CN1864829A - A hydrophilic-hydrophobic bipolar composite membrane and method for preparing same - Google Patents
A hydrophilic-hydrophobic bipolar composite membrane and method for preparing same Download PDFInfo
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- CN1864829A CN1864829A CN 200610034769 CN200610034769A CN1864829A CN 1864829 A CN1864829 A CN 1864829A CN 200610034769 CN200610034769 CN 200610034769 CN 200610034769 A CN200610034769 A CN 200610034769A CN 1864829 A CN1864829 A CN 1864829A
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Abstract
The invention discloses a hydrophilic-hydrophobic bipolar complex membrane and the method for preparing the same. Said complex membrane comprises two layers, the bottom one is porous supporting system, and upper one is ultra-fine cerebral cortex; said porous supporting system is hydrophobic membrane and nonpolar, to avoid condensation of water vapour; ultra-fine membrane is hydrophilic membrane and polar, and LiCl with 1-5% by weight of main component can be doped to increase polarity; the thickness of porous supporting system is 30-100 um, and that of ultra-fine cerebral cortex is 5-20 um. The invention is characterized by simple process and low cost. The prepared bipolar complex membrane is characterized by good penetration property and gas selectivity, high intensity and wide application in water treatment, air conditioner engineering, energy, chemical industry, metallurgy and biochemical engineering. The product is especially suitable for air dehumidification and heat recycle of air cinditioner new gas.
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 hydrophilic-hydrophobic bipolar complex membrane of realizing air dewetting and the full recuperation of heat of air-conditioning and preparation method thereof that is used to.
Background technology
At present, because people more and more pay attention to the quality of room air, and seek a kind of air dewetting and full heat recycle process of air of can making 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 full heat recovery method.And this membrane method dehumidifying and full recuperation of heat and tradition dehumidifying are compared institute and are had advantage with full heat recovery method just.
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 full recuperation of 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 are in total-heat exchanger behind heat-shift and the moisture, novel wind energy reaches the state that approaches room air, has 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%.
The full heat recovery method of traditional air 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, what at present full heat recovery technology adopted in the world is complete hot runner, 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 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 the dehumidifying and the recuperation of heat of air, 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.
The shortcoming of existing film is to be difficult to satisfy high vapor transfer rate simultaneously and to stop the contradiction of other gas molecule between seeing through.
Summary of the invention
The objective of the invention is to overcome the shortcomings and deficiencies of prior art, a kind of hydrophilic-hydrophobic bipolar complex membrane that is used to realize air dewetting and the full recuperation of heat of air-conditioning is provided, can realize high saturating wet, the high mechanical properties of air, other gas molecule is had strong barrier effect.
Another object of the present invention is to provide the preparation method of this hydrophilic-hydrophobic bipolar complex membrane.
Hydrophilic-hydrophobic bipolar complex membrane of the present invention has double-decker, and bottom is the porous supporting body layer, and the upper strata is ultra-thin cortex; Described porous supporting body layer is hydrophobic film (a nonpolar film), and ultra-thin cortex is hydrophilic membrane (a polarity film); The thickness of described porous supporting body layer is 30～100 μ m, and the thickness of ultra-thin cortex is 5～20 μ m.
Described porous supporting body layer be in Kynoar, polysulfones, polyvinyl chloride, polypropylene, the polyethylene etc. any one.
Described ultra-thin cortex main component be in polyvinyl alcohol, Sodium Polyacrylate, poly-triacetate fiber, the polymethyl methacrylate etc. any one, be to strengthen cortex polarity, can be doped with the LiCl that accounts for main component quality 1%～5% in the ultra-thin cortex.
The porous supporting body layer is the hydrophobicity film, plays to strengthen the intensity effect, avoids hydrone to condense in the micropore therein simultaneously, thereby reduces the steam permeable resistance; Ultra-thin cortex is fine and close hydrophilic film, is strong polarity, has strong wettability power, can make the hydrone selective permeation, and stop other gas molecule to see through.
Of the present invention hydrophilic-the hydrophobic bipolar film has four kinds of preparation methods at different hydrophilic active layers.
Selecting polyvinyl alcohol is the hydrophilic membrane main component, and its step is as follows:
The first step: the lithium chloride of 2～15g polyvinyl alcohol and its quality 1%～5% was stirred 1～2 hour down at 90 ℃～100 ℃ with 100～150g deionized water, be mixed with poly-vinyl alcohol solution, with above-mentioned solution left standstill 1～3 day, the formation casting solution;
Second step: above-mentioned casting solution is poured on the hydrophobic film of 30～100 μ m thickness, smoothens, with the air dry 1～2 day in air of the above-mentioned composite membrane that has coated;
Described hydrophobic film is Kynoar, polysulfones, polyvinyl chloride, polypropylene, polyethylene etc.;
The 3rd step: the configuration cross-linking agent aqueous solution, wherein the hydroxysuccinic acid mass concentration 1～3%, quality of acetic acid concentration 3～5%, above-mentioned composite membrane is immersed in the cross-linking agent aqueous solution 20～30 seconds, picks up, airing, immediately transfer in 70～100 ℃ the baking oven, baking 30～50min, preparation is finished.
Selecting Sodium Polyacrylate is the hydrophilic membrane main component, and its step is as follows:
The first step: the lithium chloride of 2～15g Sodium Polyacrylate and its quality 1%～5% was stirred 1～2 hour down at 90 ℃～100 ℃ with 100～200g deionized water, add 1～3 glycerine and 0.1～0.3g potassium peroxydisulfate and the acid of 0.01～0.03g benzene dipotassium again, stirred 1～2 hour down at 70 ℃～90 ℃, form casting solution;
Second step: above-mentioned casting solution is poured on the hydrophobic film of 30～100 μ m thickness, smoothens, the above-mentioned composite membrane that has coated in 70～100 ℃ baking oven, is dried by the fire 30～50min, preparation is finished;
Described hydrophobic film is Kynoar, polysulfones, polyvinyl chloride, polypropylene, polyethylene etc.
Selecting poly-triacetate fiber is the hydrophilic membrane main component, and its step is as follows:
The first step: the lithium chloride of the poly-triacetate fiber of 2～10g and its quality 1%～5% was stirred 1～2 hour down at 60 ℃～70 ℃ with 100～150g acetone, add 0.1g～0.3g dioxane and 0.1g～0.2g maleic acid again, stir, be mixed with solution, with above-mentioned solution left standstill 1～2 day, form casting solution;
Second step: above-mentioned casting solution is poured on the hydrophobic film of 30～100 μ m thickness, smoothens, the above-mentioned composite membrane that has coated is transferred to immediately in 50～70 ℃ the baking oven, baking 30～50min, preparation is finished;
Described hydrophobic film is Kynoar, polysulfones, polyvinyl chloride, polypropylene, polyethylene etc.
Selecting polymethyl methacrylate is the hydrophilic membrane main component, and its step is as follows:
The first step: the lithium chloride of 2～10g polymethyl methacrylate and its quality 1%～5% is dissolved with 80～120g methyl-sulfoxide, stirred 1～2 hour down at 90 ℃～100 ℃, add the stirring under 90 ℃～100 ℃ of 30～50g distilled water again and be mixed with solution in 1～2 hour, with above-mentioned solution left standstill 1～3 day, form casting solution;
Second step: above-mentioned casting solution is poured on the hydrophobic film of 30～100 μ m thickness, smoothens, the above-mentioned composite membrane that has coated in 70～100 ℃ baking oven, is dried by the fire 30～50min, preparation is finished;
Described hydrophobic film is Kynoar, polysulfones, polyvinyl chloride, polypropylene, polyethylene etc.
The present invention compared with prior art has following advantage and beneficial effect:
(1) hydrophilic-hydrophobic bipolar complex membrane of the present invention has reduced the moisture diffusion resistance because stream molecule can not condense in its hydrophobicity porous supporting body layer nanopores, has kept very high vapor transfer rate; Hydrophilic cortex can be done very thinly, stops under the situation of other gas in assurance, keeps very high water vapor permeation speed;
(2) hydrophilic-hydrophobic bipolar complex membrane of the present invention integrates high strength, high vapor transfer rate, high selectivity, test shows to this composite membrane, under the same experiment condition, the steam exchange efficiency of this composite membrane (newly, between the air draft) is higher by 50%～200% than the individual layer solid hydrophilic film of condition of equivalent thickness;
(3) cortex of hydrophilic-hydrophobic bipolar complex membrane of the present invention is ultra-thin, can reach 5 μ m thickness;
(4) preparation method of hydrophilic-hydrophobic bipolar complex membrane of the present invention is simple, easy to operate, and equipment investment is few, and different interlayer adhesion are strong, good film-forming property.
Description of drawings
Fig. 1 is the structural representation of hydrophilic-hydrophobic bipolar complex membrane of the present invention;
Fig. 2 is the dehumidifying process figure of hydrophilic-hydrophobic bipolar complex membrane shown in Figure 1;
Fig. 3 is the wet total-heat exchanger that reclaims of heat that contains hydrophilic-hydrophobic bipolar complex membrane.
Among the figure: the ultra-thin cortex 3-of 1-porous supporting body layer 2-hydrophilic-hydrophobic bipolar complex membrane 4-air compressor 5-composite membrane assembly
The specific embodiment
In order to understand the present invention better, the present invention is done to describe further below in conjunction with accompanying drawing.
As shown in Figure 1, hydrophilic-hydrophobic bipolar complex membrane of the present invention has double-decker, and bottom is a porous supporting body layer 1, and the upper strata is ultra-thin cortex 2; Porous supporting body layer 1 is hydrophobic film (a nonpolar film), and ultra-thin cortex 2 is hydrophilic membrane (polarity films); The thickness of described porous supporting body layer 1 is 30～100 μ m, and the thickness of ultra-thin cortex 2 is 5～20 μ m.
Porous supporting body layer 1 be in Kynoar, polysulfones, polyvinyl chloride, polypropylene, the polyethylene etc. any one; Ultra-thin cortex 2 main components be in polyvinyl alcohol, Sodium Polyacrylate, poly-triacetate fiber, the polymethyl methacrylate etc. any one, be to strengthen cortex polarity, can be doped with the LiCl that accounts for main component quality 1%～5% in the ultra-thin cortex 2.
As shown in Figure 2, the dehumidifying process of hydrophilic-hydrophobic bipolar complex membrane of the present invention: unstripped gas enters air compressor 4 and compresses, and the unstripped gas after the compression enters composite membrane assembly 5 again; 5 li of composite membrane assemblies, after the steam permeable hydrophilic-hydrophobic bipolar complex membrane 3 in the unstripped gas, steam and remove moisture and discharge by the above and below of composite membrane assembly 5 respectively.
As shown in Figure 3, outdoor new wind and indoor exhaust wind enter the wet total-heat exchanger that reclaims of the heat that contains hydrophilic-hydrophobic bipolar complex membrane, and outdoor new wind and indoor exhaust wind are carried out the exchange of heat and moisture, after the exchange more respectively inlet chamber interior be discharged to outdoor.
When utilizing this hydrophilic-hydrophobic bipolar complex membrane 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.
Of the present invention hydrophilic-the hydrophobic bipolar film is as follows at different hydrophilic active layer preparation methods.
One, selecting polyvinyl alcohol is the hydrophilic membrane main component
Embodiment 1
4g polyvinyl alcohol and 0.12g lithium chloride were stirred 1 hour down at 90 ℃ with the 120g deionized water, be mixed with poly-vinyl alcohol solution,, form casting solution above-mentioned solution left standstill 1 day; Above-mentioned casting solution is poured on the 100 μ m polyvinylidene fluoride films, smoothens, with the air dry 1 day in air of the above-mentioned composite membrane that has coated; The configuration cross-linking agent aqueous solution, wherein the hydroxysuccinic acid mass concentration 1%, and quality of acetic acid concentration 3% is immersed in the cross-linking agent aqueous solution 20 seconds with above-mentioned composite membrane, picks up, airing, immediately transfer in 70 ℃ the baking oven, baking 30min, preparation is finished.
Embodiment 2
2g polyvinyl alcohol and 0.10g lithium chloride were stirred 1.5 hours down at 95 ℃ with the 100g deionized water, be mixed with poly-vinyl alcohol solution,, form casting solution above-mentioned solution left standstill 2 days; Above-mentioned casting solution is poured on the 30 μ m polyethylene films, smoothens, with the air dry 1.5 days in air of the above-mentioned composite membrane that has coated; The configuration cross-linking agent aqueous solution, wherein the hydroxysuccinic acid mass concentration 2%, and quality of acetic acid concentration 4% is immersed in the cross-linking agent aqueous solution 25 seconds with above-mentioned composite membrane, picks up, airing, immediately transfer in 80 ℃ the baking oven, baking 40min, preparation is finished.
Embodiment 3
15g polyvinyl alcohol and 0.15g lithium chloride were stirred 2 hours down at 100 ℃ with the 150g deionized water, be mixed with poly-vinyl alcohol solution,, form casting solution above-mentioned solution left standstill 3 days; Above-mentioned casting solution is poured on the 70 μ m polypropylene screens, smoothens, with the air dry 2 days in air of the above-mentioned composite membrane that has coated; The configuration cross-linking agent aqueous solution, wherein the hydroxysuccinic acid mass concentration 3%, and quality of acetic acid concentration 5% is immersed in the cross-linking agent aqueous solution 30 seconds with above-mentioned composite membrane, picks up, airing, immediately transfer in 100 ℃ the baking oven, baking 50min, preparation is finished.
Two, selecting Sodium Polyacrylate is the hydrophilic membrane main component
Embodiment 4
15g Sodium Polyacrylate and 0.15g lithium chloride were stirred 2 hours down at 100 ℃ with the 200g deionized water, add 3 glycerine and 0.1g potassium peroxydisulfate and the acid of 0.01g benzene dipotassium again, stirred 1 hour down, form casting solution at 70 ℃; Above-mentioned casting solution is poured on the 50 μ m thickness polypropylene screens, smoothens, the above-mentioned composite membrane that has coated in 70 ℃ baking oven, is dried by the fire 50min, preparation is finished.
Embodiment 5
2g Sodium Polyacrylate and 0.06g lithium chloride were stirred 1 hour down at 90 ℃ with the 100g deionized water, add 1 glycerine and 0.2g potassium peroxydisulfate and the acid of 0.02g benzene dipotassium again, stirred 2 hours down, form casting solution at 80 ℃; Above-mentioned casting solution is poured on the 30 μ m thickness pdythene films, smoothens, the above-mentioned composite membrane that has coated in 100 ℃ baking oven, is dried by the fire 30min, preparation is finished.
Embodiment 6
10g Sodium Polyacrylate and 0.50g lithium chloride were stirred 1.5 hours down at 95 ℃ with the 160g deionized water, add 2 glycerine and 0.3g potassium peroxydisulfate and the acid of 0.03g benzene dipotassium again, stirred 1.5 hours down, form casting solution at 90 ℃; Above-mentioned casting solution is poured on the 100 μ m thickness PS membranes, smoothens, the above-mentioned composite membrane that has coated in 80 ℃ baking oven, is dried by the fire 40min, preparation is finished.
Three, selecting poly-triacetate fiber is the hydrophilic membrane main component
Embodiment 7
Poly-triacetate fiber of 2g and 0.08g lithium chloride were stirred 1 hour down at 60 ℃ with 100g acetone, add 0.1g dioxane and 0.1g maleic acid again, stir, be mixed with solution; With above-mentioned solution left standstill 1 day, form casting solution; Above-mentioned casting solution is poured on the 100 μ m PS membranes, smoothens, the above-mentioned composite membrane that has coated is transferred to immediately in 50 ℃ the baking oven, baking 30min, preparation is finished.
Embodiment 8
Poly-triacetate fiber of 5g and 0.25g lithium chloride were stirred 1.5 hours down at 65 ℃ with 120g acetone, add 0.2g dioxane and 0.15g maleic acid again, stir, be mixed with solution; With above-mentioned solution left standstill 1.5 days, form casting solution; Above-mentioned casting solution is poured on the 30 μ m pdythene films, smoothens, the above-mentioned composite membrane that has coated is transferred to immediately in 60 ℃ the baking oven, baking 40min, preparation is finished.
Embodiment 9
Poly-triacetate fiber of 10g and 0.10g lithium chloride were stirred 2 hours down at 70 ℃ with 150g acetone, add 0.3g dioxane and 0.2g maleic acid again, stir, be mixed with solution; With above-mentioned solution left standstill 2 days, form casting solution; Above-mentioned casting solution is poured on the 60 μ m polyvinylidene fluoride films, smoothens, the above-mentioned composite membrane that has coated is transferred to immediately in 70 ℃ the baking oven, baking 50min, preparation is finished.
Four, selecting polymethyl methacrylate is the hydrophilic membrane main component
Embodiment 10
5g polymethyl methacrylate and 0.15g lithium chloride with the dissolving of 100g methyl-sulfoxide, were stirred 1 hour down at 90 ℃, add 40g distilled water again and stir down at 95 ℃ and be mixed with solution in 1.5 hours,, form casting solution above-mentioned solution left standstill 2 days; Above-mentioned casting solution is poured on the 80 μ m pdythene films, smoothens, the above-mentioned composite membrane that has coated in 80 ℃ baking oven, is dried by the fire 40min, preparation is finished.
Embodiment 11
10g polymethyl methacrylate and 0.10g lithium chloride with the dissolving of 120g methyl-sulfoxide, were stirred 2 hours down at 100 ℃, add 50g distilled water again and stir down at 100 ℃ and be mixed with solution in 2 hours,, form casting solution above-mentioned solution left standstill 3 days; Above-mentioned casting solution is poured on the 100 μ m polyethylene films, smoothens, the above-mentioned composite membrane that has coated in 100 ℃ baking oven, is dried by the fire 50min, preparation is finished.
Embodiment 12
2g polymethyl methacrylate and 0.10g lithium chloride with the dissolving of 80g methyl-sulfoxide, were stirred 1.5 hours down at 95 ℃, add 30g distilled water again and stir down at 90 ℃ and be mixed with solution in 1 hour,, form casting solution above-mentioned solution left standstill 1 day; Above-mentioned casting solution is poured on the 30 μ m polypropylene screens, smoothens, the above-mentioned composite membrane that has coated in 70 ℃ baking oven, is dried by the fire 30min, preparation is finished.
Hydrophilic-hydrophobic bipolar complex membrane of the present invention has reduced the moisture diffusion resistance because stream molecule can not condense in its hydrophobicity porous supporting body layer nanopores, has kept very high vapor transfer rate; Hydrophilic cortex can be done very thinly, stops under the situation of other gas in assurance, keeps very high water vapor permeation speed, integrates high strength, high vapor transfer rate, high selectivity.To the test shows of hydrophilic-hydrophobic bipolar complex membrane of the present invention, under the same experiment condition, the steam exchange efficiency of this composite membrane (newly, between the air draft) is higher by 50%～200% than the individual layer solid hydrophilic film of condition of equivalent thickness.Bipolar composite membrane of the present invention has good permeability and gas-selectively, higher intensity is arranged, can be widely used in water technology, Air-conditioning Engineering, the energy, chemical industry, metallurgy, fields such as Biochemical Engineering are particularly suitable for the full recuperation of heat of air dewetting and air conditioner fresh air.
Claims (8)
1. a hydrophilic-hydrophobic bipolar complex membrane has double-decker, it is characterized in that bottom is porous supporting body layer (1), and the upper strata is ultra-thin cortex (2); Described porous supporting body layer (1) is a hydrophobic film, and ultra-thin cortex (2) is a hydrophilic membrane; The thickness of described porous supporting body layer (1) is 30～100 μ m, and the thickness of ultra-thin cortex (2) is 5～20 μ m.
2. hydrophilic-hydrophobic bipolar complex membrane according to claim 1, it is characterized in that described porous supporting body layer (1) in the Kynoar, polysulfones, polyvinyl chloride, polypropylene, polyethylene any one.
3. hydrophilic-hydrophobic bipolar complex membrane according to claim 2, it is characterized in that described ultra-thin cortex (2) main component be in polyvinyl alcohol, Sodium Polyacrylate, poly-triacetate fiber, the polymethyl methacrylate any one, the content of LiCl accounts for 1%～5% of main component quality in the ultra-thin cortex (2).
4. be the preparation method of the hydrophilic-hydrophobic bipolar complex membrane of hydrophilic membrane main component with the polyvinyl alcohol in the claim 3, it is characterized in that step is as follows:
The first step: the lithium chloride of 2～15g polyvinyl alcohol and its quality 1%～5% was stirred 1～2 hour down at 90 ℃～100 ℃ with 100～150g deionized water, be mixed with poly-vinyl alcohol solution, with above-mentioned solution left standstill 1～3 day, the formation casting solution;
Second step: above-mentioned casting solution is poured on the hydrophobic film of 30～100 μ m thickness, smoothens, with the air dry 1～2 day in air of the above-mentioned composite membrane that has coated;
The 3rd step: the configuration cross-linking agent aqueous solution, wherein the hydroxysuccinic acid mass concentration 1～3%, quality of acetic acid concentration 3～5%, above-mentioned composite membrane is immersed in the cross-linking agent aqueous solution 20～30 seconds, picks up, airing, immediately transfer in 70～100 ℃ the baking oven, baking 30～50min, preparation is finished.
5. be the preparation method of the hydrophilic-hydrophobic bipolar complex membrane of hydrophilic membrane main component with the Sodium Polyacrylate in the claim 3, it is characterized in that step is as follows:
The first step: the lithium chloride of 2～15g Sodium Polyacrylate and its quality 1%～5% was stirred 1～2 hour down at 90 ℃～100 ℃ with 100～200g deionized water, add 1～3 glycerine and 0.1～0.3g potassium peroxydisulfate and the acid of 0.01～0.03g benzene dipotassium again, stirred 1～2 hour down at 70 ℃～90 ℃, form casting solution;
Second step: above-mentioned casting solution is poured on the hydrophobic film of 30～100 μ m thickness, smoothens, the above-mentioned composite membrane that has coated in 70～100 ℃ baking oven, is dried by the fire 30～50min, preparation is finished.
6. be the preparation method of the hydrophilic-hydrophobic bipolar complex membrane of hydrophilic membrane main component with poly-triacetate fiber in the claim 3, it is characterized in that step is as follows:
The first step: the lithium chloride of the poly-triacetate fiber of 2～10g and its quality 1%～5% was stirred 1～2 hour down at 60 ℃～70 ℃ with 100～150g acetone, add 0.1g～0.3g dioxane and 0.1g～0.2g maleic acid again, stir, be mixed with solution, with above-mentioned solution left standstill 1～2 day, form casting solution;
Second step: above-mentioned casting solution is poured on the hydrophobic film of 30～100 μ m thickness, smoothens, the above-mentioned composite membrane that has coated is transferred to immediately in 50～70 ℃ the baking oven, baking 30～50min, preparation is finished.
7. be the preparation method of the hydrophilic-hydrophobic bipolar complex membrane of hydrophilic membrane main component with the polymethyl methacrylate in the claim 3, it is characterized in that step is as follows:
The first step: the lithium chloride of 2～10g polymethyl methacrylate and its quality 1%～5% is dissolved with 80～120g methyl-sulfoxide, stirred 1～2 hour down at 90 ℃～100 ℃, add the stirring under 90 ℃～100 ℃ of 30～50g distilled water again and be mixed with solution in 1～2 hour, with above-mentioned solution left standstill 1～3 day, form casting solution;
Second step: above-mentioned casting solution is poured on the hydrophobic film of 30～100 μ m thickness, smoothens, the above-mentioned composite membrane that has coated in 70～100 ℃ baking oven, is dried by the fire 30～50min, preparation is finished.
8. the preparation method of any described hydrophilic-hydrophobic bipolar complex membrane of claim 4～7, it is characterized in that described hydrophobic film be Kynoar, polysulfones, polyvinyl chloride, polypropylene, polyethylene any one.
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| CN1059356C (en) * | 1994-12-28 | 2000-12-13 | 中国科学院大连化学物理研究所 | Modified polysulphone super-filter membrane and its preparation and application |
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| CN1218774C (en) * | 2002-04-12 | 2005-09-14 | 四川大学 | Method for making composite membrane for separation of polymer fluid |
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