CN1276262A

CN1276262A - Process and special equipment for preparing anti-pollution compound plyvinyl alcohol film

Info

Publication number: CN1276262A
Application number: CN 99108061
Authority: CN
Inventors: 刘忠洲; 李娜; 续曙光; 吴光夏
Original assignee: Research Center for Eco Environmental Sciences of CAS
Current assignee: Research Center for Eco Environmental Sciences of CAS
Priority date: 1999-06-08
Filing date: 1999-06-08
Publication date: 2000-12-13
Anticipated expiration: 2019-06-08
Also published as: CN1124874C

Abstract

A process for preparing anti-pollution compound polyvinyl alcohol film includes such steps as immersing basic film in 1-20 wt% aqueous solution or alcohol solution of surfactant, aqueous solution or alcohol solution of surfactant (1-20 wt.%) plus cross-linking agent (0.1-1 vol%), aqueous solution of alcohol (20-60 vol%), aqueous solution of alcohol (20-60 vol%) and cross-linking agent (0.1-1 vol%), or aqueous solution of cross-linking agent (0.1-1 vol% at 5-70 deg.C for 0.5-24 hr, compounding the filming liquid on the surface of basic film, cross-linking drying and post treatment.

Description

A kind of preparation method of anti-pollution compound plyvinyl alcohol film and special equipment thereof

The invention belongs to the technical field of pellicle separating technology, particularly a kind of preparation method of anti-pollution compound plyvinyl alcohol film and equipment thereof.

Composite membrane generally is to be made of following two tunics: the upper strata, and---ultra-thin separating layer (cortex)---main resistance---plays centrifugation;---porous support layer (basement membrane)---less important resistance---strengthens supporting role in lower floor.

The preparation method of composite membrane makes porous support layer earlier to make basement membrane, forms the ultra-thin separating layer of one deck then on the porous membrane surface.The formation method of ultra-thin separating layer has polymer-coated method, interface condensation and interface polycondensation, monomer catalytic polymerization, plasma polymerization etc.

Because the film contamination phenomenon in the film running has become the bottleneck that the restriction membrane technology further developed and enlarged application, therefore how solving membrane pollution problem becomes the problem that current membrane separation technique field is more and more paid close attention to.Film pollute be meant with feed liquid that film contact in the big molecule of particulate, colloidal particle or solute because absorption in film surface or hole, the deposition that exists physics, chemical action or mechanism to cause with film causes membrane aperture to diminish or stops up, make the phenomenon of film generation through the irreversible change of flow and stalling characteristic.The key and the fundamental way that solve the film pollution are the films that development and exploitation have good stain resistance, and the focus that this has become current film research field is one of trend of membrane technology development.

For improving the resistance tocrocking of film, the general hydrophilic material of selecting is as the membrane material of making ultra-thin separating layer when the preparation composite membrane, its basic principle is: the raising of film surface hydrophilicity can reduce contact and the absorption combination between polluter and the film surface, thereby reduces the pollution on film surface.

Polyvinyl alcohol (PVA) has highly hydrophilic and stain resistance, has the well characteristic of anti-multiple organic solvent, is easy to film forming, and physics, chemical property are stablized, and cheap and easy to get, therefore becomes the attractive membrane material that has of making the anti-pollution film.As, day disclosure special permission communique 06,170,193[94,170,193], Japan Patent 63031501, European patent 47953 etc. also the using polymer coating method prepared the polyvinyl alcohol composite hyperfiltration membrane.

The focus that these researchs and patent are paid close attention to is the formation of the ultra-thin separating layer of hydrophily, and the result only makes the upper surface of porous basement membrane form the hydrophily superthin layer, and consequent film still exists the porous basement membrane to be easy to pollution problems.Though A.G.Fane etc. point out film and pollute the upper surface mainly occur in film, the fenestra internal contamination is less, and the fenestra internal contamination still has a significant impact film properties, and it makes film resistance tocrocking variation, and the stability of runnability reduces.If so improving the hydrophilic hydrophily that improves the fenestra inner surface simultaneously of film outer surface, then absorption and the deposition of pollutant in fenestra can reduce, the contamination resistance of film and runnability will improve greatly, especially will be even more important through the separation process of film to product.

The polymer-coated method more approaching with this patent method is that the direct hydrostomia of polymer solution is soaked in the polymer solution to make composite membrane on membrane surface or with basement membrane.The outer surface that adopts the immersion cladding process to make fenestra inner surface and film as Japan Patent 94093980 all has the almost composite hyperfiltration membrane of uniform polyvinyl alcohol thin layer of one deck.But because polyvinyl alcohol has highly hydrophilic, with glassware for drinking water close solubility parameter (23.4) is arranged, and the hydrophobicity of basement membrane is often bigger, cause the surface tension on polyvinyl alcohol molecule and basal lamina material surface bigger, so only depend on the diffusion motion of polymer molecule and intermolecular weak force Van der Waals force (Van Der Waals) to be difficult to make hydrophilic polyethene alcohol to form the composite bed of one deck even compact in the hydrophobicity membrane surface, and the composite bed fastness that forms is relatively poor, be easy to break away from, directly influenced the stain resistance of composite membrane and the stability of operation.

With coating legal system film the time, prior art is to use knifing machine, flat basement membrane is rolled on the roller bearing of knifing machine, then preparation liquid is poured into the liquid bath that is connected with scraper, control the thickness of composite bed by the distance of regulating scraper and basement membrane, but polyvinyl alcohol concentration is lower in the poly-vinyl alcohol solution that generally is suitable for during owing to the making composite membrane, cause preparation liquid viscosity lower, bad with hydrophobic basement membrane tack, make the uniform films of controllable thickness system so can't use scraper: the PVA film of scraping often will be through Overheating Treatment, because the membrane area that launches is very big, so be difficult to heat treatment; The knifing machine cost is high, and floor space is big, can only make flat film.

Also there is employing that basement membrane is immersed preparation liquid, or film liquid is poured on the basement membrane face, smoke film forming after hydrostomia is even, can make the composite membrane assembly of other kind form like this, but because surface tension is bigger, preparation liquid has the sagging phenomenon on membrane surface, the composite bed that makes is difficult to evenly, and composite bed thickness is wayward, and other film forming condition is also wayward, therefore be not easy to control the aperture of composite membrane, be difficult to make composite membrane with even composite bed with various apertures.

The object of the present invention is to provide a kind of preparation method of anti-pollution compound plyvinyl alcohol film, the ultra-thin separating layer of polyvinyl alcohol that makes the composite membrane surface of preparing is even compact more, and is more firm with combining of basement membrane; Not only can form the ultra-thin PVA gel layer of layer of even, and on the internal surface of hole of film, also form the even PVA gel layer of one deck, improve the stain resistance and the operation stability of film with this on the upper and lower surface of basement membrane.

Another object of the present invention is to provide a kind of special equipment of finishing said method, it can reach a tractor serves several purposes as the operational outfit of film separation process again as membrane equipment, saves cost of equipment; The method of operating of this equipment is flexible, membrane module convenient disassembly from the film device, operating condition is easy to control, can control the thickness and the crosslink density of ultra-thin polyvinyl alcohol composite bed by selecting suitable operating condition, thereby obtain the composite membrane of polyvinyl alcohol in various apertures according to actual needs, comprise complex reverse osmosis membrane, composite nanometer filtering film, composite hyperfiltration membrane and composite micro-filtration membrane; This membrane equipment is not subjected to the restriction of basement membrane form, can produce flat, doughnut formula, spiral wound and tubular type composite membrane of polyvinyl alcohol or membrane module.

The preparation method of anti-pollution compound plyvinyl alcohol film of the present invention is described in detail as follows:

During the system composite membrane, to be connected on the membrane equipment through pretreated basement membrane or basement membrane assembly, add depress make contain polyvinyl alcohol macromolecule polymer solution in membrane equipment with the operation of certain type of flow, the flow through upper and lower surface of basement membrane of preparation liquid, and through fenestra, upper and lower surface and internal surface of hole at basement membrane adhere to one deck high molecular polymer superthin layer equably and carry out crosslinked and post processing, finally obtain anti-pollution compound plyvinyl alcohol film.

The first step: the preliminary treatment of basement membrane.Basement membrane carries out preliminary treatment earlier before compound, purpose is the surface tension that reduces polyvinyl alcohol preparation liquid and membrane surface, and the polyvinyl alcohol molecule is attached on the basement membrane more equably.

With basement membrane 9 or be contained in basement membrane 9 in the membrane module 8 and be immersed in the pretreatment fluid of the aqueous solution of 1～20wt% aqueous surfactant solution or alcoholic solution, 1～20wt% surfactant+0.1～1vol% cross-linking agent aqueous solution or alcoholic solution, 20～60vol% alcohol solution, the 20～60vol% alcohol solution that contains 0.1～1vol% crosslinking agent or 0.1～1vol% crosslinking agent, soak time is 0.5～24 hour, the soak temperature is 5～70 ℃, obtains pretreated basement membrane 9 or is contained in basement membrane 9 in the membrane module 8.

Second step: preparation liquid is compounded on the upper and lower surface and internal surface of hole of basement membrane with filtration method.Filtration method comprises and oppositely adds dead-end filtration, oppositely adds cross-flow filtration, dead-end filtration or four kinds of methods of cross-flow filtration.Fig. 1 is the membrane equipment schematic diagram.

Adopt the dead-end filtration mode that oppositely adds:

Phase I is adopted reverse filtration earlier, pretreated basement membrane 9 is put into the membrane module 8 of membrane equipment, the membrane module 8 that film 9 maybe will be housed connects in the membrane equipment, shut off valve 2, valve 15, valve 17, valve 20, valve 28, open valve 5, valve 10, valve 13, valve 21, valve 29, with preparation liquid (I) or (II) pour material fluid bath 4 into, open pump 1, at this moment preparation liquid (I) or (II) from material fluid bath 4 triple valve 3 of flowing through, pump 1, triple valve 27, valve 29, heater 30, triple valve 31, triple valve 14, triple valve 6, valve 21, film lower surface feed liquid inflow entrance 23 by membrane module 8 enters in the membrane module 8, simultaneously another part preparation liquid (I) or (II) triple valve 14 of flowing through, valve 5 returns liquid baths 4, regulate the pressure of feed liquid inflow entrance 23 with valve 5, pressure limit is 0.01～1MPa, regulate the pressure of feed liquid flow export 25 with valve 10, make outlet pressure than the low 0.01～1MPa of inlet pressure, under pressure, enter a part of preparation liquid (I) of membrane module 8 or (II) flow through the film lower surface of basement membrane 9, by the film lower surface feed liquid flow export 25 of membrane module 8 triple valve 18 of flowing through, triple valve 26, valve 10 returns liquid baths 4, another part preparation liquid (1) or (II) see through the fenestra of basement membrane 9 is by the film upper surface feed liquid flow export 24 of membrane module 8 triple valve 11 of flowing through, valve 13 turns back to material fluid bath 4; Its reverse filtration running time is 1～30 minute, and the preparation liquid temperature is 5～90 ℃.

Second stage adopts dead-end filtration again, after reverse filtration is finished, shut off valve 2, valve 13, valve 15, valve 17, valve 21, valve 28, open valve 5, valve 10, valve 20, valve 29, pour in the material fluid bath 4 with preparation liquid (I) or (II), open pump 1, a part of preparation liquid (I) or (II) enter the membrane module 8 from the film upper surface feed liquid inflow entrance 22 of material fluid bath 4 by triple valve 3, pump 1, triple valve 27, valve 29, heater 30, triple valve 31, triple valve 14, triple valve 6, valve 20, membrane module 8; Another part preparation liquid (I) or (II) flow through in triple valve 14, the valve 5 returns liquid baths 4 simultaneously; Regulate the pressure of feed liquid inflow entrance 22 with valve 5, in pressure limit is the fenestra that enters the preparation liquid (I) of membrane module 8 under 0.01～10MPa or (II) see through basement membrane 9, by the film lower surface feed liquid flow export 25 of membrane module 8, the triple valve 18 of flowing through, triple valve 26, valve 10 turn back to material fluid bath 4; Or above-mentioned valve 15 opened, valve 10 cuts out, the pressure of the on off state of all the other valves and feed liquid inflow entrance 22 as hereinbefore, then enter the preparation liquid (I) of membrane module 8 or (II) see through the fenestra of basement membrane 9, enter into through liquid bath 16 by flow through triple valve 18, valve 15 of the film lower surface feed liquid flow export 25 of membrane module 8; Its dead-end filtration running time is 1～600 minute, and the preparation liquid temperature is 5～90 ℃, finally obtains upper and lower surface of basement membrane and internal surface of hole and scribbles one deck preparation liquid (I) or film (II) 9 or be contained in basement membrane 9 in the membrane module 8.

Or employing oppositely adds the cross-flow filtration mode:

Phase I is adopted reverse filtration earlier, pretreated basement membrane 9 is put into the membrane module 8 of membrane equipment, the membrane module 8 that film 9 maybe will be housed connects in the membrane equipment, shut off valve 2, valve 15, valve 17, valve 20, valve 28, open valve 5, valve 10, valve 13, valve 21, valve 29, with preparation liquid (I) or (II) pour material fluid bath 4 into, open pump 1, at this moment preparation liquid (I) or (II) from material fluid bath 4 triple valve 3 of flowing through, pump 1, triple valve 27, valve 29, heater 30, triple valve 31, triple valve 14, triple valve 6, valve 21, film lower surface feed liquid inflow entrance 23 by membrane module 8 enters in the membrane module 8, simultaneously another part preparation liquid (I) or (II) triple valve 14 of flowing through, valve 5 returns liquid baths 4; Regulate the pressure of feed liquid inflow entrance 23 with valve 5, making inlet pressure ranges is 0.01～1MPa, regulate the pressure of feed

liquid flow export

24 and 25 with valve 10, make outlet pressure than the low 0.01～1MPa of inlet pressure, under pressure, enter a part of preparation liquid (I) of membrane module 8 or (II) flow through the film lower surface of basement membrane 9, by the film lower surface feed liquid flow export 25 of membrane module 8 triple valve 18 of flowing through, triple valve 26, valve 10 returns liquid baths 4, another part preparation liquid (I) or (II) see through the fenestra of basement membrane 9 is by the film upper surface feed liquid flow export 24 of membrane module 8 triple valve 11 of flowing through, valve 13 turns back to material fluid bath 4; Its reverse filtration running time is 1～30 minute, and the preparation liquid temperature is 5～90 ℃.

Second stage adopts cross-flow filtration again, after reverse filtration is finished, shut off valve 2, valve 15, valve 17, valve 21, valve 28, open valve 5, valve 10, valve 13, valve 20, valve 29, pour in the material fluid bath 4 with preparation liquid (I) or (II), open pump 1, at this moment preparation liquid (I) or (II) from material fluid bath 4 triple valve 3 of flowing through, pump 1, triple valve 27, valve 29, heater 30, triple valve 31, triple valve 14, triple valve 6, valve 20, the film upper surface feed liquid inflow entrance 22 of membrane module 8 enters in the membrane module 8, simultaneously another part preparation liquid (I) or (II) triple valve 14 of flowing through, valve 5 returns liquid baths 4; Regulate the pressure of feed liquid inflow entrance 22 with valve 5, pressure limit is 0.01～10MPa, regulate the pressure of feed

liquid flow export

24 and 25 with valve 13, make outlet pressure than the low 0.01～10MPa of inlet pressure, under pressure, enter a part of preparation liquid (I) of membrane module 8 or (II) flow through the film upper surface of basement membrane 9, by the film upper surface feed liquid flow export 24 of membrane module 8 triple valve 11 of flowing through, valve 13 returns liquid baths 4, another part preparation liquid (I) or (II) see through the fenestra of basement membrane 9 is by the film lower surface feed liquid flow export 25 of membrane module 8 triple valve 18 of flowing through, triple valve 26, valve 10 turns back to material fluid bath 4; Or above-mentioned valve 15 opened, valve 10 cuts out, the pressure of the on off state of all the other valves and feed liquid inflow entrance 22 and

flow export

24 and 25 as hereinbefore, preparation liquid (I) or (II) see through the fenestra of basement membrane 9 then enters into through liquid bath 16 by flow through triple valve 18, valve 15 of the film upper surface feed liquid flow export 25 of membrane module 8; Its cross-flow filtration running time is 1～600 minute, and the preparation liquid temperature is 5～90 ℃, finally obtains upper and lower surface of basement membrane and internal surface of hole and scribbles one deck preparation liquid (I) or film (II) 9 or be contained in basement membrane 9 in the membrane module 8.

Or employing dead-end filtration mode:

Pretreated basement membrane 9 is put into the membrane module 8 of membrane equipment, the membrane module 8 that film 9 maybe will be housed connects in the membrane equipment, shut off valve 2, valve 13, valve 15, valve 17, valve 21, valve 28, open valve 5, valve 10, valve 20, valve 29, pour in the material fluid bath 4 with preparation liquid (I) or (II), open pump 1, a part of preparation liquid (I) or (II) enter the membrane module 8 from the film upper surface feed liquid inflow entrance 22 of material fluid bath 4 by triple valve 3, pump 1, triple valve 27, valve 29, heater 30, triple valve 31, triple valve 14, triple valve 6, valve 20, membrane module 8; Another part preparation liquid (I) or (II) flow through in triple valve 14, the valve 5 returns liquid baths 4 simultaneously; Regulate the pressure of feed liquid inflow entrance 22 with valve 5, in pressure limit is the fenestra that enters the preparation liquid (I) of membrane module 8 under 0.01～10MPa or (II) see through basement membrane 9, by the film lower surface feed liquid flow export 25 of membrane module 8, the triple valve 18 of flowing through, triple valve 26, valve 10 turn back to material fluid bath 4; Or above-mentioned valve 15 opened, valve 10 cuts out, the pressure of the on off state of all the other valves and feed liquid inflow entrance 22 as hereinbefore, then enter the preparation liquid (I) of membrane module 8 or (II) see through the fenestra of basement membrane 9, enter into through liquid bath 16 by flow through triple valve 18, valve 15 of the film lower surface feed liquid flow export 25 of membrane module 8; Its dead-end filtration running time is 1～600 minute, and the preparation liquid temperature is 5～90 ℃, finally obtains upper and lower surface of basement membrane and internal surface of hole and scribbles one deck preparation liquid (I) or film (II) 9 or be contained in basement membrane 9 in the membrane module 8.

Or employing cross-flow filtration mode:

Pretreated basement membrane 9 is put into the membrane module 8 of membrane equipment, the membrane module 8 that film 9 maybe will be housed connects in the membrane equipment, shut off valve 2, valve 15, valve 17, valve 21, valve 28, open valve 5, valve 10, valve 13, valve 20, valve 29, pour in the material fluid bath 4 with preparation liquid (I) or (II), open pump 1, at this moment preparation liquid (I) or (II) from material fluid bath 4 triple valve 3 of flowing through, pump 1, triple valve 27, valve 29, heater 30, triple valve 31, triple valve 14, triple valve 6, valve 20, the film upper surface feed liquid inflow entrance 22 of membrane module 8 enters in the membrane module 8, simultaneously another part preparation liquid (I) or (II) triple valve 14 of flowing through, valve 5 returns liquid baths 4; Regulate the pressure of feed liquid inflow entrance 22 with valve 5, pressure limit is 0.01～10MPa, regulate the pressure of feed

liquid flow export

flow export

The 3rd step: film 9 carries out crosslinked drying, adopts following two kinds of methods:

A. with the above-mentioned film 9 that obtains by preparation liquid (I), or be contained in film 9 in the membrane module 8, under 10～100 ℃ of temperature crosslinked dry 1～48 hour, obtain crosslinked dried film 9, or the crosslinked dried film 9 that is contained in the membrane module 8.

Or

B. with the above-mentioned film 9 that obtains by preparation liquid (II), or be contained in film 9 in the membrane module 8, drying is 1～48 hour under 10～100 ℃ of temperature, immersed then in the cross-linking agent solution 1～60 minute, the crosslinking agent weight percent concentration is 0.001～15wt%, obtain crosslinked dried film 9, or the crosslinked dried film 9 that is contained in the membrane module 8; Or adopt any one mode of above-mentioned filtration method, with cross-linking agent solution as feed liquid, move 1～60 minute, the weight percent concentration of crosslinking agent is 0.001～15wt%, then with film 9 or be contained in film 9 in the membrane module 8, under 10～100 ℃ of temperature crosslinked dry 1～48 hour, obtain crosslinked dried film 9 or the crosslinked dried film 9 that is contained in the membrane module 8.

The 4th step: the post processing of rinsing additive and film:

Above-mentioned crosslinked dried film 9 or the film 9 that is contained in the membrane module 8 were put into 10～50 ℃ of distilled water more than 24 hours, additive is disengaged and make film 9 or the film 9 that is contained in the membrane module 8 reaches swelling equilibrium; Then with film 9 or be contained in film 9 in the membrane module 8 to be immersed in weight percent concentration be in 20～60% the alcohol solution 0.5～24 hour; Or with film 9 or be contained in film 9 in the membrane module 8 and be immersed in 50～90 ℃ of distilled water and spend the night; Finally obtain anti-pollution compound plyvinyl alcohol film.

Polyvinyl alcohol preparation liquid of the present invention (I) and preparation method (II) following (weight percent concentration):

The thick preparation liquid of preparation liquid (I): under the room temperature with the polyvinyl alcohol of any molecular weight, or the polyvinyl alcohol of several different molecular weights is pressed the mixture that arbitrary proportion mixes, or polyvinyl alcohol and polymer such as polyamide-based, SPSF, polyethylene glycol oxide or piperazines, be not less than the mixture that 50% ratio is mixed in the polyvinyl alcohol weight percent concentration, be dissolved in the solvent fully, wherein said polyvinyl alcohol concentration is 0.01～15wt% in system, is preferably 0.01～5wt%; Be added in then that concentration is the additive of 1～50wt% in the system, be preferably 10～20wt% and concentration is 0.001～15wt% in system crosslinking agent, be preferably 0.1～1%, and it is dissolved fully, make the thick preparation liquid of preparation liquid (I).

The thick preparation liquid of preparation liquid (II): under the room temperature polyvinyl alcohol of any molecular weight or the polyvinyl alcohol of several different molecular weights are pressed the mixture that arbitrary proportion mixes, or polyvinyl alcohol and polyamide-based, SPSF, polymer such as polyethylene glycol oxide or piperazines, be not less than the mixture that 50% ratio is mixed in the polyvinyl alcohol weight percent concentration, be dissolved in the solvent fully, wherein said polyvinyl alcohol concentration in system is 0.01～15wt%, be preferably 0.01～5wt%. and be added in then that concentration is the additive of 1～50wt% in the system, be preferably 10～20wt%, and it is dissolved fully, make the thick preparation liquid of preparation liquid (II).

Preparation liquid of the present invention generally will carry out pre-filtering to remove impurity wherein, and pre-filtering equipment can adopt membrane equipment of the present invention (seeing accompanying drawing 1).Filter membrane and membrane module 8 are installed in the film device, filter membrane has flat, the doughnut formula, spiral wound, tubular type etc., the pore diameter range of filter membrane is 1～50 μ m, be preferably 1～10 μ m, shut off valve 2, valve 10, valve 13, valve 17, valve 21, valve 29, open valve 5, valve 15, valve 20, valve 28, with thick preparation liquid (I) or (II) pour material fluid bath 4 into, open pump 1, at this moment preparation liquid is from material fluid bath 4 triple valve 3 of flowing through, pump 1, triple valve 27, valve 28, triple valve 31, triple valve 14, triple valve 6, valve 20, film upper surface feed liquid inflow entrance 22 by membrane module 8 enters membrane module 8, another part preparation liquid triple valve 14 of flowing through simultaneously, valve 5 returns liquid baths 4, regulate the pressure of feed liquid inflow entrance 22 with valve 5, operating pressure is 0.01～5MPa, be preferably 0.01～1MPa, the thick preparation liquid that enters membrane module 8 under pressure flows through the lower surface of film through fenestra from the upper surface of filter membrane 9, by the film lower surface feed liquid flow export 25 of membrane module 8 triple valve 18 of flowing through, valve 15 enters through liquid bath 16, sees through preparation liquid in the liquid bath 16 and promptly be the preparation liquid (I) or (II) after filtering.

The polyvinyl alcohol molecular weight ranges is 10,000～300,000, and the alcoholysis degree scope is 78%～100%, has better intensity and stability for making the composite membrane that makes, and suitable molecular weight ranges is 70,000～220,000, and suitable alcoholysis degree scope is 98%～100%.The basement membrane average pore size of selecting for use should be greater than selected polyvinyl alcohol molecular size, and with the molecular size of the polymer of polyvinyl alcohol blending, all can form one deck hydrophily superthin layer on upper and lower surface of film and internal surface of hole like this.

Solvent for use has water, some alcohol compounds, dimethyl sulfoxide (DMSO), diethyl triamine, triethyl group tetramine, acid amides, oxolane, phenol-water mixed liquid etc.; Alcohols wherein has isopropyl alcohol, triethanolamine, glycerine, ethylene glycol, polyethylene glycol, ethanolamine salt etc.; Acid amides wherein has formamide, NMF, hydroxyethyl acetamide, methylacetamide, ethyl acetamide etc.; Selected solvent is the mixed solvent of above-mentioned any single solvent or several solvents, must consider during selective solvent that organic solvent can not have big swelling to membrane material, or membrane structure is had destruction.Water is solvent preferably often.

Used polyvinyl alcohol crosslinked dose has aldehyde, twain-aldehyde compound, ketone, dicarboxylic acids, alcohol, dicarboxylic anhydride, acyl chlorides, dicarbonyl compound etc.; For example formaldehyde, butyraldehyde, benzaldehyde, methacrylaldehyde, glutaraldehyde, acetone, oxalic acid, malonic acid, succinic acid, citric acid, hydroxysuccinic acid, dyhydrobutanedioic acid, inositol, poly-methyl alkene ether-alt-maleic anhydride, cis-butenedioic anhydride, PMA acid anhydride, phthalic anhydride, triphen diether tetracid acid anhydride, isophthaloyl chloride, toluene two isonitrile acid etc.

Additive in the preparation liquid not only can increase the permeable speed of film, can increase simultaneously the viscosity of preparation liquid and to the wetability of membrane material, can improve composite effect, improve preparation liquid viscosity and can cause the permeable speed of film to descend and adopt to improve the concentration of filmogen in the preparation liquid or molecular weight.Additive therefor is any material that dissolves in the polyvinyl alcohol preparation liquid simultaneously again can be water-soluble, can be inorganic salts, acylate, have surface-active polyelectrolyte, some organic matter and a high molecular polymer, for example lithium chloride, lithium nitrate, magnesium sulfate, methyl alcohol, ethanol, ethylene glycol, glycerine, season amylalcohol, ethylene glycol monoemethyl ether, ethylene glycol ethyl ether, dibutyl phthalate, methylcellulose, ethyl cellulose, butyl cellulose, PVP, polyethylene glycol, polypropylene glycol, polyacrylic acid, polyacrylamide etc.

The composition of preparation liquid is one of principal element that influences in the composite membrane aperture.The average pore size of composite membrane reduces along with the increase of filmogen concentration, crosslinker concentration, increases along with the increase of additive concentration.Can control the mean pore size of composite membrane by selecting certain material of preparing concentration, crosslinker concentration and additive concentration.

Cross-linking agent solution is dissolved in the described solvent by described crosslinking agent and makes.Also having acyl chloride (as isophthaloyl chloride), dicarbonyl compound class (as toluene two isonitrile acid) crosslinking agent in addition, is that solvent makes cross-linking agent solution with alkane, aromatic hydrocarbons or ester class etc.The weight percent concentration of all these crosslinking agents in solution is 0.001～15wt%, is preferably 1～50wt%.The concentration, running time and the temperature that contain crosslinking agent in crosslinking temperature, crosslinking time, the cross-linking agent solution all influence the average pore size of composite membrane, and average pore size reduces with the increase of the concentration, running time and the temperature that contain crosslinking agent in crosslinking temperature, crosslinking time, the cross-linking agent solution.

Composite membrane can improve the water flux of composite membrane by post processing under the prerequisite that does not influence the basement membrane performance, and rejection changes not quite or slightly improve.System film running time, film liquid temp, operating pressure etc. all directly influence the mean pore size of composite membrane.Along with prolongation running time, film liquid temp improve, the increase of operating pressure all makes the average pore size of composite membrane reduce.Can make certain average pore size composite membrane by these parameter control.

The anti-pollution compound plyvinyl alcohol film of producing by the inventive method, form by basement membrane and ultra-thin separating layer, it wherein is basement membrane with the microporous barrier, form ultra-thin separating layer by polyvinyl alcohol material or polyvinyl alcohol and hydrophilic polymer composite material on basement membrane internal surface of hole and upper and lower surface, the composite membrane pore diameter range is 10 ^-3～10 μ m.Described microporous barrier is a hydrophily or hydrophobicity is inorganic or organic micro film, and that the kit form of microporous barrier has is flat, doughnut formula, spiral wound and tubular type etc.

Basement membrane is that the method for making single film is routinely made.Basement membrane can be that any one has the hydrophily of certain mechanical strength and materialization stability or hydrophobicity is inorganic or organic micro film in principle.For making the polyvinyl alcohol molecule see through the basement membrane fenestra so that on the basement membrane inner surface, form the layer of even composite bed, have big water penetration and be easy to make the composite membrane in various apertures with the composite membrane that makes, should select that permeability rate is big for use, porosity is big, microporous barrier that have perforate is made basement membrane, the size in hole should be far longer than the molecular size of selected polyvinyl alcohol.The basement membrane pore diameter range is 0.005～100 μ m, and suitable scope is 0.05～100 μ m.That the kit form of basement membrane has is flat, doughnut formula, spiral wound and tubular type etc., can make flat, doughnut formula, spiral wound and tubular type composite membrane of polyvinyl alcohol assembly in view of the above.At other all film forming conditions one regularly, can control the size in the aperture of composite membrane by the selection of basement membrane aperture, porosity size.

Anti-pollution compound plyvinyl alcohol film preparation method's of the present invention special equipment is: have a feed liquid pipe 32 to connect triple valve 3 in the bottom of a material fluid bath 4, the two ends in addition of triple valve 3 connect valve 2 and pump 1 respectively, the other end of pump 1 connects triple valve 27, the two ends in addition of triple valve 27 connect valve 28 and 29 respectively, the other end of valve 29 connects heater 30, the other end of the other end of heater 30 and valve 28 all is connected the two ends of triple valve 31 respectively by feed liquid pipe 32, the other end of triple valve 31 connects triple valve 14, the two ends in addition of triple valve 14 connect valve 5 and Pressure gauge 7 respectively, the other end of valve 5 connects the feed liquid pipe 32 that reaches material fluid bath 4, the other end of Pressure gauge 7 connects triple valve 6, the two ends in addition of triple valve 6 connect valve 20 and valve 21 respectively, the film 9 upper surface feed liquid inflow entrances 22 of valve 20 junctional membrane assemblies 8, another feed liquid inflow entrance 23 of film 9 lower surfaces of valve 21 junctional membrane assemblies 8, the feed liquid flow export 24 of film 9 upper surfaces of membrane module 8 connects triple valve 11, the two ends in addition of triple valve 11 connect Pressure gauge 12 and valve 13 respectively, the other end of valve 13 connects the feed liquid pipe 32 that reaches material fluid bath 4, another feed liquid flow export 25 of film 9 lower surfaces of membrane module 8 connects triple valve 18, the two ends in addition of triple valve 18 connect triple valve 26 and valve 15 respectively, the other end of valve 15 connects the feed liquid pipe 32 that reaches through liquid bath 16, the feed liquid pipe 32 that stretches out through the bottom of liquid bath connects valves 17, the two ends in addition of triple valve 26 connect Pressure gauge 19 and valve 10 respectively, and the other end of valve 10 connects the feed liquid pipe 32 that reaches material fluid bath 4.

The present invention can control the thickness and the crosslink density of ultra-thin polyvinyl alcohol composite bed, thereby can make a series of composite membranes with various average pore sizes by selecting suitable operating condition.The principal element that influences film properties is by the running time and the pressure of the forming of preparation liquid, temperature, compound tense preparation liquid, the temperature and time of crosslinked drying, and the pore size of basement membrane, the preliminary treatment of basement membrane and composite membrane post processing also have certain influence in addition, can be according to actual needs in film-forming process, composite membrane by selection and control to these influence factors can obtain having various average pore sizes comprises complex reverse osmosis membrane, composite nanometer filtering film, composite hyperfiltration membrane and composite micro-filtration membrane.Accompanying drawing 7 is embodiment five, the sem photograph that the amplification of the upper surface of the basement membrane that uses among the embodiment six is 2000 times, accompanying drawing 8 is that its section amplifies 2000 times sem photograph, the film of the film of accompanying drawing 3 and 4 expressions and accompanying drawing 5 and 6 expressions is respectively the composite membrane that makes under two kinds of different film forming conditions, relatively the upper surface of three kinds of films can be found out, because film forming condition difference, the pore size difference of two kinds of composite membranes that obtain, the aperture of the composite membrane of Fig. 3 and 4 expressions is very little, reach the composite hyperfiltration membrane scope, amplify 10000 times with general ESEM and do not observe the hole, the aperture of the composite membrane of Fig. 5 and 6 expressions is seldom littler than basement membrane, belong to the composite micro-filtration membrane scope, can find out from the section photo of three kinds of films, the thickness of thin layer of the upper surface of Fig. 4 is greater than the thickness of Fig. 6, and the upper surface of Fig. 4 is the most smooth smooth, and Fig. 6 takes second place, the then very coarse as shown in Figure 8 injustice of untreated basement membrane.The raising of film surface smoothness can improve the stain resistance of film.

Membrane equipment of the present invention can also reach a tractor serves several purposes as the operational outfit of film separation process, has saved cost of equipment; And the method for operating of this equipment is flexible, membrane module convenient disassembly from the film device, and operating condition is easy to control; The polyvinyl alcohol superthin layer on the composite membrane surface of making by the inventive method is even compact more, make composite bed more firm in epilamellar combination, the composite membrane runnability is fine, the stain resistance of the composite membrane that experiment confirm obtains and operation stable fine, after polluting, wash its pure water transmission rates as this composite membrane of anti-pollution experiment confirm of three of embodiment and can basic 100% recover, and it is fine to do the feed liquid operation stability with pure water and protein solution with clear water.

Below in conjunction with accompanying drawing technical scheme of the present invention is further described.

Fig. 1 membrane equipment schematic diagram of the present invention;

The anti-fouling performance comparative experiments result of the single milipore filter of the unmodified polysulfones of Fig. 2 and the polyvinyl alcohol composite hyperfiltration membrane of preparing according to the embodiment of the invention three;

The upper surface of the composite membrane that Fig. 3 embodiment of the invention five is prepared amplifies 10,000 times stereoscan photograph;

The section of the composite membrane that Fig. 4 embodiment of the invention five is prepared amplifies 2000 times stereoscan photograph;

The upper surface of the composite membrane that Fig. 5 embodiment of the invention six is prepared amplifies 2000 times stereoscan photograph;

The section of the composite membrane that Fig. 6 embodiment of the invention six is prepared amplifies 2000 times stereoscan photograph;

The upper surface of Fig. 7 embodiment of the invention five, six used basement membranes amplifies 2000 times stereoscan photograph;

The section of Fig. 8 embodiment of the invention five, six used basement membranes amplifies 2000 times stereoscan photograph.

Label in the accompanying drawing: 1.

pump

2,5,10,13,15,17,20,21,28,29.

valve

3,6,11,14,18,26,27,31. triple valve 4.

material fluid baths

7,12,19. Pressure gauge 8. membrane modules 9. films 16. are through the film lower surface feed liquid flow export 30. heaters 32. feed liquid pipes of film lower surface feed liquid inflow entrance 25. membrane modules of film upper surface feed liquid flow export 23. membrane modules of film upper surface feed liquid inflow entrance 24. membrane modules of liquid bath 22. membrane modules---PS membrane-◆-Modified Membrane

Embodiment one:

Present embodiment has illustrated preparation method and the process for preparing flat polyvinyl alcohol composite nanometer filtering film.

Basement membrane is that molecular cut off is about 500,000 flat polyacrylonitrile film, and its pure water transmission rates is 180ml/cm under the 0.1MPa pressure ².h.

At first prepare preparation liquid.Under the room temperature be that (molecular weight is 79150 for 1% polyvinyl alcohol with mass concentration, alcoholysis degree is a complete alcoholysis), mass concentration is that (molecular weight is 11 for 1% polyvinyl alcohol, 000～30,000, alcoholysis degree is a complete alcoholysis) mix and be dissolved in the aqueous solvent fully, in system, add mass concentration then and be 10% PEG400, and it is dissolved fully, make the thick preparation liquid of preparation liquid (II).

The above-mentioned phase preparation liquid for preparing is carried out pre-filtering.Polyacrylonitrile filter membrane and membrane module 8 are installed in the membrane equipment, the aperture of its filter membrane is 2 μ m, shut off valve 2,10,13,17,21,29, open valve 5,15,20,28, thick preparation liquid is poured in the material fluid bath 4, open pump 1, at this moment solution is from material fluid bath 4 triple valve 3 of flowing through, pump 1, triple valve 27, valve 28, triple valve 31, triple valve 14, triple valve 6, valve 20, film upper surface feed liquid inflow entrance 22 by membrane module 8 enters in the membrane module 8, the thick preparation liquid of another part triple valve 14 of flowing through simultaneously, in the valve 5 returns liquid baths 4, regulate the pressure of feed liquid inflow entrance 22 with valve 5, operating pressure is 0.05MPa, the thick preparation liquid that enters membrane module 8 under pressure sees through fenestra from the upper surface of filter membrane 9, flow through the lower surface of film, by the film lower surface feed liquid flow export 25 of membrane module 8 triple valve 18 of flowing through, valve 15 enters through liquid bath 16, sees through preparation liquid in the liquid bath 16 and promptly be the preparation liquid (II) after filtering.

Above-mentioned filter membrane is taken out from membrane equipment, and basement membrane soaks the membrane module 8 of putting into membrane equipment after 12 hours in 20 ℃ 60% ethanol water, then preparation liquid (II) is poured in the material fluid bath 4, adopts the dead-end filtration mode that oppositely adds.In the phase I, shut off valve 2,15,17,20,28, open valve 5,10,13,21,29, preparation liquid is poured in the material fluid bath 4, open pump 1, at this moment preparation liquid is from material fluid bath 4 triple valve 3 of flowing through, pump 1, triple valve 27, valve 29, heater 30, triple valve 31, triple valve 14, triple valve 6, valve 21, film lower surface feed liquid inflow entrance 23 by membrane module 8 enters in the membrane module 8, another part preparation liquid triple valve 14 of flowing through simultaneously, in the valve 5 returns liquid baths 4, the pressure of regulating feed liquid inflow entrance 23 with valve 5 is 0.2MPa, the pressure that valve 10 is regulated the feed liquid flow export is 0.05MPa, the a part of preparation liquid that enters membrane module 8 under pressure flows through the film lower surface of basement membrane 9, by the film lower surface feed liquid flow export 25 of membrane module 8 triple valve 18 of flowing through, triple valve 26, in the valve 10 returns liquid baths 4, another part preparation liquid sees through the fenestra of basement membrane 9, by the film upper surface feed liquid flow export 24 of membrane module 8 triple valve 11 of flowing through, valve 13 turns back in the material fluid bath 4, the preparation liquid temperature is 45 ℃, and be 2 minutes running time.

In second stage, shut off

valve

2,10,13,17,21,28, open valve 5,15,20,29, preparation liquid is poured in the material fluid bath 4, open pump 1, at this moment preparation liquid enters the membrane module 8 from the film upper surface feed liquid inflow entrance 22 of material fluid bath 4 by triple valve 3, pump 1, triple valve 27, valve 29, heater 30, triple valve 31, triple valve 14, triple valve 6, valve 20, membrane module 8; While another part preparation liquid is flowed through in triple valve 14, the valve 5 returns liquid baths 4, regulate the pressure of feed liquid inflow entrance 22 with valve 5, at pressure is under the 0.8MPa, the preparation liquid that enters membrane module 8 sees through the fenestra of basement membrane 9, enter through liquid bath 16 by flow through triple valve 18, valve 15 of the film lower surface flow export 25 of membrane module 8, the preparation liquid temperature is 45 ℃, and be 5 minutes running time, finally obtains the film 9 that upper and lower surface of basement membrane and internal surface of hole scribble one deck preparation liquid (II).

The above-mentioned film made taken out put into 50 ℃ of baking ovens crosslinked dry 4 hours, immersed then in the cross-linking agent solution 2 minutes.Cross-linking agent solution is solvent with water, and crosslinking agent is the glutaraldehyde of 0.5% (volumetric concentration); Add catalyst methyl alcohol, acetate, each 0.05% (volumetric concentration) of sulfuric acid again, to put into 50 ℃ of baking ovens crosslinked dry 10 hours after the film taking-up, put into 20 ℃ of distilled water then more than 24 hours, put into 20 ℃ 50wt% ethanol water 10 hours again, obtain anti-pollution compound plyvinyl alcohol film at last.

This composite membrane is the MgSO of 1000ppm to concentration ₄The salt rejection rate of the aqueous solution is 80.7%, and the pure water transmission rates under the 0.8MPa is 9ml/cm ².h, reach the desalination scope of NF membrane.

Embodiment two:

Present embodiment has illustrated that the preparation molecular cut off is the preparation method and the process of 35,000 doughnut formula polyvinyl alcohol composite hyperfiltration membrane.

Basement membrane is that molecular cut off is 150,000 doughnut formula Kynoar composite hyperfiltration membrane assembly, and this basement membrane is that the pure water transmission rates is 43ml/cm under the 0.05MPa at pressure ².h.

At first prepare preparation liquid.Under the room temperature be that (molecular weight is 79150 for 0.2% polyvinyl alcohol with mass concentration, alcoholysis degree is a complete alcoholysis) be dissolved in the aqueous solvent fully, in system, add volumetric concentration then and be 0.15% glutaraldehyde cross-linking agent, be respectively 0.02%, 0.03%, 0.01% methyl alcohol, acetate and sulfuric acid catalyst with volumetric concentration in system, volumetric concentration is 12% PEG400 in system, and it is dissolved fully, make the thick preparation liquid of preparation liquid (I).

The above-mentioned thick preparation liquid for preparing is carried out pre-filtering.Vinylidene filter membrane and membrane module 8 are installed in the membrane equipment, and the aperture of its filter membrane is 1 μ m, and operating process is with embodiment one, and operating pressure is 0.05MPa, the preparation liquid (I) after obtaining filtering.

Above-mentioned filter membrane is taken out from membrane equipment, and the membrane module that film 9 is housed 8 that will soak 12 hours in 20 ℃ 60% ethanol water is put into membrane equipment, then preparation liquid (II) is poured in the material fluid bath 4, adopts oppositely to add cross-flow filtration mode system film.In the phase I, shut off valve 2,15,17,20,28, open valve 5,10,13,21,29, preparation liquid is poured in the material fluid bath 4, open pump 1, at this moment preparation liquid is from material fluid bath 4 triple valve 3 of flowing through, pump 1, triple valve 27, valve 29, heater 30, triple valve 31, triple valve 14, triple valve 6, valve 21, film lower surface feed liquid inflow entrance 23 by membrane module 8 enters in the membrane module 8, another part preparation liquid triple valve 14 of flowing through simultaneously, in the valve 5 returns liquid baths 4, the pressure of regulating feed liquid inflow entrance 23 with valve 5 is 0.1MPa, it is 0.05MPa that valve 10 is regulated feed liquid flow export pressure, the a part of preparation liquid that enters membrane module 8 under pressure flows through the film lower surface of basement membrane 9, by the film lower surface feed liquid flow export 25 of membrane module 8 triple valve 18 of flowing through, triple valve 26, in the valve 10 returns liquid baths 4, another part preparation liquid sees through the fenestra of basement membrane 9, the film upper surface feed liquid flow export 24 of membrane module 8 triple valve 11 of flowing through, valve 13 turns back in the material fluid bath 4, be 2 minutes running time, and the preparation liquid temperature is 45 ℃.

In second stage, shut off valve 2,15,17,21,28, open valve 5,10,13,20,29, preparation liquid is poured in the material fluid bath 4, open pump 1, at this moment preparation liquid enters the membrane module 8 from the flow through film upper surface feed liquid inflow entrance 22 of triple valve 3, pump 1, triple valve 27, valve 29, heater 30, triple valve 31, triple valve 14, triple valve 6, valve 20, membrane module 8 of material fluid bath 4, and another part preparation liquid is flowed through in triple valve 14, the valve 5 returns liquid baths 4 simultaneously; The pressure of regulating feed liquid inflow entrance 22 with valve 5 is 0.1MPa, the pressure that valve 13 is regulated feed liquid flow export 24 and 25 is 0.05MPa, the a part of preparation liquid that enters membrane module 8 under pressure flows through the film upper surface of basement membrane 9, by the film upper surface feed liquid flow export 24 of membrane module 8 triple valve 11 of flowing through, in the valve 13 returns liquid baths 4, another part preparation liquid sees through the fenestra of basement membrane 9, by the film lower surface feed liquid flow export 25 of membrane module 8 triple valve 18 of flowing through, triple valve 26, valve 10 turns back in the material fluid bath 4, preparation liquid running time is 2 minutes, the preparation liquid temperature is 45 ℃, finally obtains on the basement membrane, lower surface and internal surface of hole scribble the film 9 of one deck preparation liquid (I).

The above-mentioned membrane module of making that film 9 is housed 8 is taken out, put it into 50 ℃ of baking ovens, make film 9 crosslinked dry 12 hours, immersed then in the cross-linking agent solution 20 minutes.Cross-linking agent solution is solvent with water, and crosslinking agent is the glutaraldehyde of 0.5% (volumetric concentration); Add catalyst methyl alcohol, acetate, each 0.05% (volumetric concentration) of sulfuric acid again, to put into 50 ℃ of baking ovens crosslinked dry 20 hours after the film taking-up, at room temperature put into distilled water then more than at least 24 hours, put into 80 ℃ of distilled water at last 10 hours, and obtained anti-pollution compound plyvinyl alcohol film at last.

This Modified Membrane is that the rejection of 35,000 stomach cardia is 91.2% to molecular weight, and the pure water transmission rates under the 0.1MPa is 10ml/cm ².h.

Embodiment three:

Present embodiment has illustrated that the preparation molecular cut off is the preparation method and the process of 60,000 flat polyvinyl alcohol composite hyperfiltration membrane.

Select for use average pore size be 0.1 micron flat polyacrylonitrile micro-filtration membrane as micropore basal membrane, its pure water transmission rates is 180ml/cm under the 0.1MPa pressure ².h.

At first prepare preparation liquid.Under the room temperature be that (molecular weight is 79150 for 0.6% polyvinyl alcohol with mass concentration, alcoholysis degree is a complete alcoholysis) be dissolved in the aqueous solvent fully, in system, add volumetric concentration then and be 0.1% glutaraldehyde cross-linking agent, be respectively 0.02%, 0.03%, 0.01% methyl alcohol, acetate and sulfuric acid as catalyst and buffer with volumetric concentration in system, volumetric concentration is that 12% PEG400 is an additive in system, and it is dissolved fully, make the thick preparation liquid of preparation liquid (I).

The above-mentioned thick preparation liquid for preparing is carried out pre-filtering.Polyacrylonitrile filter membrane and membrane module 8 are installed in the membrane equipment, and the aperture of its filter membrane is 1 μ m, and operating process is with embodiment one, and operating pressure is 0.05MPa, the preparation liquid (I) after obtaining filtering.

Above-mentioned filter membrane is taken out from membrane equipment, basement membrane soaks the membrane module 8 of putting into membrane equipment after 5 hours in 20 ℃ 0.1% glutaraldehyde water solution, then preparation liquid (I) is poured in the material fluid bath 4, the operation flow process is with embodiment one, phase I is moved into, outlet pressure is respectively 0.05MPa and 0.02MPa, be 2 minutes running time, the second stage operating pressure is 0.2MPa, be 5 minutes running time, the preparation liquid temperature is 45 ℃, puts into 50 ℃ of baking ovens crosslinked dry 6 hours after film is taken out, and puts into 20 ℃ of distilled water then more than 24 hours, put into 60% ethanol water at last 24 hours, and obtained anti-pollution compound plyvinyl alcohol film at last.

This composite membrane is that the rejection of 60,000 bovine serum albumin(BSA) is 93.7% to molecular weight, is 71.7% to pepsic rejection.Test this Modified Membrane stain resistance and with molecular cut off be that the anti-fouling performance of 60,000 unmodified PS membrane contrasts, experimental result is seen Fig. 2.Fig. 2 illustrates that Modified Membrane is very stable to the runnability of pure water, the pure water transmission rates than unmodified PS membrane decay seldom, and be that 0.1% bovine serum albumin feed liquid runnability is very stable to the mass concentration of pH=7, decay seldom, the saturating rate recovery extent of pure water reaches 100% substantially after cleaning, and is even move repeatedly and clean, still very stable to the transmission rates of pure water and feed liquid, the composite membrane stain resistance that this method making is described is good, and is easy to clean.

Embodiment four:

Present embodiment has illustrated that the preparation molecular cut off is the preparation method and the process of 156,000 flat polyvinyl alcohol composite hyperfiltration membrane.

Selecting average pore size for use is that 0.1 micron flat polyacrylonitrile micro-filtration membrane is as micropore basal membrane.

At first prepare preparation liquid.Under the room temperature be that (molecular weight is 79150 for 0.2% polyvinyl alcohol with mass concentration, alcoholysis degree is a complete alcoholysis) be dissolved in the aqueous solvent fully, in system, add volumetric concentration then and be 0.2% 50% glutaraldehyde cross-linking agent, be respectively 0.02%, 0.03%, 0.01% methyl alcohol, acetate and sulfuric acid as catalyst and buffer with volumetric concentration in system, volumetric concentration is that 12% PEG400 is an additive in system, and it is dissolved fully, make the thick preparation liquid of preparation liquid (I).

Above-mentioned filter membrane is taken out from membrane equipment, basement membrane soaks the membrane module 8 of putting into membrane equipment after 24 hours in 10 ℃ 60% ethanol water, then preparation liquid (I) is poured in the material fluid bath 4, operating process is with embodiment one, phase I is moved into, outlet pressure is respectively 0.05MPa and 0.02MPa, be 2 minutes running time, the second stage operating pressure is 0.2MPa, be 3 minutes running time, the preparation liquid temperature is 45 ℃, then film is taken out and put into 50 ℃ of baking ovens crosslinked dry 6 hours, put into 20 ℃ of distilled water then more than 24 hours: 20% ethanol water that immerses 20 ℃ at last carried out post processing in 2 hours, obtained anti-pollution compound plyvinyl alcohol film at last.

This film is that the rejection of 156,000 r-globulin is 90.3% to molecular weight, and the pure water transmission rates is 65ml/cm under the 0.1MPa pressure ².h.

Embodiment five:

Present embodiment has illustrated that the preparation molecular cut off is about the preparation method and the process of 200,000 flat polyvinyl alcohol composite hyperfiltration membrane.

Basement membrane is that average pore size is 1 micron a flat nylon micro-filtration membrane, in advance through 24 hours preliminary treatment of immersion in 60% ethanol water.

At first prepare preparation liquid.Under the room temperature be that (molecular weight is 79150 for 3% polyvinyl alcohol with mass concentration, alcoholysis degree is a complete alcoholysis), (molecular weight is 11 to mass concentration 2% polyvinyl alcohol, 000～30,000, alcoholysis degree is a complete alcoholysis) be dissolved in the aqueous solvent fully after mixing, adding mass concentration then and be 2% Macrogol 6000 in system is additive, and it is dissolved fully, makes the thick preparation liquid of preparation liquid (II).

The above-mentioned thick preparation liquid for preparing is carried out pre-filtering.Nylon micro-filtration membrane and membrane module 8 are installed in the membrane equipment, and the aperture of its filter membrane is 2 μ m, and operating process is with embodiment one, and operating pressure is 0.1MPa, the preparation liquid (II) after obtaining filtering.

Above-mentioned filter membrane is taken out from membrane equipment, basement membrane soaks the membrane module 8 of putting into membrane equipment after 24 hours in 20 ℃ 60% ethanol water, then preparation liquid (II) is poured in the material fluid bath 4, operating process is with embodiment one, phase I advances, outlet pressure is respectively 0.05MPa and 0.02MPa, be 2 minutes running time, the second stage operating pressure is 0.1MPa, be 10 minutes running time, the preparation liquid temperature is 45 ℃, then film is taken out and put into 50 ℃ of oven dryings 2.5 hours, immersed in the cross-linking agent solution 2 minutes, cross-linking agent solution is for being solvent with water, comprise 0.5% (volumetric concentration) glutaraldehyde, contain methyl alcohol, acetate, each 0.05% (volumetric concentration) of sulfuric acid was put into 50 ℃ of baking ovens crosslinked dry 10 hours then, put into 20 ℃ of distilled water more than 24 hours, immerse at last in 80 ℃ of distilled water and to carry out post processing in 10 hours, obtain anti-pollution compound plyvinyl alcohol film at last.

This film is that 225,000 catalatic rejection is 92.1% to molecular weight, and the pure water transmission rates is 86ml/cm under the 0.1MPa pressure ².h.The upper surface of this film and section SEM scanned photograph are seen Fig. 3, Fig. 4.

Embodiment six:

Present embodiment has illustrated that the preparation aperture is the preparation method and the process of the flat polyvinyl alcohol composite micro-filtration membrane of 0.6 μ m.

Basement membrane is that average pore size is about 1 micron flat nylon micro-filtration membrane.

At first prepare preparation liquid.Under the room temperature be that (molecular weight is 79150 for 1.5% polyvinyl alcohol with mass concentration, alcoholysis degree is a complete alcoholysis), (molecular weight is 11 to mass concentration 1% polyvinyl alcohol, 000～30,000, alcoholysis degree is a complete alcoholysis) be dissolved in the aqueous solvent fully after mixing, adding mass concentration then and be 2% Macrogol 6000 in system is additive, and it is dissolved fully, makes the thick preparation liquid of preparation liquid (II).

Above-mentioned filter membrane is taken out from membrane equipment, basement membrane soaks the membrane module 8 of putting into membrane equipment after 24 hours in 20 ℃ 60% ethanol water, then preparation liquid (II) is poured in the material fluid bath 4, adopt dead-end filtration, all the other operating processes are with embodiment one, its operating pressure is 0.1MPa, be 5 minutes running time, the preparation liquid temperature is 45 ℃, then film is taken out and put into 50 ℃ of oven dryings 3 hours, immersed in the cross-linking agent solution 2 minutes, cross-linking agent solution is for containing 0.5% (volumetric concentration) glutaraldehyde, contain methyl alcohol, acetate, the aqueous solution of sulfuric acid each 0.05% (volumetric concentration) was put into 50 ℃ of baking ovens crosslinked and dry 3 hours then, put into 20 ℃ of distilled water more than 24 hours, immerse at last in 80 ℃ of distilled water and to carry out post processing in 10 hours, obtain anti-pollution compound plyvinyl alcohol film at last.

The average pore size of this film is 0.6 micron, and the pure water transmission rates is 170ml/cm under the 0.05MPa pressure ².h.The upper surface of this film and section SEM scanned photograph are seen Fig. 5, Fig. 6.

Stain resistance experiment of the present invention divided for five steps carried out:

(1) equipment of composite membrane being put into Fig. 1 is surveyed the pure water transmission rates of film, until recording three consecutive identical numerical value (every 5 minutes);

(2) be feed liquid (albumen among the embodiment three is pepsin) with 0.1% protein solution, under 0.1MPa pressure, survey the transmission rates of film, until recording three consecutive identical numerical value (every 10 minutes) to this feed liquid;

(3) film is taken out and with distilled water flushing about 5 minutes, put into then, use pure water instead, the pure water transmission rates of surveying film under 0.1Ma again is until recording three consecutive identical numerical value (every 5 minutes);

(4) repeated for (2) step;

(5) repeated for (3) step.

The type of flow of fluid is the dead-end filtration mode, shut off

valve

2,10,13,17,21,29,

open valve

5,15,20,28, pour pure water or protein solution into material fluid bath 4, open pump 1, at this moment pure water or protein solution pass through triple valve 3 from material fluid bath 4, pump 1, triple valve 27, valve 28, triple valve 31, triple valve 14 and triple valve 6, valve 20 enters membrane module 8, a part of pure water or the protein solution triple valve 14 of flowing through simultaneously, valve 5 returns liquid baths 4, regulating inlet pressure with valve 5 is 0.1MPa, under pressure, enter fenestra that the pure water of membrane module 8 or protein solution see through basement membrane 9 triple valve 18 of flowing through, valve 15 enters through liquid bath 16, operating pressure is 0.1MPa, and the temperature of pure water and protein solution is a room temperature.

Claims

1. the method for making of an anti-pollution compound plyvinyl alcohol film is characterized in that:

The first step: the preliminary treatment of basement membrane,

With basement membrane (9) or be contained in basement membrane (9) in the membrane module (8) and be immersed in the pretreatment fluid of the aqueous solution of 1～20wt% aqueous surfactant solution or alcoholic solution, 1～20wt% surfactant+0.1～1vol% cross-linking agent aqueous solution or alcoholic solution, 20～60vol% alcohol solution, the 20～60vol% alcohol solution that contains 0.1～1vol% crosslinking agent or 0.1～1vol% crosslinking agent, soak time is 0.5～24 hour, the soak temperature is 5～70 ℃, obtains pretreated basement membrane (9) or is contained in basement membrane (9) in the membrane module (8);

Second step: preparation liquid is compounded on the upper and lower surface and internal surface of hole of basement membrane with filtration method,

Adopt the dead-end filtration mode that oppositely adds:

Phase I is adopted reverse filtration earlier, pretreated basement membrane (9) is put into the membrane module (8) of membrane equipment, the membrane module (8) that film (9) maybe will be housed connects in the membrane equipment, shut off valve (2), valve (15), valve (17), valve (20), valve (28), open valve (5), valve (10), valve (13), valve (21), valve (29), with preparation liquid (I) or (II) pour material fluid bath (4) into, open pump (1), at this moment preparation liquid. (I) or (II) from material fluid bath (4) triple valve (3) of flowing through, pump (1), triple valve (27), valve (29), heater (30), triple valve (31), triple valve (14), triple valve (6), valve (21), film lower surface feed liquid inflow entrance (23) by membrane module (8) enters in the membrane module (8), simultaneously another part preparation liquid (I) or (II) triple valve (14) of flowing through, valve (5) returns liquid bath (4), regulate the pressure of feed liquid inflow entrance (23) with valve (5), pressure limit is 0.01～1MPa, regulate the pressure of feed liquid flow export (25) with valve (10), make outlet pressure than the low 0.01～1MPa of inlet pressure, under pressure, enter a part of preparation liquid (I) of membrane module (8) or (II) flow through the film lower surface of basement membrane (9), by the film lower surface feed liquid flow export (25) of membrane module (8) triple valve (18) of flowing through, triple valve (26), valve (10) returns liquid bath (4), another part preparation liquid (I) or (II) see through the fenestra of basement membrane (9) is by the film upper surface feed liquid flow export (24) of membrane module (8) triple valve (11) of flowing through, valve (13) turns back to material fluid bath (4); Its reverse filtration running time is 1～30 minute, and the preparation liquid temperature is 5～90 ℃;

Second stage adopts dead-end filtration again, after reverse filtration is finished, shut off valve (2), valve (13), valve (15), valve (17), valve (21), valve (28), open valve (5), valve (10), valve (20), valve (29), pour in the material fluid bath (4) with preparation liquid (I) or (II), open pump (1), a part of preparation liquid (I) or (II) from material fluid bath (4) by triple valve (3), pump (1), triple valve (27), valve (29), heater (30), triple valve (31), triple valve (14), triple valve (6), valve (20), the film upper surface feed liquid inflow entrance (22) of membrane module (8) enters in the membrane module (8); Another part preparation liquid (I) or (II) flow through in triple valve (14), valve (5) the returns liquid bath (4) simultaneously; Regulate the pressure of feed liquid inflow entrance (22) with valve (5), in pressure limit is the fenestra that enters the preparation liquid (I) of membrane module (8) under 0.01～10MPa or (II) see through basement membrane (9), by the film lower surface feed liquid flow export (25) of membrane module (8), the triple valve of flowing through (18), triple valve (26), valve (10) turn back to material fluid bath (4); Or above-mentioned valve (15) opened, valve (10) cuts out, the pressure of the on off state of all the other valves and feed liquid inflow entrance (22) as hereinbefore, then enter the preparation liquid (I) of membrane module (8) or (II) see through the fenestra of basement membrane (9), enter into through liquid bath (16) by flow through triple valve (18), valve (15) of the film lower surface feed liquid flow export (25) of membrane module (8); Its dead-end filtration running time is 1～600 minute, and the preparation liquid temperature is 5～90 ℃, finally obtains upper and lower surface of basement membrane and internal surface of hole and scribbles one deck preparation liquid (I) or film (II) (9) or be contained in basement membrane (9) in the membrane module (8);

Or employing oppositely adds the cross-flow filtration mode:

Phase I is adopted reverse filtration earlier, pretreated basement membrane (9) is put into the membrane module (8) of membrane equipment, the membrane module (8) that film (9) maybe will be housed connects in the membrane equipment, shut off valve (2), valve (15), valve (17), valve (20), valve (28), open valve (5), valve (10), valve (13), valve (21), valve (29), with preparation liquid (I) or (II) pour material fluid bath (4) into, open pump (1), at this moment preparation liquid (I) or (II) from material fluid bath (4) triple valve (3) of flowing through, pump (1), triple valve (27), valve (29), heater (30), triple valve (31), triple valve (14), triple valve (6), valve (21), film lower surface feed liquid inflow entrance (23) by membrane module (8) enters in the membrane module (8), simultaneously another part preparation liquid (I) or (II) triple valve (14) of flowing through, valve (5) returns liquid bath (4); Regulate the pressure of feed liquid inflow entrance (23) with valve (5), making inlet pressure ranges is 0.01～1MPa, regulate the pressure of feed liquid flow export (24) and (25) with valve (10), make outlet pressure than the low 0.01～1MPa of inlet pressure, under pressure, enter a part of preparation liquid (I) of membrane module (8) or (II) flow through the film lower surface of basement membrane (9), by the film lower surface feed liquid flow export (25) of membrane module (8) triple valve (18) of flowing through, triple valve (26), valve (10) returns liquid bath (4), another part preparation liquid (I) or (II) see through the fenestra of basement membrane (9) is by the film upper surface feed liquid flow export (24) of membrane module (8) triple valve (11) of flowing through, valve (13) turns back to material fluid bath (4); Its reverse filtration running time is 1～30 minute, and the preparation liquid temperature is 5～90 ℃;

Second stage adopts cross-flow filtration again, after reverse filtration is finished, shut off valve (2), valve (15), valve (17), valve (21), valve (28), open valve (5), valve (10), valve (13), valve (20), valve (29), pour in the material fluid bath (4) with preparation liquid (I) or (II), open pump (1), at this moment preparation liquid (I) or (II) from material fluid bath (4) triple valve (3) of flowing through, pump (1), triple valve (27), valve (29), heater (30), triple valve (31), triple valve (14), triple valve (6), valve (20), the film upper surface feed liquid inflow entrance (22) of membrane module (8) enters in the membrane module (8), simultaneously another part preparation liquid (I) or (II) triple valve (14) of flowing through, valve (5) returns liquid bath (4); Regulate the pressure of feed liquid inflow entrance (22) with valve (5), pressure limit is 0.01～10MPa, regulate the pressure of feed liquid flow export (24) and (25) with valve (13), make outlet pressure than the low 0.01～10MPa of inlet pressure, under pressure, enter a part of preparation liquid (I) of membrane module (8) or (II) flow through the film upper surface of basement membrane (9), by the film upper surface feed liquid flow export (24) of membrane module (8) triple valve (11) of flowing through, valve (13) returns liquid bath (4), another part preparation liquid (I) or (II) see through the fenestra of basement membrane (9) is by the film lower surface feed liquid flow export (25) of membrane module (8) triple valve (18) of flowing through, triple valve (26), valve (10) turns back to material fluid bath (4); Or above-mentioned valve (15) opened, valve (10) cuts out, the pressure of the on off state of all the other valves and feed liquid inflow entrance (22) and flow export (24) and (25) as hereinbefore, preparation liquid (I) or (II) see through the fenestra of basement membrane (9) then enters into through liquid bath (16) by flow through triple valve (18), valve (15) of the film upper surface feed liquid flow export (25) of membrane module (8); Its cross-flow filtration running time is 1～600 minute, and the preparation liquid temperature is 5～90 ℃, finally obtains upper and lower surface of basement membrane and internal surface of hole and scribbles one deck preparation liquid (I) or film (II) (9) or be contained in basement membrane (9) in the membrane module (8);

Or employing dead-end filtration mode:

Pretreated basement membrane (9) is put into the membrane module (8) of membrane equipment, the membrane module (8) that film (9) maybe will be housed connects in the membrane equipment, shut off valve (2), valve (13), valve (15), valve (17), valve (21), valve (28), open valve (5), valve (10), valve (20), valve (29), pour in the material fluid bath (4) with preparation liquid (I) or (II), open pump (1), a part of preparation liquid (I) or (II) from material fluid bath (4) by triple valve (3), pump (1), triple valve (27), valve (29), heater (30), triple valve (31), triple valve (14), triple valve (6), valve (20), the film upper surface feed liquid inflow entrance (22) of membrane module (8) enters in the membrane module (8); Another part preparation liquid (I) or (II) flow through in triple valve (14), valve (5) the returns liquid bath (4) simultaneously; Regulate the pressure of feed liquid inflow entrance (22) with valve (5), in pressure limit is the fenestra that enters the preparation liquid (I) of membrane module (8) under 0.01～10MPa or (II) see through basement membrane (9), by the film lower surface feed liquid flow export (25) of membrane module (8), the triple valve of flowing through (18), triple valve (26), valve (10) turn back to material fluid bath (4); Or above-mentioned valve (15) opened, valve (10) cuts out, the pressure of the on off state of all the other valves and feed liquid inflow entrance (22) as hereinbefore, then enter the preparation liquid (I) of membrane module (8) or (II) see through the fenestra of basement membrane (9), enter into through liquid bath (16) by flow through triple valve (18), valve (15) of the film lower surface feed liquid flow export (25) of membrane module (8); Its dead-end filtration running time is 1～600 minute, and the preparation liquid temperature is 5～90 ℃, finally obtains upper and lower surface of basement membrane and internal surface of hole and scribbles one deck preparation liquid (I) or film (II) (9) or be contained in basement membrane (9) in the membrane module (8);

Or employing cross-flow filtration mode:

Pretreated basement membrane (9) is put into the membrane module (8) of membrane equipment, the membrane module (8) that film (9) maybe will be housed connects in the membrane equipment, shut off valve (2), valve (15), valve (17), valve (21), valve (28), open valve (5), valve (10), valve (13), valve (20), valve (29), pour in the material fluid bath (4) with preparation liquid (I) or (II), open pump (1), at this moment preparation liquid (I) or (II) from material fluid bath (4) triple valve (3) of flowing through, pump (1), triple valve (27), valve (29), heater (30), triple valve (31), triple valve (14), triple valve (6), valve (20), the film upper surface feed liquid inflow entrance (22) of membrane module (8) enters in the membrane module (8), simultaneously another part preparation liquid (I) or (II) triple valve (14) of flowing through, valve (5) returns liquid bath (4); Regulate the pressure of feed liquid inflow entrance (22) with valve (5), pressure limit is 0.01～10MPa, regulate the pressure of feed liquid flow export (24) and (25) with valve (13), make outlet pressure than the low 0.01～10MPa of inlet pressure, under pressure, enter a part of preparation liquid (I) of membrane module (8) or (II) flow through the film upper surface of basement membrane (9), by the film upper surface feed liquid flow export (24) of membrane module (8) triple valve (11) of flowing through, valve (13) returns liquid bath (4), another part preparation liquid (I) or (II) see through the fenestra of basement membrane (9) is by the film lower surface feed liquid flow export (25) of membrane module (8) triple valve (18) of flowing through, triple valve (26), valve (10) turns back to material fluid bath (4); Or above-mentioned valve (15) opened, valve (10) cuts out, the pressure of the on off state of all the other valves and feed liquid inflow entrance (22) and flow export (24) and (25) as hereinbefore, preparation liquid (I) or (II) see through the fenestra of basement membrane (9) then enters into through liquid bath (16) by flow through triple valve (18), valve (15) of the film upper surface feed liquid flow export (25) of membrane module (8); Its cross-flow filtration running time is 1～600 minute, and the preparation liquid temperature is 5～90 ℃, finally obtains upper and lower surface of basement membrane and internal surface of hole and scribbles one deck preparation liquid (I) or film (II) (9) or be contained in basement membrane (9) in the membrane module (8);

The 3rd step: film (9) carries out crosslinked drying, adopts following two kinds of methods:

A. with the above-mentioned film (9) that obtains by preparation liquid (I), or be contained in film (9) in the membrane module (8), under 10～100 ℃ of temperature crosslinked dry 1～48 hour, obtain crosslinked dried film (9), or the crosslinked dried film (9) that is contained in the membrane module (8);

Or

B. with the above-mentioned film (9) that obtains by preparation liquid (II), or be contained in film (9) in the membrane module (8), drying is 1～48 hour under 10～100 ℃ of temperature, immersed then in the cross-linking agent solution 1～60 minute, the crosslinking agent weight percent concentration is 0.001～15wt%, obtain crosslinked dried film (9), or the crosslinked dried film (9) that is contained in the membrane module (8); Or adopt any one mode of above-mentioned filtration method, with cross-linking agent solution as feed liquid, move 1～60 minute, the weight percent concentration of crosslinking agent is 0.001～15wt%, then with film (9) or be contained in film (9) in the membrane module (8), under 10～100 ℃ of temperature crosslinked dry 1～48 hour, obtain crosslinked dried film (9) or the crosslinked dried film (9) that is contained in the membrane module (8);

The 4th step: the post processing of rinsing additive and film:

Above-mentioned crosslinked dried film (9) or the film (9) that is contained in the membrane module (8) were put into 10～50 ℃ of distilled water more than 24 hours, additive is disengaged and make film (9) or the film (9) that is contained in the membrane module (8) reaches swelling equilibrium; Then with film (9) or be contained in film (9) in the membrane module (8) to be immersed in weight percent concentration be in 20～60% the alcohol solution 0.5～24 hour; Or with film (9) or be contained in film (9) in the membrane module (8) and be immersed in 50～90 ℃ of distilled water and spend the night; Finally obtain anti-pollution compound plyvinyl alcohol film.

2. the method for making of anti-pollution compound plyvinyl alcohol film as claimed in claim 1 is characterized in that described preparation liquid (I) and preparation method (II) are as follows:

The thick preparation liquid of preparation liquid (I): under the room temperature with the polyvinyl alcohol of any molecular weight, or the polyvinyl alcohol of several different molecular weights is pressed the mixture that arbitrary proportion mixes, or polyvinyl alcohol and polyamide-based, SPSF, polyethylene glycol oxide or piperazines polymer, be not less than the mixture that 50% ratio is mixed in the polyvinyl alcohol weight percent concentration, be dissolved in the solvent fully, wherein said polyvinyl alcohol concentration is 0.01～15wt% in system, be added in then that concentration is the additive of 1～50wt% in the system, with concentration in system be the crosslinking agent of 0.001～15wt%, and it is dissolved fully, make the thick preparation liquid of preparation liquid (I);

The thick preparation liquid of preparation liquid (II): under the room temperature polyvinyl alcohol of any molecular weight or the polyvinyl alcohol of several different molecular weights are pressed the mixture that arbitrary proportion mixes, or polyvinyl alcohol and polyamide-based, SPSF, polyethylene glycol oxide or piperazines polymer, be not less than the mixture that 50% ratio is mixed in the polyvinyl alcohol weight percent concentration, be dissolved in the solvent fully, wherein said polyvinyl alcohol concentration in system is 0.01～15wt%, be added in then that concentration is the additive of 1～50wt% in the system, and it is dissolved fully, make the thick preparation liquid of preparation liquid (II);

Filter membrane and membrane module (8) are installed in the film device, the pore diameter range of filter membrane is 1～50 μ m, shut off valve (2), valve (10), valve (13), valve (17), valve (21), valve (29), open valve (5), valve (15), valve (20), valve (28), with thick preparation liquid (I) or (II) pour material fluid bath (4) into, open pump (1), at this moment preparation liquid is from material fluid bath (4) triple valve (3) of flowing through, pump (1), triple valve (27), valve (28), triple valve (31), triple valve (14), triple valve (6), valve (20), film upper surface feed liquid inflow entrance (22) by membrane module (8) enters membrane module (8), another part preparation liquid triple valve (14) of flowing through simultaneously, valve (5) returns liquid bath (4), regulate the pressure of feed liquid inflow entrance (22) with valve (5), operating pressure is 0.01～5MPa, the thick preparation liquid that enters membrane module (8) under pressure flows through the lower surface of film through fenestra from the upper surface of filter membrane (9), by the film lower surface feed liquid flow export (25) of membrane module (8) triple valve (18) of flowing through, valve (15) enters through liquid bath (16), sees through preparation liquid in the liquid bath (16) and promptly be the preparation liquid (I) or (II) after filtering.

3. as the method for making of right 1 described anti-pollution compound plyvinyl alcohol film, it is characterized in that described polyvinyl alcohol molecular weight ranges is 10,000～300,000, the alcoholysis degree scope is 78%～100%.

4. as the method for making of right 3 described anti-pollution compound plyvinyl alcohol films, it is characterized in that described polyvinyl alcohol molecular weight ranges is 70,000～220,000, the alcoholysis degree scope is 98%～100%.

5. as the method for making of right 1 or 2 described anti-pollution compound plyvinyl alcohol films, it is characterized in that described solvent is water, alcohol compound, dimethyl sulfoxide (DMSO), diethyl triamine, triethyl group tetramine, acid amides, oxolane, phenol-water mixed liquid; Described polyvinyl alcohol crosslinked dose is aldehyde, twain-aldehyde compound, ketone, dicarboxylic acids, alcohol, dicarboxylic anhydride, acyl chlorides, dicarbonyl compound; Described additive is for being dissolved in inorganic salts, acylate that the polyvinyl alcohol preparation liquid simultaneously again can be water-soluble, having surface-active polyelectrolyte or organic matter and high molecular polymer.

6. as the method for making of right 5 described anti-pollution compound plyvinyl alcohol films, it is characterized in that described alcohol compound is isopropyl alcohol, triethanolamine, glycerine, ethylene glycol, polyethylene glycol or ethanolamine salt; Described acid amides is formamide, NMF, hydroxyethyl acetamide, methylacetamide or ethyl acetamide; Described aldehyde is formaldehyde, butyraldehyde or benzaldehyde; Described twain-aldehyde compound is methacrylaldehyde or glutaraldehyde; Described ketone is an acetone; Described dicarboxylic acids is oxalic acid, malonic acid, succinic acid, citric acid, hydroxysuccinic acid or dyhydrobutanedioic acid; Described alcohol is inositol; Described dicarboxylic anhydride is poly-methyl alkene ether-alt-maleic anhydride, cis-butenedioic anhydride, PMA acid anhydride, phthalic anhydride or triphen diether tetracid acid anhydride; Described acyl chlorides is an isophthaloyl chloride; Described dicarbonyl compound is toluene two isonitrile acid; Described inorganic salts are lithium chloride, lithium nitrate or magnesium sulfate; Described have surface-active polyelectrolyte or organic matter and high molecular polymer be methyl alcohol, ethanol, ethylene glycol, glycerine, season amylalcohol, ethylene glycol monoemethyl ether, ethylene glycol ethyl ether, dibutyl phthalate, methylcellulose, ethyl cellulose, butyl cellulose, PVP, polyethylene glycol, polypropylene glycol, polyacrylic acid, polyacrylamide.

7. as the method for making of right 1 described anti-pollution compound plyvinyl alcohol film, it is characterized in that described basement membrane is to have the hydrophily of mechanical strength and materialization stability or hydrophobicity is inorganic or the microporous barrier of organically flat, doughnut formula, spiral wound or tubular type, pore diameter range is 0.005～100 μ m.

8. as the method for making of right 7 described anti-pollution compound plyvinyl alcohol films, it is characterized in that described basement membrane pore diameter range is 0.05～100 μ m.

9. as the method for making of right 1 described anti-pollution compound plyvinyl alcohol film, the soak time that it is characterized in that described basement membrane (9) or be contained in the basement membrane (9) in the membrane module (8) is 10～24 hours, and the soak temperature is 30～50 ℃.

10. as the special equipment of right 1 described anti-pollution compound plyvinyl alcohol film method for making, the bottom that it is characterized in that a material fluid bath (4) has a feed liquid pipe (32) to connect triple valve (3), the two ends in addition of triple valve (3) connect valve (2) and pump (1) respectively, the other end of pump (1) connects triple valve (27), the two ends in addition of triple valve (27) connect valve (28) and (29) respectively, the other end of valve (29) connects heater (30), the other end of the other end of heater (30) and valve (28) all is connected the two ends of triple valve (31) respectively by feed liquid pipe (32), the other end of triple valve (31) connects triple valve (14), the two ends in addition of triple valve (14) connect valve (5) and Pressure gauge (7) respectively, the other end of valve (5) connects the feed liquid pipe (32) that reaches material fluid bath (4), the other end of Pressure gauge (7) connects triple valve (6), the two ends in addition of triple valve (6) connect valve (20) and valve (21) respectively, film (9) the upper surface feed liquid inflow entrance (22) of valve (20) junctional membrane assembly (8), another feed liquid inflow entrance (23) of film (9) lower surface of valve (21) junctional membrane assembly (8), the feed liquid flow export (24) of film (9) upper surface of membrane module (8) connects triple valve (11), the two ends in addition of triple valve (11) connect Pressure gauge (12) and valve (13) respectively, the other end of valve (13) connects the feed liquid pipe (32) that reaches material fluid bath (4), another feed liquid flow export (25) of film (9) lower surface of membrane module (8) connects triple valve (18), the two ends in addition of triple valve (18) connect triple valve (26) and valve (15) respectively, the other end of valve (15) connects the feed liquid pipe (32) that reaches through liquid bath (16), the feed liquid pipe (32) that stretches out through the bottom of liquid bath connects valve (17), the two ends in addition of triple valve (26) connect Pressure gauge (19) and valve (10) respectively, and the other end of valve (10) connects the feed liquid pipe (32) that reaches material fluid bath (4).