) casting solution that will prepare at last is coated to the above-mentioned both sides of having fixed the porous supporting body layer of liquid film phase, composite membrane after the coating places under 100 ℃ of temperature and evaporated 15 minutes, drying was 2 days under composite membrane after the evaporation placed 30 ℃ again, and dried composite membrane is finished film.
Three, adopt the wet method solution-deposition method to prepare composite support liquid film.
Embodiment 7
Under (1) 25 ℃, the preparation mass fraction is 30% LiCl solution in an airtight glass container, and stirs, and this LiCl solution is the liquid film phase;
(2) be thickness that the porous hydrophilic polymeric membrane of 80 μ m carries out 2 hours vacuum degassing again, porous hydrophilic polymeric membrane after the degasification is immersed in the above-mentioned liquid film Xiangli that has prepared, take out and be placed on one after 15 hours with on the clean glassware of alcohol wash, unnecessary LiCl solution is with paper handkerchief wiping slowly on the porous hydrophilic polymeric membrane surface, and this process is the infiltration fixation procedure of porous supporting body layer to the liquid film phase;
Above-mentioned porous hydrophilic polymeric membrane is poly-CAM, nitrocellulose filter, carbonic acid cellulose membrane, cellulose mixture film, polysulfones or polyimide film;
(3) again 6 gram Kynoar are dissolved in the dimethylacetylamide of 50ml 3%, add 0.5 grams lithium chloride and do additive, and the back placement slaking in 3 days that stirs, this process is the process for preparation of casting solution;
(4) be 25 ℃ in temperature then, humidity is under 70% the condition, the above-mentioned casting solution that has prepared to be coated to the above-mentioned both sides of having fixed the how empty support body layer of liquid film phase, and to volatilize 25 hours, and this process is the coating deposition process;
(5) at last the above-mentioned good composite membrane that applied deposition is put into the water of 50 ℃ of solidification liquids, with the film water rinse, the film after the rinsing is cold soaking 20 hours again, and the film behind the cold soaking is finished film.
Embodiment 8
Under (1) 30 ℃, the preparation mass fraction is 45% LiCl solution in an airtight glass container, and stirs, and this LiCl solution is the liquid film phase;
(2) be thickness that the porous hydrophilic polymeric membrane of 100 μ m carries out 3 hours vacuum degassing again, porous hydrophilic polymeric membrane after the degasification is immersed in the above-mentioned liquid film Xiangli that has prepared, take out and be placed on one after 30 hours with on the clean glassware of alcohol wash, unnecessary LiCl solution is with paper handkerchief wiping slowly on the porous hydrophilic polymeric membrane surface, and this process is the infiltration fixation procedure of porous supporting body layer to the liquid film phase;
Above-mentioned porous hydrophilic polymeric membrane is poly-CAM, nitrocellulose filter, carbonic acid cellulose membrane, cellulose mixture film, polysulfones or polyimide film;
(3) again 5 gram Kynoar are dissolved in the dimethylacetylamide of 50ml 2%, add 0.2 grams lithium chloride and do additive, and the back placement slaking in 2 days that stirs, this process is the process for preparation of casting solution;
(4) be 20 ℃ in temperature then, humidity is under 40% the condition, the above-mentioned casting solution that has prepared to be coated to the above-mentioned both sides of having fixed the porous supporting body layer of liquid film phase, and to volatilize 15 hours, and this process is the coating deposition process;
(5) at last the above-mentioned good composite membrane that applied deposition is put into the water of 40 ℃ of solidification liquids, with the film water rinse, the film after the rinsing is cold soaking 15 hours again, and the film behind the cold soaking is finished film.
Embodiment 9
Under (1) 20 ℃, the preparation mass fraction is 20% LiCl solution in an airtight glass container, and stirs, and this LiCl solution is the liquid film phase;
(2) be thickness that the porous hydrophilic polymeric membrane of 50 μ m carries out 1 hour vacuum degassing again, porous hydrophilic polymeric membrane after the degasification is immersed in the above-mentioned liquid film Xiangli that has prepared, take out and be placed on one after 25 hours with on the clean glassware of alcohol wash, unnecessary LiCl solution is with paper handkerchief wiping slowly on the porous hydrophilic polymeric membrane surface, and this process is the infiltration fixation procedure of porous supporting body layer to the liquid film phase;
Above-mentioned porous hydrophilic polymeric membrane is poly-CAM, nitrocellulose filter, carbonic acid cellulose membrane, cellulose mixture film, polysulfones or polyimide film;
(3) again 7 gram Kynoar are dissolved in the dimethylacetylamide of 50ml 5%, add 1.0 grams lithium chlorides and do additive, and the back placement slaking in 60 hours that stirs, this process is the process for preparation of casting solution;
(4) be 30 ℃ in temperature then, humidity is under 80% the condition, the above-mentioned casting solution that has prepared to be coated to the above-mentioned both sides of having fixed the porous supporting body layer of liquid film phase, and to volatilize 30 hours, and this process is the coating deposition process;
(5) at last the above-mentioned good composite membrane that applied deposition is put into the water of 80 ℃ of solidification liquids, with the film water rinse, the film after the rinsing is cold soaking 15 hours again, and the film behind the cold soaking is finished film.
Composite support liquid film that the present invention obtained and goods can be widely used in various fields, as: fields such as water technology, the new full heat recovery technology of wind, air conditioner energy saving technology, chemical industry metallurgical, environmental protection, Biochemical Engineering.
Claims (10)
1. a composite support liquid film is the film with three-decker, is the porous supporting body layer in the middle of it is characterized in that, both sides are ultra-thin cortex; The liquid film phase has been fixed in described porous supporting body layer the inside, and ultra-thin cortex is a polyvinylidene fluoride film; The thickness of described porous supporting body layer is 50～100 μ m, and the thickness of ultra-thin cortex is 10～20 μ m.
2. composite support liquid film according to claim 1 is characterized in that described porous supporting body layer is the porous hydrophilic polymeric membrane, is poly-CAM, nitrocellulose filter, carbonic acid cellulose membrane, cellulose mixture film, polysulfones or polyimide film.
3. composite support liquid film according to claim 1 and 2 is characterized in that described liquid film is that mass fraction is 20%～45% LiCl solution mutually.
4. composite support liquid film according to claim 3 is characterized in that described ultra-thin cortex is a polyvinylidene fluoride film.
5. method for preparing the described composite support liquid film of claim 4, its step is as follows:
Under (1) 20～30 ℃, the preparation mass fraction is 20%～45% LiCl solution in an airtight glass container, and stirs, and the LiCl solution of being prepared is the liquid film phase;
(2) be thickness that the porous hydrophilic polymeric membrane of 50～100 μ m carries out 1～3 hour vacuum degassing again, porous hydrophilic polymeric membrane after the degasification is immersed in the above-mentioned liquid film Xiangli that has prepared, take out and be placed on one after 15～30 hours with on the clean glassware of alcohol wash, unnecessary LiCl solution is with paper handkerchief wiping slowly on the porous hydrophilic polymeric membrane surface, and this process is the infiltration fixation procedure of porous supporting body layer to the liquid film phase;
(3) on two surfaces of the porous supporting body layer of having fixed the liquid film phase, smear polyvinyl chloride glue, and on a surface of the thick ultra-thin cortex of Kynoar of 10～20 μ m, smear above-mentioned polyvinyl chloride glue simultaneously, both sticking together tightly, this process is the bonding process then;
(4) at last the above-mentioned composite membrane that has bondd is placed on the aeration-drying of carrying out in the ventilating kitchen 15～30 hours, the composite membrane after the ventilation is finished film.
6. method according to claim 5 is characterized in that the porous hydrophilic polymeric membrane in the described step (2) is poly-CAM, nitrocellulose filter, carbonic acid cellulose membrane, cellulose mixture film, polysulfones or polyimide film.
7. method for preparing the described composite support liquid film of claim 4, its step is as follows:
Under (1) 20～30 ℃, the preparation mass fraction is 20%～45% LiCl solution in an airtight glass container, and stirs, and this LiCl solution is the liquid film phase;
(2) be thickness that the porous hydrophilic polymeric membrane of 50～100 μ m carries out 1～3 hour vacuum degassing again, porous hydrophilic polymeric membrane after the degasification is immersed in the above-mentioned liquid film Xiangli that has prepared, take out and be placed on one after 15～30 hours with on the clean glassware of alcohol wash, unnecessary LiCl solution is with paper handkerchief wiping slowly on the porous hydrophilic polymeric membrane surface, and this process is the infiltration fixation procedure of porous supporting body layer to the liquid film phase;
(3) 1～3 gram Kynoar is dissolved in 20～50ml dimethyl sulfoxide (DMSO) or the dimethylacetylamide, adds 0.2～1.0 grams lithium chloride and do additive, and the back that stirs place 2～5 days stand-by, this process is the process for preparation of casting solution;
(4) casting solution that will prepare is coated to the above-mentioned both sides of having fixed the porous supporting body layer of liquid film phase, composite membrane after the coating places under 50～100 ℃ of temperature and evaporated 15～30 minutes, drying was 1～2 day under composite membrane after the evaporation placed 20～30 ℃ again, and dried composite membrane is finished film.
8. method according to claim 7 is characterized in that the porous hydrophilic polymeric membrane in the described step (2) is poly-CAM, nitrocellulose filter, carbonic acid cellulose membrane, cellulose mixture film, polysulfones or polyimide film.
9. method for preparing the described composite support liquid film of claim 4, its step is as follows:
Under (1) 20～30 ℃, the preparation mass fraction is 20%～45% LiCl solution in an airtight glass container, and stirs, and this LiCl solution is the liquid film phase;
(2) be thickness that the porous hydrophilic polymeric membrane of 50～100 μ m carries out 1～3 hour vacuum degassing again, porous hydrophilic polymeric membrane after the degasification is immersed in the above-mentioned liquid film Xiangli that has prepared, take out and be placed on one after 15～30 hours with on the clean glassware of alcohol wash, unnecessary LiCl solution is with paper handkerchief wiping slowly on the porous hydrophilic polymeric membrane surface, and this process is the infiltration fixation procedure of porous supporting body layer to the liquid film phase;
(3) 5～7 gram Kynoar are dissolved in the dimethylacetylamide of 50ml 2～5%, add 0.2～1.0 grams lithium chloride and do additive, and the back placement slaking in 2～3 days that stirs, this process is the process for preparation of casting solution;
(4) be 20～30 ℃ in temperature then, humidity is under 40～80% the condition, the above-mentioned casting solution that has prepared to be coated to the above-mentioned both sides of having fixed the porous supporting body layer of liquid film phase, and to volatilize 15～30 hours, and this process is the coating deposition process;
(5) the above-mentioned good composite membrane that applied deposition is put into the water of 40～80 ℃ of solidification liquids, with the film water rinse, the film after the rinsing is cold soaking 15～30 hours again, and the film behind the cold soaking is finished film.
10. method according to claim 9 is characterized in that the porous hydrophilic polymeric membrane in the described step (2) is poly-CAM, nitrocellulose filter, carbonic acid cellulose membrane, cellulose mixture film, polysulfones or polyimide film.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100486919C (en) * | 2007-05-22 | 2009-05-13 | 同济大学 | Method for preparing semiconductor nano-material and processing organic-inorganic wastewater synchronously |
| CN103411267A (en) * | 2013-07-15 | 2013-11-27 | 叶立英 | Method and system for total heat exchange based on films and moisture absorption solution |
| CN105597556A (en) * | 2016-03-02 | 2016-05-25 | 山东美诺邦马节能科技有限公司 | High-thermal-conductivity compound supported liquid membrane and preparation method thereof |
| CN105597566A (en) * | 2016-03-04 | 2016-05-25 | 山东美诺邦马节能科技有限公司 | Preparation method and application of novel total heat exchange film |
| CN114471191A (en) * | 2021-12-13 | 2022-05-13 | 华南理工大学 | Anti-adhesion coating composite film with high moisture permeability and preparation method thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4710205A (en) * | 1987-03-16 | 1987-12-01 | Honeywell Inc. | Stabilized liquid films |
| CN2689109Y (en) * | 2004-03-25 | 2005-03-30 | 华南理工大学 | Air heat recovering apparatus |
| CN1563829A (en) * | 2004-03-25 | 2005-01-12 | 华南理工大学 | All air heat recovery method, its appts and application |
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2006
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100486919C (en) * | 2007-05-22 | 2009-05-13 | 同济大学 | Method for preparing semiconductor nano-material and processing organic-inorganic wastewater synchronously |
| CN103411267A (en) * | 2013-07-15 | 2013-11-27 | 叶立英 | Method and system for total heat exchange based on films and moisture absorption solution |
| CN103411267B (en) * | 2013-07-15 | 2016-03-09 | 叶立英 | Based on full-heat exchange method and the system of film and hygroscopic solution |
| CN105597556A (en) * | 2016-03-02 | 2016-05-25 | 山东美诺邦马节能科技有限公司 | High-thermal-conductivity compound supported liquid membrane and preparation method thereof |
| CN105597566A (en) * | 2016-03-04 | 2016-05-25 | 山东美诺邦马节能科技有限公司 | Preparation method and application of novel total heat exchange film |
| CN114471191A (en) * | 2021-12-13 | 2022-05-13 | 华南理工大学 | Anti-adhesion coating composite film with high moisture permeability and preparation method thereof |
| CN114471191B (en) * | 2021-12-13 | 2022-11-04 | 华南理工大学 | Anti-adhesion coating composite film with high moisture permeability and preparation method thereof |
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