CN101879416A - Method for preparing cellulose composite sodium filter membrane - Google Patents
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- CN101879416A CN101879416A CN 201010161641 CN201010161641A CN101879416A CN 101879416 A CN101879416 A CN 101879416A CN 201010161641 CN201010161641 CN 201010161641 CN 201010161641 A CN201010161641 A CN 201010161641A CN 101879416 A CN101879416 A CN 101879416A
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Abstract
The invention discloses a method for preparing a cellulose composite sodium filter membrane, which comprises the following steps of: (1) dissolving cellulose or cellulose derivates into ionic liquid under a heating condition to obtain solution for preparing the membrane; (2) uniformly coating the solution for preparing the membrane on a non-woven fabric support and then soaking the support into a coagulating bath for coagulation to obtain a cellulose composite membrane; and (3) placing the obtained cellulose composite membrane into the solution of polyacid, poly-acyl chloride or poly-anhydride to perform crosslinking to prepare the cellulose composite sodium filter membrane. In the invention, the ionic liquid has high cellulose and cellulose derivates dissolving capability is used as the membrane-preparing solvent, so the membrane formation performance is high; and the ionic liquid can be recycled and repeatedly used. The crosslinked cellulose selective zone has high hydrophilism and selectivity, and the composite sodium filter membrane has a high flux and a high rejection ratio and can be widely applied in the separation and concentration of dyes, neutral particles, medicaments, food additives and the like.
Description
Technical field
The present invention relates to a kind of technology of preparing of NF membrane material, a kind of preparation method's of cellulose composite sodium filter membrane method specifically is provided.
Background technology
NF membrane is all novel pressure drive membranes between milipore filter and reverse osmosis membrane of a kind of flux of growing up the nearly more than ten years and separating effect, and its appearance has promoted the development of membrane technology and association area greatly.Nanofiltration membrane component has had very fast progress at the mid-80, and has been implemented in industrialization, uses widely having obtained aspect field such as petrochemical industry, biochemistry, medicine, food, papermaking, weaving, printing and dyeing and the water treatment.For the research of NF membrane, China starts late, beginning and the later stage eighties.Though research unit is in continuous increase, major part all is in laboratory stage.
Compare with traditional film separation process, NF membrane has following characteristics: 1) nano level hollow structure; 2) operating pressure is low; 3) have densification preferably and stronger contamination resistance; 4) can replace a plurality of steps in the processing procedure in the tradition, thereby have high economic benefit.
In order to make the low NF membrane of high flux operating pressure, people often adopt the preparation method of preparation composite membrane.Promptly on the big support membrane of the good flux of intensity, cover one deck selection separating layer as thin as a wafer.The method that generally adopts has cladding process, interfacial polymerization, plasma irradiation grafting, chemical gaseous phase deposition method and uv photo initiated grafting polymerization etc. now.Present industrialized product major part all is to adopt the method for interfacial polymerization.
The macromolecular polysaccharide that cellulose (cellulose) is made up of glucose is the main component of plant cell wall.Cellulose is a kind of polysaccharide that the occurring in nature distribution is the widest, content is maximum, accounts for more than 50% of plant kingdom's carbon content.The content of cellulose of cotton is near 100%, is natural pure cellulose source.In the general timber, cellulose comprises 40～50%, 10～30% hemicellulose and 20～30% lignin in addition.With respect to non-renewable energy resources such as coal and oil,, cellulose is inexhaustible, the nexhaustible renewable organic resource of occurring in nature.And cellulosic material itself is nontoxic, water-resistance is strong, meets the requirement of biodegradability, environment compatibility material, so cellulose is very extensive as the potential range of application of host material.
As everyone knows, cellulose is insoluble to usual vehicle, uses widely thereby limit it.But the recent findings ionic liquid can dissolving cellulos, receives researchers' very big concern.Ionic liquid is a class in room temperature or closes on the liquid organic salt of being made up of the yin, yang ion fully under the room temperature, it has excellent chemical stability and heat endurance, be difficult to oxidized, not flammable, decomposition temperature can reach more than 400 ℃, and vapour pressure is extremely low, hardly volatilization, and can reclaim easily and reuse, thereby be considered to the supercritical CO that continues
2" green " solvent of another very attractive afterwards; Ionic liquid has " designability ", can design different anion/cation combinations as required, regulates ion liquid physico-chemical property and functional characteristic, and trillion kinds of possible ionic liquids of surpassing are arranged in theory.
At present, more existing reports of the research of ion liquid dissolving cellulose aspect membrane technology.Patent CNCN101463137 utilizes ionic liquid to prepare good natural polymer blended membrane as the cosolvent of cellulose, starch, lignin and protein.It is solvent with the ionic liquid that patent CN101234297 discloses a kind of, utilize various celluloses to be raw material, adopt dry-wet spinning technology spinning to prepare the cellulose hollow fiber film of mechanical strength height, stable chemical performance, in this kind method, also need add big molecule of hydrophily and organic matter pore-foaming agent and just can obtain hollow-fibre membrane.It is the preparation method of the cellulose membrane of solvent with the ionic liquid that patent CN101284913 has described a kind of, be about to cotton-shaped or pulverize after cellulose and the ionic liquid mixed dissolution after make film, be used for packaging material, ornament materials, printing material, it is solvent that patent CN101074287 provides with the ionic liquid, cellulose and polyacrylonitrile dissolving are dissolved in the ionic liquid jointly the preparation homogeneous mixed solution; Can adopt water is coagulating agent, preparation cellulose/polyacrylonitrile blend laminated film or composite fibre.Dissolve in cellulose, fiber crops, polyacrylonitrile and the ionic liquid that the high and low degree of polymerization that patent CN101230494 will pulverize is mixed, the spinning solution that cellulose, fiber crops, polyacrylonitrile are formed is spun into hollow-fibre membrane then, is used for the film of using of manufacture of intraocular internal organs and water purifier.
The characteristics of the method that this patent provided are that ionic liquid is applied in the NF membrane preparation, select for use suitable ionic liquid that the dissolving of cellulose or derivatives thereof is obtained preparation liquid, preparation liquid evenly is coated on the nonwoven supporter, immerse in the coagulating bath together with supporter then and solidify, obtain cellulose composite membrane, use crosslinking agent that the cellulose or derivatives thereof is crosslinked at last, obtain the composite nanometer filtering film of flux height, good hydrophilic property.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of cellulose composite sodium filter membrane comprises the steps: with a kind of preparation method of cellulose composite sodium filter membrane
The preparation method of cellulose composite sodium filter membrane comprises the steps:
1) be that 1.0～20.0% cellulose or derivatives thereof and mass percent are that 80.0～99.0% ionic liquid adds in the high-temperature resistant container with mass percent, be heated to 80～150 ℃ under argon shield, dissolving evenly obtains film making solution under the mechanical agitation;
2) with the even blade coating of film making solution on the nonwoven supporter, the film making solution layer thickness is the 50-300 micron;
3) nonwoven that will be coated with film making solution exposed to the sun 5～60 seconds in air hollow, immersed temperature then and be in 0～60 ℃ the coagulating bath to solidify, and obtained cellulose composite membrane;
4) cellulose composite membrane being immersed mass percentage concentration is cross-linking reaction 5 minutes～1 hour in 0.1～10% the cross-linking agent solution, takes out then to place 60～120 ℃ baking oven to stop 5～120 minutes, obtains cellulose composite sodium filter membrane.
Described cellulose or derivatives thereof is ethyl cellulose, cellulose powder or methylcellulose.Described ionic liquid is made up of cation and anion, and cation is 1-pi-allyl-3-methylimidazole ion or 1-butyl-3-methylimidazole ion, and anion is TFMS ion, chlorion or bromide ion.Described coagulating bath be a kind of in water, the ethanol or both with any than the mixture of forming.Described crosslinking agent is glutaraldehyde, succinic anhydride, pyromellitic dianhydride, succinic acid, adipic acid, PMA, terephthalic acid (TPA), pyromellitic trimethylsilyl chloride or paraphthaloyl chloride.The solvent of described crosslinking agent is n-hexane, normal heptane or normal octane.Not having described nonwoven is polypropylene fibre (PP), terylene (PET), polyamide fibre (PA), viscose rayon, acrylic fibers, polyethylene (HDPE), polyvinyl chloride fibre (PVC), polysulfones (PSf).The cellulosic mass fraction of described step 1) is preferably 4%～12%, and heating-up temperature is preferably 80～120 ℃.Described step 2) coating thickness is preferably 100～200 microns.The sky time of exposing to the sun of described step 3) is preferably 10～60 seconds, and coagulation bath temperature is preferably 10～35 ℃.The crosslinker concentration of described step 4) is preferably 0.5%～5%, and crosslinking time is preferably 10～30 minutes, and oven temperature is preferably 60～80 ℃, and the time is preferably 5～60 minutes.
The invention has the beneficial effects as follows:
1. prepared composite nanometer filtering film with ultra-thin fine and close separating layer, its separating layer thickness can be controlled the separating layer densification and the zero defect that obtain by regulating coating thickness and coating liquid concentration.
2. the employed solvent of patternmaking process is an ionic liquid, and vapour pressure is extremely low, volatilization hardly, and can reclaim and reuse environmental protection easily.
3. cellulose conveniently obtains, and cheap, makes the preparation method of this cross-linked cellulose composite nanometer filtering film be easier to realize industrialization.
4. prepared cellulose composite sodium filter membrane with ultra-thin fine and close separating layer reaches 100% to the rejection of multiple dyestuff, and flux is big.
The specific embodiment
The invention provides a kind of preparation method of cellulose composite sodium filter membrane, be made up of four steps, the specific embodiment of each step is followed successively by:
1) be that 1.0～20.0% cellulose or derivatives thereof and mass percent are that 60.0～99.0% ionic liquid adds in the high-temperature resistant container with mass percent, under argon shield, be heated to 80～150 ℃, dissolving evenly obtains film making solution under mechanical agitation;
Optimum condition: cellulosic mass fraction is 4%～12%, and heating-up temperature is 80～120 ℃.
2) on the nonwoven supporter, the film making solution layer thickness is the 50-300 micron to the employing scraper with the even blade coating of film making solution;
Optimum condition: coating thickness: 100～200 microns.
3) nonwoven that will be coated with film making solution exposed to the sun 5～80 seconds in air hollow, immersed temperature then and be in 0～60 ℃ the coagulating bath to solidify, and obtained cellulose composite membrane;
Optimum condition: sky exposes to the sun 10～60 seconds time, and coagulation bath temperature is 10～35 ℃.
4) cellulose composite membrane being immersed mass percentage concentration is cross-linking reaction 5 minutes～1 hour in 0.1～10% the cross-linking agent solution, takes out then to place 50～120 ℃ baking oven to stop 5～120 minutes, obtains cellulose composite sodium filter membrane.
Optimum condition: crosslinker concentration is 0.5%～5%, crosslinking time 10～30 minutes, and oven temperature: 60～80 ℃, the time: 5～60 minutes.
After film preparation finishes, can separate containing ion liquid extractant rectifying, so that ionic liquid is recycled.
The invention will be further described below in conjunction with embodiment, but described embodiment is not construed as limiting the invention for example.
Embodiment 1:
With the quality percentage composition is that 1% cellulose (a-cellulose) quality percentage composition is that ionic liquid 1 pi-allyl-3-methylimidazole villaumite ([AMIM] Cl) of 98% adds in the high-temperature resistant container, under argon shield, be warming up to 80 ℃, cellulose fully dissolves evenly under mechanical agitation, the coating liquid that obtains clarifying; The cellulose coating liquid is coated on polypropylene fibre (PP) nonwoven uniformly, and coating thickness is 300 microns; The sky time of exposing to the sun is 20 seconds, is immersed in then in 10 ℃ the coagulating bath, and coagulating bath is a deionized water, and the cellulose solution of coating solidifies, and obtains cellulose composite membrane; Cellulose composite membrane is dried in the shade, be immersed in the hexane solution of pyromellitic trimethylsilyl chloride, mass fraction is to take out after 0.1%, 5 minute; Then film is placed 60 ℃ baking oven to keep 10 minutes, obtain cellulose composite sodium filter membrane.Be that the light blue of 0.1g/L, Congo red and methyl orange are tested with concentration under the pressure of 0.4Mpa, the water flux of this film is 345.5L/m
2H, wherein the removal efficiency of light blue is 70.5%, and Congo red removal efficiency is 88.6%, and the removal efficiency of methyl orange is 9.4%.
Embodiment 2:
With the quality percentage composition is that 4% cellulose (a-cellulose) quality percentage composition is that ionic liquid 1 pi-allyl-3-methylimidazole villaumite ([AMIM] Cl) of 96% adds in the high-temperature resistant container, under argon shield, be warming up to 80 ℃, cellulose fully dissolves evenly under mechanical agitation, the coating liquid that obtains clarifying; The cellulose coating liquid is coated on terylene (PET) nonwoven uniformly, and coating thickness is 150 microns; The sky time of exposing to the sun is 10 seconds, is immersed in then in 15 ℃ the coagulating bath, and coagulating bath is a deionized water, and the cellulose solution of coating solidifies, and obtains cellulose composite membrane; Cellulose composite membrane is dried in the shade, be immersed in the hexane solution of succinic anhydride, mass fraction is 1%,, take out after 10 minutes; Then film is placed 70 ℃ baking oven to keep 20 minutes, obtain cellulose composite sodium filter membrane.Be that the light blue of 0.1g/L, Congo red and methyl orange are tested with concentration under the pressure of 0.4Mpa, the water flux of this film is 338.5L/m
2H, wherein the removal efficiency of light blue is 88.3%, and Congo red removal efficiency is 96.5%, and the removal efficiency of methyl orange is 55.1%.
Embodiment 3:
With the quality percentage composition is that 4% cellulose (a-cellulose) quality percentage composition is ionic liquid 1-butyl-3-methylimidazole fluoroform sulphonate ([BMIM] CF of 96%
3SO
3) add in the high-temperature resistant container, under argon shield, being warming up to 90 ℃, cellulose fully dissolves evenly under mechanical agitation, the coating liquid that obtains clarifying; The cellulose coating liquid is coated on polyamide fibre (PA) nonwoven uniformly, and coating thickness is 200 microns; The sky time of exposing to the sun is 20 seconds, is immersed in then in 60 ℃ the coagulating bath, and coagulating bath is a deionized water, and the cellulose solution of coating solidifies, and obtains cellulose composite membrane; Cellulose composite membrane is dried in the shade, be immersed in the normal octane solution of succinic acid, mass fraction is to take out after 2%, 20 minute; Then film is placed 70 ℃ baking oven to keep 30 minutes, obtain cellulose composite sodium filter membrane.Be that the light blue of 0.1g/L, Congo red and methyl orange are tested with concentration under the pressure of 0.4Mpa, the water flux of this film is 288.5L/m
2H, wherein the removal efficiency of light blue is 90.5%, and Congo red removal efficiency is 100%, and the removal efficiency of methyl orange is 65.7%.
Embodiment 4:
With the quality percentage composition is that 6% methylcellulose (Methyl cellulose) quality percentage composition is that ionic liquid 1-butyl-3-methylimidazole villaumite ([BMIM] Cl) of 94% adds in the high-temperature resistant container, under argon shield, be warming up to 90 ℃, cellulose fully dissolves evenly under mechanical agitation, the coating liquid that obtains clarifying; The cellulose coating liquid is coated on the viscose rayon nonwoven uniformly, and coating thickness is 150 μ m; The sky time of exposing to the sun is 30 seconds, is immersed in then in 20 ℃ the coagulating bath, and coagulating bath is an ethanol, and the cellulose solution of coating solidifies, and obtains cellulose composite membrane; Cellulose composite membrane is dried in the shade, be immersed in the n-heptane solution of pyromellitic dianhydride, mass fraction is to take out after 3%, 30 minute; Then film is placed 70 ℃ baking oven to keep 30 minutes, obtain cellulose composite sodium filter membrane.Be that the light blue of 0.1g/L, Congo red and methyl orange are tested with concentration under the pressure of 0.4Mpa, the water flux of this film is 188.5L/m
2H, wherein the removal efficiency of light blue is 100%, and Congo red removal efficiency is 100%, and the removal efficiency of methyl orange is 90.2%.
Embodiment 5:
With the quality percentage composition is that 6% cellulose (a-cellulose) quality percentage composition is that ionic liquid 1 pi-allyl-3-methylimidazole villaumite ([AMIM] Cl) of 94% adds in the high-temperature resistant container, under argon shield, be warming up to 100 ℃, cellulose fully dissolves evenly under mechanical agitation, the coating liquid that obtains clarifying; The cellulose coating liquid is coated on the acrylic fibers nonwoven uniformly, and coating thickness is 180 microns; The sky time of exposing to the sun is 30 seconds, is immersed in then in 15 ℃ the coagulating bath, and coagulating bath is an ethanol, and the cellulose solution of coating solidifies, and obtains cellulose composite membrane; Cellulose composite membrane is dried in the shade, be immersed in the normal octane solution of glutaraldehyde, mass fraction is to take out after 4%, 40 minute; Then film is placed 80 ℃ baking oven to keep 40 minutes, obtain cellulose composite sodium filter membrane.Be that the light blue of 0.1g/L, Congo red and methyl orange are tested with concentration under the pressure of 0.4Mpa, the water flux of this film is 158.5L/m
2H, wherein the removal efficiency of light blue is 100%, and Congo red removal efficiency is 100%, and the removal efficiency of methyl orange is 98.2%.
Embodiment 6:
With the quality percentage composition is that 8% cellulose (a-cellulose) quality percentage composition is that ionic liquid 1-butyl-3-methylimidazole bromine salt ([BMIM] Br) of 92% adds in the high-temperature resistant container, under argon shield, be warming up to 100 ℃, cellulose fully dissolves evenly under mechanical agitation, the coating liquid that obtains clarifying; The cellulose coating liquid is coated on polyvinyl chloride fibre (PVC) nonwoven uniformly, and coating thickness is 120 μ m; The sky time of exposing to the sun is 30 seconds, is immersed in then in 5 ℃ the coagulating bath, and coagulating bath is a deionized water, and the cellulose solution of coating solidifies, and obtains cellulose composite membrane; Cellulose composite membrane is dried in the shade, be immersed in the normal octane solution of PMA, mass fraction is to take out after 3%, 10 minute; Then film is placed 60 ℃ baking oven to keep 30 minutes, obtain cellulose composite sodium filter membrane.Be that the light blue of 0.1g/L, Congo red and methyl orange are tested with concentration under the pressure of 0.4Mpa, the water flux of this film is 116.7L/m
2H, wherein the removal efficiency of light blue is 100%, and Congo red removal efficiency is 100%, and the removal efficiency of methyl orange is 99.4%.
Embodiment 7:
With the quality percentage composition is that 8% cellulose (a-cellulose) quality percentage composition is that ionic liquid 1 pi-allyl-3-methylimidazole villaumite ([AMIM] Cl) of 92% adds in the high-temperature resistant container, under argon shield, be warming up to 110 ℃, cellulose fully dissolves evenly under mechanical agitation, the coating liquid that obtains clarifying; The cellulose coating liquid is coated on polyethylene (HDPE) nonwoven uniformly, and coating thickness is 150 microns; The sky time of exposing to the sun is 60 seconds, is immersed in then in 15 ℃ the coagulating bath, and coagulating bath is an ethanol, and the cellulose solution of coating solidifies, and obtains cellulose composite membrane; Cellulose composite membrane is dried in the shade, be immersed in the hexane solution of paraphthaloyl chloride, mass fraction is to take out after 4%, 20 minute; Then film is placed 80 ℃ baking oven to keep 40 minutes, obtain cellulose composite sodium filter membrane.Be that the light blue of 0.1g/L, Congo red and methyl orange are tested with concentration under the pressure of 0.4Mpa, the water flux of this film is 98.5L/m
2H, wherein light blue, removal efficiency Congo red, methyl orange are 100%.
Embodiment 8:
With the quality percentage composition is that 10% cellulose (a-cellulose) quality percentage composition is that ionic liquid 1 pi-allyl-3-methylimidazole bromine salt ([AMIM] Br) of 90% adds in the high-temperature resistant container, under argon shield, be warming up to 110 ℃, cellulose fully dissolves evenly under mechanical agitation, the coating liquid that obtains clarifying; The cellulose coating liquid is coated on the PET nonwoven uniformly, and coating thickness is 100 microns; The sky time of exposing to the sun is 1 minute, is immersed in then in 25 ℃ the coagulating bath, and coagulating bath is ethanol and deionized water (volume fraction is 1: 1), and the cellulose solution of coating solidifies, and obtains cellulose composite membrane; Cellulose composite membrane is dried in the shade, be immersed in the normal octane solution of pyromellitic dianhydride, mass fraction is to take out after 4%, 10 minute; Then film is placed 60 ℃ baking oven to keep 40 minutes, obtain cellulose composite sodium filter membrane.Be that the light blue of 0.1g/L, Congo red and methyl orange are tested with concentration under the pressure of 0.4Mpa, the water flux of this film is 78.5L/m
2H, wherein light blue, removal efficiency Congo red, methyl orange are 100%.
Embodiment 9:
With the quality percentage composition is that 10% ethyl cellulose (Ethyl cellulose) quality percentage composition is that ionic liquid 1 pi-allyl-3-methylimidazole villaumite ([AMIM] Cl) of 90% adds in the high-temperature resistant container, under argon shield, be warming up to 120 ℃, cellulose fully dissolves evenly under mechanical agitation, the coating liquid that obtains clarifying; The cellulose coating liquid is coated on polysulfones (PSf) nonwoven uniformly, and coating thickness is 150 microns; The sky time of exposing to the sun is 30 seconds, is immersed in then in 15 ℃ the coagulating bath, and coagulating bath is a deionized water, and the cellulose solution of coating solidifies, and obtains cellulose composite membrane; Cellulose composite membrane is dried in the shade, be immersed in the hexane solution of pyromellitic trimethylsilyl chloride, mass fraction is to take out after 5%, 20 minute; Then film is placed 80 ℃ baking oven to keep 15 minutes, obtain cellulose composite sodium filter membrane.Be that the light blue of 0.1g/L, Congo red and methyl orange are tested with concentration under the pressure of 0.4Mpa, the water flux of this film is 66.7L/m
2H, wherein light blue, removal efficiency Congo red, methyl orange are 100%.
Embodiment 10:
With the quality percentage composition is that 20% cellulose (a-cellulose) quality percentage composition is that ionic liquid 1 pi-allyl-3-methylimidazole villaumite ([AMIM] Cl) of 88% adds in the high-temperature resistant container, under argon shield, be warming up to 150 ℃, cellulose fully dissolves evenly under mechanical agitation, the coating liquid that obtains clarifying; The cellulose coating liquid is coated on the PET nonwoven uniformly, and coating thickness is 50 microns; The sky time of exposing to the sun is 40 seconds, is immersed in then in 20 ℃ the coagulating bath, and coagulating bath is a deionized water, and the cellulose solution of coating solidifies, and obtains cellulose composite membrane; Cellulose composite membrane is dried in the shade, be immersed in the n-heptane solution of pyromellitic dianhydride, mass fraction is to take out after 10%, 60 minute; Then film is placed 120 ℃ baking oven to keep 2 hours, obtain cellulose composite sodium filter membrane.Be that the light blue of 0.1g/L, Congo red and methyl orange are tested with concentration under the pressure of 0.4Mpa, the water flux of this film is 36.5L/m
2H, wherein light blue, removal efficiency Congo red, methyl orange are 100%.
Claims (10)
1. the preparation method of a cellulose composite sodium filter membrane is characterized in that comprising the steps:
1) be that 1.0～20.0% cellulose or derivatives thereof and mass percent are that 80.0～99.0% ionic liquid adds in the high-temperature resistant container with mass percent, be heated to 80～150 ℃ under argon shield, dissolving evenly obtains film making solution under the mechanical agitation;
2) with the even blade coating of film making solution on the nonwoven supporter, the film making solution layer thickness is the 50-300 micron;
3) nonwoven that will be coated with film making solution exposed to the sun 5～60 seconds in air hollow, immersed temperature then and be in 5～60 ℃ the coagulating bath to solidify, and obtained cellulose composite membrane;
4) cellulose composite membrane being immersed mass percentage concentration is cross-linking reaction 5 minutes～1 hour in 0.1～10% the cross-linking agent solution, takes out then to place 60～100 ℃ baking oven to stop 5～120 minutes, obtains cellulose composite sodium filter membrane.
2. the preparation method of a kind of cellulose composite sodium filter membrane according to claim 1 is characterized in that, described cellulose or derivatives thereof is ethyl cellulose, cellulose powder or methylcellulose.
3. the preparation method of a kind of cellulose composite sodium filter membrane according to claim 1, it is characterized in that, described ionic liquid is made up of cation and anion, cation is 1-pi-allyl-3-methylimidazole ion or 1-butyl-3-methylimidazole ion, and anion is TFMS ion, chlorion or bromide ion.
4. the preparation method of a kind of cellulose composite sodium filter membrane according to claim 1 is characterized in that, described coagulating bath be a kind of in water, the ethanol or both with any than the mixture of forming.
5. the preparation method of a kind of cellulose composite sodium filter membrane according to claim 1, it is characterized in that, described crosslinking agent is glutaraldehyde, succinic anhydride, pyromellitic dianhydride, succinic acid, adipic acid, PMA, terephthalic acid (TPA), pyromellitic trimethylsilyl chloride or paraphthaloyl chloride, and the solvent of described crosslinking agent is n-hexane, normal heptane or normal octane.
6. the preparation method of a kind of cellulose composite sodium filter membrane according to claim 1, it is characterized in that described nonwoven is polypropylene fibre (PP), terylene (PET), polyamide fibre (PA), viscose rayon, acrylic fibers, polyethylene (HDPE), polyvinyl chloride fibre (PVC), polysulfones (PSf).
7. the preparation method of a kind of cellulose composite sodium filter membrane according to claim 1 is characterized in that, the cellulosic mass fraction of described step 1) is 4%～12%, and heating-up temperature is 80～120 ℃.
8. the preparation method of a kind of cellulose composite sodium filter membrane according to claim 1 is characterized in that, described step 2) coating thickness be 100～200 microns.
9. the preparation method of a kind of cellulose composite sodium filter membrane according to claim 1 is characterized in that, the sky time of exposing to the sun of described step 3) is 10～60 seconds, and coagulation bath temperature is 10～35 ℃.
10. the preparation method of a kind of cellulose composite sodium filter membrane according to claim 1 is characterized in that, the crosslinker concentration of described step 4) is 0.5%～5%, and crosslinking time is 10～30 minutes, and oven temperature is 60～80 ℃, and the time is 5～60 minutes.
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| CN102580578A (en) * | 2012-02-21 | 2012-07-18 | 东华大学 | Degradable hollow fiber membrane and application thereof |
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| CN105032202A (en) * | 2015-07-01 | 2015-11-11 | 上海洁晟环保科技有限公司 | Multilayer composite ultrafiltration membrane and preparation method thereof |
| CN105056777A (en) * | 2015-07-16 | 2015-11-18 | 宁波大学 | Lignin-crosslinking modified polymer separation membrane and application thereof |
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