CN101947416A - High-selectivity asymmetric moisture-permeable film as well as preparation method and application thereof - Google Patents
High-selectivity asymmetric moisture-permeable film as well as preparation method and application thereof Download PDFInfo
- Publication number
- CN101947416A CN101947416A CN2010102862298A CN201010286229A CN101947416A CN 101947416 A CN101947416 A CN 101947416A CN 2010102862298 A CN2010102862298 A CN 2010102862298A CN 201010286229 A CN201010286229 A CN 201010286229A CN 101947416 A CN101947416 A CN 101947416A
- Authority
- CN
- China
- Prior art keywords
- film
- permeable membrane
- moisture permeable
- air
- high selectivity
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Abstract
The invention discloses a high-selectivity asymmetric moisture-permeable film as well as a preparation method and application thereof. The preparation method is a one-step method, includes a dry method and a wet method and comprises the following specific steps: (1) dissolving hydrophilic polymer in a corresponding solvent to prepare into a hydrophilic polymer solution, uniformly stirring while heating, standing and defoaming for later use as a film casting solution, wherein the hydrophilic polymer content of the solution is 5-20wt.%; (2) preparing a film by using the dry method or the wet method; and (3) drying the film to obtain the moisture-permeable film. The film has a two-layer structure composed of a porous support layer and an ultrathin skin layer, wherein the porous support layer is a spongy porous cellulose structure with the thickness of 30-80 mu m; and the ultrathin skin layer is a compact cellulose structure with thickness of 2-10 mu m. By using the low poisonous solvent and the nonpoisonous additives, the invention enables the production process to be more environment friendly, effectively simplifies the preparation process and greatly saves the production cost.
Description
Technical field
The invention belongs to the full recuperation of heat of air dewetting and air-conditioning field, be specifically related to a kind of asymmetric moisture permeable membrane of high selectivity of realizing air dewetting and the full recuperation of heat of air-conditioning and preparation method thereof that is used to.
Background technology
Along with epidemic disease SARS, H1N1 etc. threaten people's life, improve indoor air quality and are subjected to people and pay close attention to greatly.New wind circulation remains a kind of effective and economic method and improves indoor air quality.Yet the energy consumption of handling new wind accounts for the 20-40% of air-conditioning total energy consumption, China's south heat wet summer this in addition also much bigger.For conserve energy effectively, recent decades, the HVAC researchers were constantly sought a kind of wet removal process of new wind-heat of low energy consumption.Membrane method dehumidifying and embrane method heat is wet to be reclaimed because no etching problem need not valve switching, movement-less part, the system reliability height, and easy care, advantage such as energy consumption is little has caused the very big interest of researcher.
Air-to-air total heat exchanger is the technology of a key of the full recuperation of heat of new wind.This device is just as between new wind passage and indoor exhaust wind air channel a flat air to air heat exchanger being installed.Summer, outdoor new wind was often wet and hot, and indoor exhaust wind is done and be 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, through behind the total-heat exchanger, new wind warms wet, also reaches the state that approaches room air, saves the warming and humidifying power consumption, the same new wind load of saving, the energy consumption that makes air-conditioning handle new wind has saved 70%～80%.With the great advantage of traditional metallic recuperator be: this film not only can reclaim sensible heat, and can effectively reclaim latent heat in the impervious while of dirty gas in guaranteeing indoor exhaust wind.
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 enthalpy recover 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.Someone adopts the method for similar liquids absorption dehumidifying to carry out the wet recovery of heat, relies on hygroscopic salt solution circulating between new wind and air draft, carries out continuous moisture absorption and wet recovery of the new wind-heat of regeneration realization, obtains better effects.But the trouble of liquid absorption dehumidifying maximum is its corrosion problems to pipeline, heat exchanger, promptly so-called spittle problem.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 steam blanket that air is dehumidified, this steam blanket has very high selection permeability, when the air stream 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, owing to exist the partial pressure of water vapour poor, water vapour will be removed air-flow and is discharged from along with one, and this removing air-flow compares with inlet air stream that to have a lower water vapour partial pressure poor.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 preferably 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 solid
-8Cm
2/ s) very little, the shortcoming of existing film maximum be difficult to coordinate high osmosis and high selectivity this to contradiction, and preparation cost is too high, material therefor is environmental friendliness not.
Summary of the invention
The objective of the invention is to overcome the shortcomings and deficiencies of prior art, provide a kind of high selectivity asymmetric moisture permeable membrane.
Another object of the present invention is to provide the preparation method of the asymmetric moisture permeable membrane of described high selectivity, adopt the one-step method preparation, do not need the two-step film forming process, implementation structure regulation and control automatically simultaneously form asymmetric moisture permeable membrane in film forming procedure.
A further object of the present invention provides the asymmetric moisture permeable membrane of described high selectivity and is used to realize the wet application of reclaiming of air dewetting and heat.
Purpose of the present invention realizes by following proposal:
The preparation method of the asymmetric moisture permeable membrane of a kind of high selectivity is characterized in that, comprises the steps:
(1) preparation casting solution: hydrophilic polymer is dissolved in coordinative solvent is made into hydrophilic polymer solution, hydrophilic polymer is 5-20wt.% in the solution, and heating (40-80 ℃) stirs as casting solution, and it is stand-by to leave standstill (about 24h) deaeration;
(2) adopt dry method system film: casting solution is carried out knifing handle, film thickness is controlled at 100～300 μ m, then this film is placed 24h in air solvent is volatilized naturally;
Perhaps adopt wet method system film: casting solution is carried out knifing handle (can adopt direct knifing or scrape) in the first-class mode of nonwoven, film thickness is controlled at 100～300 μ m, then this film is dropped into wet method film forming in coagulation bath, after 5-10 minute film is put into clean running water and leave standstill 24h and desolvate;
(3) drying of film: the film after desolvating promptly obtains the asymmetric moisture permeable membrane of high selectivity after further drying is handled (50-100 ℃ of dry 2-6h).
Preferably, when adopting wet method system film, dry again after the film after described the desolvating of step (3) will flatten.
Preferably, to handle be to carry out manual knifing or carry out machinery system film with the thickness of mechanical film applicator controlling diaphragm with scraper to the described knifing of step (1).
Preferably, the described hydrophilic polymer of step (1) is cellulose acetate, polyethylene glycol, shitosan, polyamide, polyimides, Kynoar or modified polyvinilidene fluoride.
Preferably, the solvent of the described cellulose acetate of step (1) is an acetic acid aqueous solution, and wherein acetic acid content is greater than 50wt.%; The solvent of polyethylene glycol is a water; The solvent of shitosan is an aqueous hydrochloric acid solution, and pH is 5～6; The solvent of polyamide, polyimides, Kynoar and modified polyvinilidene fluoride is dimethylacetylamide.
Preferably, the coagulation bath of the described cellulose acetate of step (2) is a water; The coagulation bath of shitosan is the acetic acid aqueous solution of 1～6wt.%; The coagulation bath of polyamide, polyimides and Kynoar is the isobutanol aqueous solution of 1～5wt.%; The coagulation bath of polyethylene glycol is that the ratio according to every 1000ml solution adds NaOH 50～100g in the saturated metabisulfite solution.
The asymmetric moisture permeable membrane of the high selectivity that said method makes is the film with double-layer structure that is made of porous supporting body layer and ultra-thin cortex, and described porous supporting body layer is spongy porous cellulose structure, and the thickness of porous support layer is 30～80 μ m; Described ultra-thin cortex is fine and close cellulosic structure, and the thickness of ultra-thin cortex is 2～10 μ m.
The asymmetric moisture permeable membrane of described high selectivity can be used for realizing the wet recovery of air dewetting and heat, and the full recuperation of heat of air.
Described moisture permeable membrane is used for air dewetting and reclaims with heat is wet, concrete steps are as follows: unstripped gas at first enters air compressor and compresses, unstripped gas after the compression enters the asymmetric moisture permeable membrane assembly of high selectivity again, in above-mentioned membrane module, new wind and air draft are carried out heat and wet exchange by the asymmetric moisture permeable membrane of high selectivity, the steam after the exchange and remove moisture and discharged by the above and below of the asymmetric moisture permeable membrane assembly of high selectivity respectively.
Described moisture permeable membrane is used for the full recuperation of heat of air, and concrete steps are as follows: outdoor new wind and indoor exhaust wind enter total-heat exchanger, and in the total-heat exchanger the inside, the exchange of heat and moisture is carried out in new wind and air draft, thereby realizes full heat exchange.
Ultra-thin dense layer surface is to realize optionally key, also is the most important factor of decision infiltration rate size.Steam transmits with the mechanism of adsorption and diffusion in the dense layer surface.The adsorption capacity power of hydrophily decision steam in film of cortical material, the hydrophily of film is good more, and suction-operated is strong more, helps infiltration more.The diffusion coefficient of steam in solid about 10
-8Cm
2/ s, little diffusion rate has a strong impact on the infiltration of steam, so dense layer surface is thin more, the diffusion of steam in solid is just easy more, so more helps the infiltration of steam in film.Therefore, select suitable material and preparation technology, make film can guarantee that selectivity can guarantee simultaneously that again high infiltration efficient is the key of preparation air dewetting film.
The asymmetric moisture permeable membrane of high selectivity that has among the present invention mainly is to adopt the phase-inversion technologies one-step method to finish preparation.Wherein, wet method phase-inversion technologies and dry method phase-inversion technologies have been selected in the preparation process for use.The solid content of mainly selecting hydrophilic polymer as the preparation film for use of the present invention decides solvent, additive and gel media according to the characteristics and the character of polymer.The selection principle of selective solvent, additive and gel media is under situation about being complementary with polymer property, selects for use nontoxic and the hypotoxicity material as far as possible.
Asymmetric moisture permeable membrane of the high selectivity that the present invention obtained and goods; not only can be used for realizing the wet recovery of air dewetting and heat; and the full recuperation of heat of air; also 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.
The present invention compared with prior art has following beneficial effect:
(1) a kind of wet asymmetric moisture permeable membrane of high selectivity that reclaims of air dewetting and heat that is used to realize of the present invention, to the test shows of the anisotropic membrane of this high selectivity infiltration, under the same experiment condition, flow velocity is 0.18m
3/ h, its steam exchange rate (newly, between the air draft) (1.8kgm
-2S) than traditional solid composite membrane (1.1kgm
-2S) improved a lot.
(2) the present invention is when reaching highly effective air dehumidifying and high selectivity separation requirement, only used single step reaction to prepare the anisotropic membrane of described high selectivity infiltration, compared with prior art, this method has advantages such as simple, easy to operate, the energy-conservation and preparation process environmental protection of technology.
(3) the present invention adopts wet method or dry method phase-inversion technologies to prepare described composite support liquid film, adopts low-toxic solvent and nontoxic additive, production process environmental protection more, effective simplification preparation technology, saved production cost greatly.
(4) anisotropic membrane of high selectivity of the present invention infiltration has advantages such as cortex is ultra-thin.
Description of drawings
Fig. 1 is a kind of structural representation sketch that is used to realize air dewetting and the wet asymmetric moisture permeable membrane of high selectivity that reclaims of heat of the present invention.
Fig. 2 is the dehumidifying process figure of the asymmetric moisture permeable membrane of high selectivity shown in Figure 1.
Fig. 3 is the wet schematic diagram that reclaims of the heat of the asymmetric moisture permeable membrane of high selectivity shown in Figure 1.
The specific embodiment
Below in conjunction with specific embodiment the present invention is done further concrete detailed description the in detail, but embodiments of the present invention are not limited thereto, the technological parameter for not indicating especially can carry out with reference to routine techniques.
Dispose acetic acid aqueous solution in conical flask, wherein the quality of acetate is that the quality of 58.7g and water is 29.3g, adds cellulose acetate 12g.50 ℃ add thermal agitation 3h extremely evenly as casting solution, and standing and defoaming 24h is stand-by.Casting solution is coated on the clean glass plate, is 150 μ m with the thickness of scraper controlling diaphragm.Drop into wet method film forming in the coagulation bath immediately, used gel media is a water.After 5 minutes film is taken off from glass plate, the running water of putting into cleaning leaves standstill 36h and desolvates.Film after desolvating flattens with glass plate, promptly makes the asymmetric moisture permeable membrane of high selectivity behind 70 ℃ of dry 2h.
The asymmetric moisture permeable membrane of the high selectivity that said method makes is a kind of film with double-layer structure.As shown in Figure 1, described double-layer structure is made up of porous supporting body layer 1 and ultra-thin cortex 2, and described porous support layer 1 is spongy porous cellulose structure, and surperficial ultra-thin cortex 2 is fine and close cellulosic structures; The thickness of described porous support layer is 38 μ m, and the thickness of ultra-thin cortex is 4.8 μ m.When utilizing this film to dehumidify with the wet recovery of heat, can realize sensible heat organic efficiency 0.85, latent heat organic efficiency 0.80 to air.
Dispose acetic acid aqueous solution in conical flask, the quality of acetate is that the quality of 49.5g and water is 40.5g, adds cellulose acetate 10g.45 ℃ add thermal agitation 4h extremely evenly as casting solution, and standing and defoaming 12h is stand-by.Nonwoven is layered on the glass plate, again casting solution is coated on the nonwoven, be adjusted to 300 μ m scraping film thickness, in air, place 24h behind the knifing solvent is volatilized naturally with mechanical knifing machine.The film that forms after solvent volatilizees naturally places 70 ℃ of dry 2h of hot air drier, makes the asymmetric moisture permeable membrane of high selectivity after solvent volatilizees naturally.
The asymmetric moisture permeable membrane of the high selectivity that said method makes is a kind of film with double-layer structure.As shown in Figure 1, described double-layer structure is made up of porous supporting body layer 1 and ultra-thin cortex 2, and described porous support layer 1 is spongy porous cellulose structure, and surperficial ultra-thin cortex 2 is fine and close cellulosic structures; The thickness of described porous support layer is 67 μ m, and the thickness of ultra-thin cortex is 5.4 μ m.When utilizing this film to dehumidify with the wet recovery of heat, can realize sensible heat organic efficiency 0.82, latent heat organic efficiency 0.78 to air.
Embodiment 3
The preparation polyethylene glycol aqueous solution in conical flask, polyvinyl alcohol 14g wherein, the quality of water is 86g.80 ℃ add thermal agitation 6h extremely evenly as casting solution, and standing and defoaming 24h is stand-by.Nonwoven being layered on the glass plate, casting solution being coated on the nonwoven again, is 200 μ m with the thickness of mechanical film applicator controlling diaphragm.Drop into immediately that wet method prepares film forming in the coagulation bath.This method selects for use in the saturated metabisulfite solution ratio according to every 1000ml solution to add NaOH 80g as gel media.After 5 minutes film is taken off from glass plate, put into clean running water and leave standstill 36h removal impurity.Film after desolvating flattens with glass plate, promptly makes the asymmetric moisture permeable membrane of high selectivity behind 70 ℃ of dry 2h.
The asymmetric moisture permeable membrane of the high selectivity that said method makes is a kind of film with double-layer structure.As shown in Figure 1, described double-layer structure is made up of porous supporting body layer 1 and ultra-thin cortex 2, and described porous support layer 1 is spongy porous cellulose structure, and surperficial ultra-thin cortex 2 is fine and close cellulosic structures; The thickness of described porous support layer is 50 μ m, and the thickness of ultra-thin cortex is 6.2 μ m.When utilizing this film to dehumidify with the wet recovery of heat, can realize sensible heat organic efficiency 0.89, latent heat organic efficiency 0.85 to air.
Embodiment 4
The preparation polyethylene glycol aqueous solution in conical flask, polyvinyl alcohol 10g wherein, the quality of water is 90g.70 ℃ add thermal agitation 6h extremely evenly as casting solution, and standing and defoaming 24h is stand-by.Nonwoven being layered on the glass plate, casting solution being coated on the nonwoven again, is 180 μ m with the thickness of scraper controlling diaphragm.After then this film being placed 24h in air solvent is volatilized naturally, promptly make the asymmetric moisture permeable membrane of high selectivity after placing hot air drier to regulate 80 ℃ of dry 1h of temperature again.
The asymmetric moisture permeable membrane of the high selectivity that said method makes is a kind of film with double-layer structure.As shown in Figure 1, described double-layer structure is made up of porous supporting body layer 1 and ultra-thin cortex 2, and described porous support layer 1 is spongy porous cellulose structure, and surperficial ultra-thin cortex 2 is fine and close cellulosic structures; The thickness of described porous support layer is 47 μ m, and the thickness of ultra-thin cortex is 5.8 μ m.When utilizing this film to dehumidify with the wet recovery of heat, can realize sensible heat organic efficiency 0.91, latent heat organic efficiency 0.85 to air.
Embodiment 5
In conical flask, prepare chitosan aqueous solution, shitosan 15g wherein, the quality of hydrochloric acid is that the quality of 1.5g and water is 83.5g.40 ℃ add thermal agitation 3h extremely evenly as casting solution, and standing and defoaming 24h is stand-by.Nonwoven being layered on the glass plate, casting solution being coated on the nonwoven again, is 300 μ m with the thickness of scraper controlling diaphragm.Drop into film forming in the coagulation bath immediately.This method selects for use the acetic acid aqueous solution of 1wt.% as gel media.After 5 minutes film is taken off from glass plate, the running water of putting into cleaning leaves standstill 36h and desolvates.Film after desolvating flattens with glass plate, promptly makes the asymmetric moisture permeable membrane of high selectivity behind 70 ℃ of dry 2h.
The asymmetric moisture permeable membrane of the high selectivity that said method makes is a kind of film with double-layer structure.As shown in Figure 1, described double-layer structure is made up of porous supporting body layer 1 and ultra-thin cortex 2, and described porous support layer 1 is spongy porous cellulose structure, and surperficial ultra-thin cortex 2 is fine and close cellulosic structures; The thickness of described porous support layer is 80 μ m, and the thickness of ultra-thin cortex is 9.6 μ m.When utilizing this film to dehumidify with the wet recovery of heat, can realize sensible heat organic efficiency 0.75, latent heat organic efficiency 0.68 to air.
Embodiment 6
In conical flask, prepare chitosan aqueous solution, shitosan 10g wherein, the quality of hydrochloric acid is that the quality of 1g and water is 89g.40 ℃ add thermal agitation 2h extremely evenly as casting solution, and standing and defoaming 24h is stand-by.Nonwoven being layered on the glass plate, casting solution being coated on the nonwoven again, is 250 μ m with the thickness of mechanical film applicator controlling diaphragm, places 24h in air solvent is volatilized naturally.Behind the 24h film is taken off from glass plate, promptly made the asymmetric moisture permeable membrane of high selectivity after placing hot air drier to regulate temperature to 70 ℃ dry 2h again.
The asymmetric moisture permeable membrane of the high selectivity that said method makes is a kind of film with double-layer structure.As shown in Figure 1, described double-layer structure is made up of porous supporting body layer 1 and ultra-thin cortex 2, and described porous support layer 1 is spongy porous cellulose structure, and surperficial ultra-thin cortex 2 is fine and close cellulosic structures; The thickness of described porous support layer is 72, and the thickness of ultra-thin cortex is 6.2 μ m.When utilizing this film to dehumidify with the wet recovery of heat, can realize sensible heat organic efficiency 0.75, latent heat organic efficiency 0.70 to air.
Embodiment 7
Preparation Kynoar solution in conical flask, Kynoar 10g wherein, dimethylacetylamide is 90g.60 ℃ add thermal agitation 2h extremely evenly as casting solution, and standing and defoaming 24h is stand-by.Nonwoven being layered on the glass plate, casting solution being coated on the nonwoven again, is 250 μ m with the thickness of scraper controlling diaphragm.Drop into immediately that wet method prepares film forming in the coagulation bath.This method selects for use the isobutanol aqueous solution of 5wt.% as gel media.After 5 minutes film is taken off from glass plate, the running water of putting into cleaning leaves standstill 36h and desolvates.Film after desolvating flattens with glass plate, promptly makes the asymmetric moisture permeable membrane of high selectivity behind 70 ℃ of dry 2h.
The asymmetric moisture permeable membrane of the high selectivity that said method makes is a kind of film with double-layer structure.As shown in Figure 1, described double-layer structure is made up of porous supporting body layer 1 and ultra-thin cortex 2, and described porous support layer 1 is spongy porous cellulose structure, and surperficial ultra-thin cortex 2 is fine and close cellulosic structures; The thickness of described porous support layer is 71 μ m, and the thickness of ultra-thin cortex is 5.6 μ m.When utilizing this film to dehumidify with the wet recovery of heat, can realize sensible heat organic efficiency 0.70, latent heat organic efficiency 0.68 to air.
Embodiment 8
Preparation Kynoar solution in conical flask, Kynoar 15g wherein, dimethylacetylamide is 88g and deionized water 2g.60 ℃ add thermal agitation 2h extremely evenly as casting solution, and standing and defoaming 24h is stand-by.Casting solution is coated on the clean glass plate, is 200 μ m with the thickness of mechanical knifing machine controlling diaphragm, and placement 24h volatilizees solvent naturally in air.Promptly make the asymmetric moisture permeable membrane of high selectivity after placing 60 ℃ of dry 3h of hot air drier again.
The asymmetric moisture permeable membrane of the high selectivity that said method makes is a kind of film with double-layer structure.As shown in Figure 1, described double-layer structure is made up of porous supporting body layer 1 and ultra-thin cortex 2, and described porous support layer 1 is spongy porous cellulose structure, and surperficial ultra-thin cortex 2 is fine and close cellulosic structures; The thickness of described porous support layer is 68 μ m, and the thickness of ultra-thin cortex is 5.8 μ m.When utilizing this film to dehumidify with the wet recovery of heat to air, can realize sensible heat organic efficiency 0.7, the latent heat organic efficiency is more than 0.65.
In conical flask, prepare polyamide solution, polyamide 15g wherein, dimethylacetylamide is 85g.60 ℃ add thermal agitation 3h extremely evenly as casting solution, and standing and defoaming 24h is stand-by.Casting solution is coated on the clean glass plate, is 150 μ m with the thickness of scraper controlling diaphragm.Leave standstill 5min in air after, wet method prepares film forming in the input coagulation bath.This method selects for use the acetic acid aqueous solution of 5wt.% as gel media.After 5 minutes film is taken off from glass plate, the running water of putting into cleaning leaves standstill 36h and desolvates.Film after desolvating flattens with glass plate, promptly makes the asymmetric moisture permeable membrane of high selectivity behind 70 ℃ of dry 2h.
The asymmetric moisture permeable membrane of the high selectivity that said method makes is a kind of film with double-layer structure.As shown in Figure 1, described double-layer structure is made up of porous supporting body layer 1 and ultra-thin cortex 2, and described porous support layer 1 is spongy porous cellulose structure, and surperficial ultra-thin cortex 2 is fine and close cellulosic structures; The thickness of described porous support layer is 67 μ m, and the thickness of ultra-thin cortex is 4.8 μ m.When utilizing this film to dehumidify with the wet recovery of heat, can realize sensible heat organic efficiency 0.7, latent heat organic efficiency 0.65 to air.
Embodiment 10
In conical flask, prepare polyamide solution, polyamide 15g wherein, dimethylacetylamide is 85g.60 ℃ add thermal agitation 2h extremely evenly as casting solution, and standing and defoaming 24h is stand-by.Nonwoven being layered on the glass plate, casting solution being coated on the nonwoven again, is 250 μ m with the thickness of mechanical film applicator controlling diaphragm.Volatilize the naturally film of postforming of solvent, place hot air drier to regulate temperature to 80 ℃ further dry 1.5h again, be the asymmetric moisture permeable membrane of high selectivity after the drying.
The asymmetric moisture permeable membrane of the high selectivity that said method makes is a kind of film with double-layer structure.As shown in Figure 1, described double-layer structure is made up of porous supporting body layer 1 and ultra-thin cortex 2, and described porous support layer 1 is spongy porous cellulose structure, and surperficial ultra-thin cortex 2 is fine and close cellulosic structures; The thickness of described porous support layer is 78 μ m, and the thickness of ultra-thin cortex is 7.6 μ m.When utilizing this film to dehumidify with the wet recovery of heat, can realize sensible heat organic efficiency 0.7, latent heat organic efficiency 0.62 to air.
Embodiment 11
As shown in Figure 2, the present invention is a kind of to be used to realize that air dewetting is as follows with the dehumidifying process of the wet asymmetric moisture permeable membrane of high selectivity that reclaims of heat: unstripped gas 3 at first enters air compressor 4 and compresses, unstripped gas 5 after the compression enters the asymmetric moisture permeable membrane assembly 6 of high selectivity again, 6 li of the asymmetric moisture permeable membrane assemblies of described high selectivity, new wind and air draft are carried out heat and wet exchange by the asymmetric moisture permeable membrane of high selectivity, the steam 8 after the exchange and remove moisture 7 and discharged by the above and below of the asymmetric moisture permeable membrane assembly 6 of high selectivity respectively.
Embodiment 12
As shown in Figure 3, the full heat recovery method of air of the present invention is as follows: outdoor new wind (air-flow 2 is gone into) and indoor exhaust wind (air-flow 1 is gone into) adverse current or distributary enter total-heat exchanger 9, in total-heat exchanger 9 the insides, outdoor new wind (air-flow 2 is gone into) and indoor exhaust wind (air-flow 1 is gone into) are carried out the exchange of heat and moisture, obtain new wind (air-flow 2 goes out) and air draft (air-flow 1 goes out) after the exchange.Fresh new wind (air-flow 2 goes out) inflow through full recuperation of heat is indoor, and the dirty gas that carries in the indoor exhaust wind is discharged to outdoor.Improve indoor air quality and purpose of energy saving thereby reach.
The foregoing description is a preferred implementation of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under spiritual essence of the present invention and the principle, substitutes, combination, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (10)
1. the preparation method of the asymmetric moisture permeable membrane of high selectivity is characterized in that, comprises the steps:
(1) preparation casting solution: hydrophilic polymer is dissolved in coordinative solvent is made into hydrophilic polymer solution, hydrophilic polymer is 5-20wt.% in the solution, and heating stirs as casting solution, and standing and defoaming is stand-by;
(2) adopt dry method system film: casting solution is carried out knifing handle, film thickness is controlled at 100～300 μ m, then this film is placed 24h in air solvent is volatilized naturally;
Perhaps adopt wet method system film: casting solution is carried out knifing handle, film thickness is controlled at 100～300 μ m, then this film is dropped into wet method film forming in coagulation bath, after 5-10 minute film is put into clean running water and leave standstill 24～48h and desolvate;
(3) drying of film: the film after desolvating promptly obtains the asymmetric moisture permeable membrane of high selectivity after further drying is handled.
2. preparation method according to claim 1 is characterized in that, and is when adopting wet method system film, dry again after the film after described the desolvating of step (3) will flatten.
3. preparation method according to claim 1 is characterized in that, it is to carry out manual knifing or carry out machinery system film with the thickness of mechanical film applicator controlling diaphragm with scraper that the described knifing of step (1) is handled.
4. according to claim 1 or 2 or 3 described preparation methods, it is characterized in that the described hydrophilic polymer of step (1) is cellulose acetate, polyethylene glycol, shitosan, polyamide, polyimides, Kynoar or modified polyvinilidene fluoride.
5. preparation method according to claim 4 is characterized in that, the solvent of the described cellulose acetate of step (1) is an acetic acid aqueous solution, and wherein acetic acid content is greater than 50wt.%; The solvent of polyethylene glycol is a water; The solvent of shitosan is an aqueous hydrochloric acid solution, and pH is 5～6; The solvent of polyamide, polyimides, Kynoar and modified polyvinilidene fluoride is dimethylacetylamide.
6. preparation method according to claim 5 is characterized in that, the coagulation bath of the described cellulose acetate of step (2) is a water; The coagulation bath of shitosan is the acetic acid aqueous solution of 1～6wt.%; The coagulation bath of polyamide, polyimides and Kynoar is the isobutanol aqueous solution of 1～5wt.%; The coagulation bath of polyethylene glycol is that the ratio according to every 1000ml solution adds NaOH 50～100g in the saturated metabisulfite solution.
7. the asymmetric moisture permeable membrane of high selectivity that makes according to any method of claim 1～6, it is characterized in that, it is the film with double-layer structure that is made of porous supporting body layer and ultra-thin cortex, described porous supporting body layer is spongy porous cellulose structure, and the thickness of porous support layer is 30～80 μ m; Described ultra-thin cortex is fine and close cellulosic structure, and the thickness of ultra-thin cortex is 2～10 μ m.
8. the application of the asymmetric moisture permeable membrane of high selectivity according to claim 7 is characterized in that, this film is used to realize the wet recovery of air dewetting and heat, and the full recuperation of heat of air.
9. the application of the asymmetric moisture permeable membrane of high selectivity according to claim 8, it is characterized in that, described moisture permeable membrane is used for air dewetting and reclaims with heat is wet, concrete steps are as follows: unstripped gas at first enters air compressor and compresses, unstripped gas after the compression enters the asymmetric moisture permeable membrane assembly of high selectivity again, in above-mentioned membrane module, new wind and air draft are carried out heat and wet exchange by the asymmetric moisture permeable membrane of high selectivity, the steam after the exchange and remove moisture and discharged by the above and below of the asymmetric moisture permeable membrane assembly of high selectivity respectively.
10. the application of the asymmetric moisture permeable membrane of high selectivity according to claim 8, it is characterized in that, described moisture permeable membrane is used for the full recuperation of heat of air, concrete steps are as follows: outdoor new wind and indoor exhaust wind enter total-heat exchanger, in the total-heat exchanger the inside, the exchange of heat and moisture is carried out in new wind and air draft, thereby realizes full heat exchange.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010286229 CN101947416B (en) | 2010-09-16 | 2010-09-16 | High-selectivity asymmetric moisture-permeable film as well as preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010286229 CN101947416B (en) | 2010-09-16 | 2010-09-16 | High-selectivity asymmetric moisture-permeable film as well as preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101947416A true CN101947416A (en) | 2011-01-19 |
| CN101947416B CN101947416B (en) | 2013-01-09 |
Family
ID=43451117
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201010286229 Active CN101947416B (en) | 2010-09-16 | 2010-09-16 | High-selectivity asymmetric moisture-permeable film as well as preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101947416B (en) |
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103194058A (en) * | 2013-04-08 | 2013-07-10 | 桂林电子科技大学 | High-thermal-conductive moisture permeable film and preparation method thereof |
| CN103342828A (en) * | 2013-06-27 | 2013-10-09 | 华南理工大学 | Efficient moisture-permeable film prepared by a one-step process and application thereof |
| CN103877870A (en) * | 2013-01-30 | 2014-06-25 | 中国科学院宁波材料技术与工程研究所 | Total heat exchange membrane with antibacterial and mildewproof functions and total heat exchanger |
| CN104877164A (en) * | 2015-05-27 | 2015-09-02 | 浙江大学 | Preparation method for through-hole ordered film |
| 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 |
| CN105833736A (en) * | 2016-05-24 | 2016-08-10 | 华南理工大学 | High-selectivity low-thermal conductivity asymmetric permeable membrane as well as preparation method and application thereof |
| CN106378014A (en) * | 2016-10-17 | 2017-02-08 | 同济大学 | Composite humidifying membrane based on asymmetrical structure and preparation method thereof |
| CN108486687A (en) * | 2018-02-28 | 2018-09-04 | 海信（山东）空调有限公司 | Hygroscopic coatings material, preparation method and its application |
| CN109289541A (en) * | 2018-11-07 | 2019-02-01 | 温州莲华环保科技有限公司 | A kind of preparation method of organic forward osmosis membrane |
| CN110057085A (en) * | 2019-03-26 | 2019-07-26 | 淮南市知产创新技术研究有限公司 | A kind of heat exchange mechanism |
| CN110057091A (en) * | 2019-03-26 | 2019-07-26 | 淮南市知产创新技术研究有限公司 | A kind of symmetrical structure Total heat exchange core |
| CN113289462A (en) * | 2021-05-19 | 2021-08-24 | 华南理工大学 | Hydrate membrane device and method for gas separation |
| CN113578078A (en) * | 2021-07-12 | 2021-11-02 | 太原理工大学 | Preparation method and application of mixed matrix membrane based on nitrogen-doped porous carbon spheres |
| CN114210180A (en) * | 2021-12-17 | 2022-03-22 | 宁波威霖住宅设施有限公司 | Dehumidifying device |
| 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 |
| CN115253714A (en) * | 2022-08-26 | 2022-11-01 | 太原理工大学 | Mixed matrix membrane doped with molybdenum disulfide nanosheet modified material, and preparation method and application thereof |
| WO2023082229A1 (en) * | 2021-11-15 | 2023-05-19 | 青岛科技大学 | Gel composite film, preparation method therefor, and use thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003088722A (en) * | 2001-09-18 | 2003-03-25 | Japan Science & Technology Corp | Energy saving type dehumidification system |
| CN1864829A (en) * | 2006-03-31 | 2006-11-22 | 华南理工大学 | A hydrophilic-hydrophobic bipolar composite membrane and method for preparing same |
| JP2007203280A (en) * | 2005-03-29 | 2007-08-16 | Forestry & Forest Products Research Institute | Separation membrane and composite membrane having the same, humidification element, dehumidification element, humidifier, dehumidifier, and humidifying system |
-
2010
- 2010-09-16 CN CN 201010286229 patent/CN101947416B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003088722A (en) * | 2001-09-18 | 2003-03-25 | Japan Science & Technology Corp | Energy saving type dehumidification system |
| JP2007203280A (en) * | 2005-03-29 | 2007-08-16 | Forestry & Forest Products Research Institute | Separation membrane and composite membrane having the same, humidification element, dehumidification element, humidifier, dehumidifier, and humidifying system |
| CN1864829A (en) * | 2006-03-31 | 2006-11-22 | 华南理工大学 | A hydrophilic-hydrophobic bipolar composite membrane and method for preparing same |
Non-Patent Citations (2)
| Title |
|---|
| LIXIA PEI ET AL.: "Preparation and Characterization of Porous Poly(vinylidene fluoride) Membranes for Dehumidification with Poly(ethylene glycol) as an Additive", 《JOURNAL OF APPLIED POLYMER SCIENCE》 * |
| 徐强强: "具有致密皮层的整体型非对称聚酰亚胺渗透汽化膜的研制", 《中国优秀硕士学位论文全文数据库（电子期刊）工程科技I辑》 * |
Cited By (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103877870A (en) * | 2013-01-30 | 2014-06-25 | 中国科学院宁波材料技术与工程研究所 | Total heat exchange membrane with antibacterial and mildewproof functions and total heat exchanger |
| CN103877870B (en) * | 2013-01-30 | 2016-01-13 | 中国科学院宁波材料技术与工程研究所 | There is Total heat exchange film and the total-heat exchanger of antibacterial and antimildew function |
| CN103194058A (en) * | 2013-04-08 | 2013-07-10 | 桂林电子科技大学 | High-thermal-conductive moisture permeable film and preparation method thereof |
| CN103342828A (en) * | 2013-06-27 | 2013-10-09 | 华南理工大学 | Efficient moisture-permeable film prepared by a one-step process and application thereof |
| CN104877164A (en) * | 2015-05-27 | 2015-09-02 | 浙江大学 | Preparation method for through-hole ordered film |
| CN104877164B (en) * | 2015-05-27 | 2018-03-16 | 浙江大学 | A kind of preparation method of through hole Ordered Film |
| 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 |
| CN105833736A (en) * | 2016-05-24 | 2016-08-10 | 华南理工大学 | High-selectivity low-thermal conductivity asymmetric permeable membrane as well as preparation method and application thereof |
| CN106378014A (en) * | 2016-10-17 | 2017-02-08 | 同济大学 | Composite humidifying membrane based on asymmetrical structure and preparation method thereof |
| CN108486687A (en) * | 2018-02-28 | 2018-09-04 | 海信（山东）空调有限公司 | Hygroscopic coatings material, preparation method and its application |
| CN109289541A (en) * | 2018-11-07 | 2019-02-01 | 温州莲华环保科技有限公司 | A kind of preparation method of organic forward osmosis membrane |
| CN110057085A (en) * | 2019-03-26 | 2019-07-26 | 淮南市知产创新技术研究有限公司 | A kind of heat exchange mechanism |
| CN110057091A (en) * | 2019-03-26 | 2019-07-26 | 淮南市知产创新技术研究有限公司 | A kind of symmetrical structure Total heat exchange core |
| CN113289462A (en) * | 2021-05-19 | 2021-08-24 | 华南理工大学 | Hydrate membrane device and method for gas separation |
| CN113578078A (en) * | 2021-07-12 | 2021-11-02 | 太原理工大学 | Preparation method and application of mixed matrix membrane based on nitrogen-doped porous carbon spheres |
| WO2023082229A1 (en) * | 2021-11-15 | 2023-05-19 | 青岛科技大学 | Gel composite film, preparation method therefor, and use thereof |
| 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 |
| CN114210180A (en) * | 2021-12-17 | 2022-03-22 | 宁波威霖住宅设施有限公司 | Dehumidifying device |
| CN115253714A (en) * | 2022-08-26 | 2022-11-01 | 太原理工大学 | Mixed matrix membrane doped with molybdenum disulfide nanosheet modified material, and preparation method and application thereof |
| CN115253714B (en) * | 2022-08-26 | 2023-10-10 | 太原理工大学 | Mixed matrix membrane doped with molybdenum disulfide nanosheet modified material, and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101947416B (en) | 2013-01-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101947416B (en) | High-selectivity asymmetric moisture-permeable film as well as preparation method and application thereof | |
| CN100395008C (en) | A hydrophilic-hydrophobic bipolar composite membrane and method for preparing same | |
| CN105597566A (en) | Preparation method and application of novel total heat exchange film | |
| CN103194058A (en) | High-thermal-conductive moisture permeable film and preparation method thereof | |
| CN103342828B (en) | Efficient moisture-permeable film prepared by a one-step process and application thereof | |
| CN105879706A (en) | Graphene oxide-polymer hybridized all-heat exchange membrane and preparation method and application thereof | |
| ES2924560T3 (en) | heat and moisture exchanger | |
| CN107335345A (en) | A kind of self-supporting high moisture-inhibiting thermal insulation aerogel and preparation method thereof | |
| CN109107399B (en) | Water molecule permeable membrane and preparation method and application thereof | |
| CN206257941U (en) | Inner-outer circulation drying system and outer circulation drying system | |
| CN102741469A (en) | Polymer composite materials for building air conditioning or dehumidification and preparation method thereof | |
| CN105833736A (en) | High-selectivity low-thermal conductivity asymmetric permeable membrane as well as preparation method and application thereof | |
| CN103170257A (en) | Compound forward osmosis membrane and preparation method thereof | |
| CN106000117A (en) | Low thermal conductivity hydrophilic-hydrophobic bipolar composite membrane as well as preparation method and application thereof | |
| CN205351583U (en) | Heat pump driven hollow fiber membrane liquid dehydrating unit | |
| CN105771674A (en) | Tubular hollow fiber membrane, preparation method and application | |
| CN100348304C (en) | Composite support liquid film and its preparing method | |
| CN110016814B (en) | Antibacterial asymmetric total heat exchange membrane, total heat exchange core and total heat exchanger | |
| CN105299783A (en) | Solar-driven solution membrane concentration and solution dehumidification device and dehumidification method | |
| WO2006128366A1 (en) | Air treatment method and an apparatus using the method | |
| CN206377795U (en) | The humidifier of the air conditioner of the automatic water-returning draining of low power consuming | |
| CN206875662U (en) | Possess the Fresh air handling units of humidity conditioning function | |
| CN106545945A (en) | The humidifier of the air-conditioner of the automatic water-returning draining of low power consuming | |
| CN110302687A (en) | Wet film of a kind of intelligence control and its preparation method and application | |
| CN108225001A (en) | Marine environment is prepared and heat pump drying integrated apparatus with fresh water |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |