CN103028331A - Preparation method of hydroxyethyl cellulose-silicon dioxide pervaporation hybrid membrane - Google Patents
Preparation method of hydroxyethyl cellulose-silicon dioxide pervaporation hybrid membrane Download PDFInfo
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Abstract
The invention discloses a pervaporation hybrid membrane for separating a methanol aqueous solution and a preparation method of the pervaporation hybrid membrane. The hybrid membrane comprises the raw materials as follows: hydroxyethyl cellulose, a rubbery polymer and hydrophilic nanosilicon dioxide. The preparation method of the hybrid membrane comprises the steps that hydroxyethyl cellulose, the rubbery polymer and hydrophilic nanosilicon dioxide are blended and hybridized to form a casting membrane solution; a membrane is formed by a solution casting method; the membrane is slightly crosslinked with a chemical cross-linking agent; and the hydroxyethyl cellulose-silicon dioxide pervaporation hybrid membrane used for separating the methanol aqueous solution is prepared. The organic-inorganic hybrid membrane prepared by the preparation method is a high-hydrophilicity pervaporation membrane, is suitable for dehydration of organic solvents, particularly has a good separation effect on the methanol aqueous solution which difficultly achieves effective separation of other membranes, and has a better separation effect on aqueous solutions such as alcohol and isopropanol.
Description
Technical field
The invention belongs to the infiltrating and vaporizing membrane technical field, be specifically related to a kind of hydroxyethylcellulose for separating of methanol aqueous solution-silica infiltrates vaporization hybridized film and preparation method thereof.
Background technology
One of the most promising new and high technology can be used for organics dehydration, reclaims organic matter infiltration evaporation, organic matter separates as 21 century, wherein the organics dehydration most study.At present, be tending towards ripe about the infiltration evaporation isolation technics of the alcohol solutions such as ethanol, isopropyl alcohol, butanols, tentatively realized industrialization, but the infiltration evaporation of methanol aqueous solution separates and still be in laboratory stage, relevant research report both domestic and external is few.Reason is to compare with ethanol, isopropyl alcohol equimolecular, and the molecular structure of methyl alcohol, polarity are very similar to water, cause methyl alcohol and the suction-operated of water in diffusion barrier to be competed mutually, thereby makes methyl alcohol and shipwreck to separate.So Methanol-biodiesel ﹠ Its manufacturing enterprise adopts the method separating-purifying methanol aqueous solutions such as ion exchange resin, rectifying usually at present, but its process is complicated, and energy consumption is higher, and the production cost of biodiesel is increased, and advantage is not obvious in market competition; Developing separation of methanol aqueous solution infiltrating and vaporizing membrane can reach in the methanol removal a small amount of water and obtain high-purity methyl alcohol or break fast alcohol-water azeotropic point.Therefore obtaining high score is vital from the application of factor pair methanol crossover vaporization.
At present, the advantages such as organic polymer films has that pliability is good, good penetrability, density are low, low price and good film-forming property, but its anti-solvent, corrosion-resistant and heat resistance is all relatively poor, can not provide enough selective and permeation fluxs to some systems.And high, corrosion-resistant, the anti-solvent of inoranic membrane intensity and high temperature resistant, but inorganic material is crisp, is difficult for processing, and film forming is poor, and price is also relatively more expensive at present.In order to concentrate organic film and inoranic membrane advantage separately, people have designed hybrid organic-inorganic film.This film has good physical and chemical stability and separating property, and good film-forming property, has become the study hotspot in the fields such as macromolecule and material science, membrane material preparation.According to the interaction type between organic and inorganic component, hybrid inorganic-organic materials can be divided into two large classes: a class be between organic and inorganic component with the hybrid material of weak interaction-secondary bond (Van der Waals force, hydrogen bond or weak electrostatic interaction) combination, form the composite with embedding phase.Another kind of is with the hybrid material of strong interaction-chemical bond (such as covalent bond, ion-covalent bond and coordinate bond) combination between organic and inorganic component.Combine closely by strong chemical bond between organic and inorganic component in this class hybridized film and form the good hybrid material of compatibility, improved the performance of homogenous material.
The rubbery state main chain is soft, with inorganic particulate preferably compatibility is arranged, and this is so that inorganic particulate and Polymers physical efficiency are compatible well, and alternate combination is tight; And the glassy polymers chain is harder, and itself and inorganic particulate compatibility are undesirable, easily is separated around inorganic particulate, forms the non-selectivity hole, the reduction film selectively.Therefore the research before mainly concentrates on rubbery feel polymer, such as dimethyl silicone polymer (PDMS), acrylic nitrile-butadiene-styrene terpolymer (ABS), shitosan (CS), ethylene propylene diene rubber (EPDM) etc.And in glassy polymers, main chain is a kind of rigid chain, and motion only is confined to the vibration of segment, and free volume is little than rubbery feel polymer, and infiltration component is had higher permselective property, but permeation flux is generally lower.In the glassy polymers film, fill inorganic particulate and can improve permeability of the membrane.Also some glassy polymers are studied at present, such as polysulfones (PSF), polyimides (PI), cellulose acetate (CA) and poly-acetimide (PEI) etc.
Chinese patent application 201010523943.4 discloses and has been used for a kind of method that removes the saturating pure hybridized film of infiltration evaporation of waste water methyl alcohol, and this is a kind of preferential alcohol permselective membrane, be applicable to the processing of the low concentration methanol aqueous solution, and separation factor is lower.
Chinese patent application 200710040764.3 has been announced a kind of at the chemical vapour deposition (CVD) of macropore ceramic membrane surface, glycerol polymerization and the hydrophilic osmotic vaporization compound membrane of ring-opening reaction preparation take inorganic ceramic membrane as carrier, has shown very excellent performance in the separation of methanol aqueous solution.But the method preparation process is complicated, and severe reaction conditions is with high costs, and needs the organic solvent that uses toxicity larger in the preparation process.
Chinese patent application 200610052633.2 discloses a kind of preparation method of hollow fiber osmosis vaporation permeable complex, and polyvinyl alcohol and sodium alginate blended cross linking are made hollow fiber composite membrane.The method technique is simple, and is easy to operate, the separating of applicable and multiple alcohol solution.But polyvinyl alcohol-based hollow fiber memberane is in use easily by the organic matter swelling, and strength decreased after use a period of time the fracture of wire problem occurs, and resistance tocrocking is poor, and system is difficult for operation steady in a long-term, and Flat Membrane has greater advantage in this respect.
Chinese patent 201210247999.0 discloses a kind of sodium alginate infiltration evaporation hybridized film for separating of methanol aqueous solution.The hybrid organic-inorganic film that makes is a kind of infiltrating and vaporizing membrane of high-hydrophilic, other films are difficult to realize that the methanol aqueous solution of effective separation has good separating effect, but separation factor is still waiting further raising.
At present, have no the research that utilizes the hydroxyethylcellulose hybridized film separation of methanol aqueous solution in the patent.Cellulose since its main chain on circulus so that its strand seems rigidity; But because etherification reaction has destroyed hydrogen bond action strong between the cellulosic molecule, greatly reduce cellulosic degree of crystallinity, make its can be water-soluble, dilute alkaline soln and organic solvent, and has thermoplasticity, the hydrophilic polymer that belongs to glassy state, its wide material sources, cheap, has the gel-free characteristic, and not with ionization, compatibility is good, has simultaneously good biological degradability and biological safety, can be used for preparing the various types of films material, but the mechanical property of film and solvent resistance await further to improve.Because of the particularity of hydroxyethylcellulose molecular structure, the membrane structure of its preparation is fine and close, and the methanol molecules approaching to molecular structure and water has good interception function, and the film separation factor is higher.But the film-formation result of pure hydroxyethylcellulose is not so good, and the polymer substance that need add therein rubbery state improves its film-formation result, such as polyvinyl alcohol, sodium alginate, shitosan etc.
Because the requirement that single organic matter homogeneous membrane does not often reach actual process in indexs such as selective, permeation flux and stability, and filling-modifiedly obtained extensive concern as a kind of mild condition and simple physical modification method.In numerous polymer hybridisation materials, because nano silicon has the characteristics such as nontoxic, tasteless, pollution-free, be cotton-shaped and network structure, and specific area is large, there is the hydroxyl of undersaturated residual bond and different bond styles in its surface, is oxygen debt and departs from the silica structure of stable state.Small-size effect and macro quanta tunnel effect make it produce what to ooze effect, can be deep near the unsaturated bond of macromolecular chain, and have an effect with the electron cloud of unsaturated bond, thereby improve heat endurance and the chemical stability of polymer.The content of silicon dioxide granule can produce great impact with performance to the structure of hybridized film with size: different structure and the larger diffusion barriers of performance difference of forming of content.Usually, improve inorganic particulate content, the structure of film will be porous, loose shape gradually, selectively will increase, and permeation flux will reduce.Along with the further increase of inorganic particulate content, film selectively will reach maximum, and permeation flux will reach minimum of a value; Continue to increase, inorganic particulate will be assembled, and film produces defective, and it selectively descends, and permeation flux increases.Dioxide-containing silica is certain, and less its quantity of particle is just more, can be evenly dispersed in the polymeric matrix, divide bulk density large, form comparatively loose porous structure, the phase contact area of particle and polymer also increases simultaneously, has increased the selective and permeation flux of infiltration component.
For preventing that film long-time immersion in methanol aqueous solution from swelling occuring, usually add chemical cross-linking agent and carry out lightly crosslinked to keep the stable of size.Crosslinking agent is of a great variety, for-OH commonly used aldehydes, acids, diisocyanates, urea-formaldehyde-sulfuric acid mixture liquid arranged, can produce cross-linking reaction between mutually at organic and inorganic and form covalent bond.Slight crosslinked being conducive to suppresses to be separated, but the crosslinked permeation flux of film that excessively can cause sharply reduces.
Summary of the invention
The objective of the invention is to overcome existing methanol aqueous solution infiltrating and vaporizing membrane separation factor not high, or the shortcoming such as the preparation process of film is complicated, with high costs.Provide a kind of separation to methanol aqueous solution to have high selectivity, organic-inorganic hybridized osmotic vaporization film that has good stability and preparation method thereof.
One aspect of the present invention relates to a kind of infiltration evaporation hybridized film for separating of methanol aqueous solution, it is characterized in that, the raw material of preparation hybridized film comprises hydroxyethylcellulose, rubbery feel polymer and hydrophilic nano silica, and the step of preparation hybridized film comprises: utilize hydroxyethylcellulose, rubbery feel polymer and silica to carry out blend hydridization and obtain casting solution; Utilize solution casting method to make hydroxyethylcellulose for separating of methanol aqueous solution-silica infiltrates vaporization hybridized film.
The present invention also relates to the preparation method of the infiltration evaporation hybridized film of the above-mentioned separation of methanol aqueous solution on the other hand, comprises the steps:
A) configuration of casting solution: preparation hydroxyethylcellulose-rubbery feel polymer aqueous solution, hydrophilic nano silica is mixed with water, fully stir and make its dissolving, then slowly join in hydroxyethylcellulose-rubbery feel polymer aqueous solution, and continue to stir formation homogeneous phase transparent colloidal sol;
B) film: polyacrylonitrile micropore counterdie is placed mould, with scraping hymenotome casting solution evenly is coated on the counterdie surface, gelation and dry 48h under room temperature, then at 60-70 ℃ of lower vacuum drying 24h, be soaked in the crosslinker solution gained film crosslinked, remove unreacted impurity with the deionized water cyclic washing at last, drying obtains the cellulose ether hybridized film.
In a preferred embodiment of the present invention
,It is characterized in that rubbery feel polymer is one or more the mixture in sodium alginate, shitosan or the polyvinyl alcohol.
In a preferred embodiment of the present invention, it is characterized in that, the mass fraction of hydroxy ethyl fiber cellulose solution is 2-10% among the described step a, be preferably 4-6%, the content of rubbery feel polymer (with respect to hydroxyethylcellulose) is 0-35wt%, does not comprise 0, is preferably 10-25wt%; The mass fraction of hydrophilic nano silica is 4-20%, is preferably 6-12%.
In a preferred embodiment of the present invention, it is characterized in that, the coagulant liquid that obtains among the described step a needs to filter through the 2# sand core funnel, removes insoluble matter, leaves standstill, and deaeration gets casting solution.
In a preferred embodiment of the present invention, it is characterized in that, mould is any in glass mold, the polytetrafluoroethylene (PTFE) mould among the described step b.
In a preferred embodiment of the present invention, it is characterized in that, described crosslinking agent be in vulcabond, glutaraldehyde, phosphoric acid, citric acid or urea-formaldehyde-sulfuric acid mixture liquid one or more, preferably glutaraldehyde, urea-formaldehyde-sulfuric acid mixture liquid.
The present invention also relates to the resulting infiltration evaporation hybridized film of above-mentioned preparation method on the other hand for separating of methanol aqueous solution.
The present invention's advantage compared with prior art: raw material of the present invention is cheap and easy to get, and the preparation method of its hybridized film is simple, is easy to grasp, and efficient is high, the controllability of membrane structure and production good reproducibility.And have good structural behaviour, in the separation of methanol water solution system, show good permeation flux and separating effect.Be particularly useful for from low discharge, the high concentration methanol aqueous solution, sloughing minor amount of water, need not follow-up purification step.Simultaneously, the aqueous solution such as ethanol, isopropyl alcohol also there is preferably separating effect.
Description of drawings
Fig. 1 is the surface scan Electronic Speculum figure of hydroxyethylcellulose/silica (8wt%) hybridized film of preparing of the present invention.
Fig. 2 is the section surface sweeping Electronic Speculum figure of hydroxyethylcellulose/silica (8wt%) hybridized film of preparing of the present invention.
The specific embodiment
The present invention is described in detail below in conjunction with the drawings and specific embodiments.
Embodiment 1: take by weighing simultaneously 4.0g hydroxyethylcellulose (HEC), 1.0g(25wt%, with respect to HEC) polyvinyl alcohol (PVA) is dissolved in the 100g distilled water, 70 ℃ of lower stirrings until then dissolve complete takes by weighing 0.24g hydrophilic nano SiO
2Be dissolved in the HEC/PVA solution, continue to stir until form homogeneous phase transparent colloidal sol.Gained colloidal sol is filtered through the 2# sand core funnel, remove insoluble matter, leave standstill, deaeration gets casting solution.With scraping hymenotome colloidal sol is coated on polyacrylonitrile counterdie surface, gelation and dry 48h under the room temperature are then at 60-70 ℃ of lower vacuum drying 24h, the gained film is soaked in the crosslinker solution crosslinked, crosslinker solution is the acetone-water solution (1:2, v/v) of 180mL, 2.5mL hydrochloric acid, the 2.5mL glutaraldehyde.Remove unreacted impurity with the deionized water cyclic washing at last, drying obtains the hydroxyethylcellulose hybridized film.The film of gained carries out the osmotic, evaporating and dewatering experiment of methanol aqueous solution, feed liquid is the methanol aqueous solution of variable concentrations, place there-necked flask, and by heating water bath, temperature maintains 30 ℃, feed liquid enters in the membrane module through the peristaltic pump coutroi velocity, then refluxes in there-necked flask, and the effective area of film is 12.56cm
2, approximately behind the 2h, the vavuum pump of opening the film downstream vacuumizes until whole system stable operation, and vacuum maintains 1.5kPa, and penetrant is collected through cold-trap (liquid nitrogen, its fusing point be-196 ℃) cooling, lasting 5h.When feed concentration (methyl alcohol wt%) when being respectively 90%, 95%, permeation flux J(g/m
2H) be respectively 325,259, separation factor alpha is respectively 217,435.
Embodiment 2: such as the processing step of example 1, wherein, only change hydrophilic nano SiO
2Addition be 0.40g(10wt%, with respect to HEC), make hydroxyethylcellulose hybrid organic-inorganic film of the present invention.When feed concentration (methyl alcohol wt%) when being respectively 90%, 95%, permeation flux J(g/m
2H) be respectively 289,237, separation factor alpha is respectively 356,527.
When being understood that; specific embodiments of the invention only are the purposes of property explanation presented for purpose of illustration; it limits protection scope of the present invention never in any form; those skilled in the art can be improved or conversion according to the above description, and all these improvement and conversion all should belong to the protection domain of claims of the present invention.
Claims (8)
1. infiltration evaporation hybridized film for separating of methanol aqueous solution, it is characterized in that, the raw material of preparation hybridized film comprises hydroxyethylcellulose, rubbery feel polymer and hydrophilic nano silica, and the step of preparation hybridized film comprises: utilize hydroxyethylcellulose, rubbery feel polymer and hydrophilic nano silica to carry out blend hydridization and obtain casting solution; Utilize solution casting method to make cellulose ether infiltration evaporation hybridized film for separating of methanol aqueous solution.
2. the preparation method of the infiltration evaporation hybridized film for separating of methanol aqueous solution according to claim 1 is characterized in that, comprises the steps:
A) configuration of casting solution: preparation hydroxyethylcellulose-rubbery feel polymer aqueous solution, hydrophilic nano silica is mixed with water, fully stir and make its dissolving, then slowly join in hydroxyethylcellulose-rubbery feel polymer aqueous solution, and continue to stir formation homogeneous phase transparent colloidal sol;
B) film: polyacrylonitrile micropore counterdie is placed mould, with scraping hymenotome casting solution evenly is coated on the counterdie surface, gelation and dry 48h under room temperature, then at 60-70 ℃ of lower vacuum drying 24h, be soaked in the crosslinker solution gained film crosslinked, remove unreacted impurity with the deionized water cyclic washing at last, drying obtains hydroxyethylcellulose/SiO 2 hybrid film.
3. the raw material of preparation hybridized film according to claim 1 is characterized in that rubbery feel polymer is one or more the mixture in sodium alginate, shitosan or the polyvinyl alcohol.
4. the preparation method of the infiltration evaporation hybridized film for separating of methanol aqueous solution according to claim 2, it is characterized in that, the mass fraction of hydroxy ethyl fiber cellulose solution is 2-10% among the described step a, be preferably 4-6%, the content of rubbery feel polymer (with respect to hydroxyethylcellulose) is 0-35wt%, do not comprise 0, be preferably 10-25wt%; The mass fraction of hydrophilic nano silica is 4-20%, is preferably 6-12%.
5. the preparation method of the infiltration evaporation hybridized film for separating of methanol aqueous solution according to claim 2 is characterized in that, the coagulant liquid that obtains among the described step a needs to filter through the 2# sand core funnel, remove insoluble matter, leaves standstill, and deaeration gets casting solution.
6. the preparation method of the infiltration evaporation hybridized film for separating of methanol aqueous solution according to claim 2 is characterized in that, mould is any in glass mold, the polytetrafluoroethylene (PTFE) mould among the described step b.
7. the preparation method of the infiltration evaporation hybridized film for separating of methanol aqueous solution according to claim 2, it is characterized in that, described crosslinking agent be in vulcabond, glutaraldehyde, phosphoric acid, citric acid or urea-formaldehyde-sulfuric acid mixture liquid one or more, preferably glutaraldehyde, urea-formaldehyde-sulfuric acid mixture liquid.
8. the preparation-obtained infiltration evaporation hybridized film for separating of methanol aqueous solution of the described preparation method of claim 2-7 any one.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103446899A (en) * | 2013-09-13 | 2013-12-18 | 天津工业大学 | Organic and inorganic surface chemically-crosslinked alginate-based hybrid hydrogel filter membrane, and preparation method thereof |
| CN103752184A (en) * | 2014-01-23 | 2014-04-30 | 成都新柯力化工科技有限公司 | Inorganic-organic composite ultrafiltration membrane and preparation method thereof |
| CN104707488A (en) * | 2015-04-03 | 2015-06-17 | 深圳市诚德来实业有限公司 | Hollow fiber composite membrane and preparation method thereof |
| CN108889142A (en) * | 2018-06-15 | 2018-11-27 | 长春工业大学 | A kind of polyvinyl alcohol-hydroxyethyl cellulose/polyacrylonitrile gas dehumidification membrane preparation method |
| CN109847592A (en) * | 2019-01-04 | 2019-06-07 | 广州汉至蓝能源与环境技术有限公司 | A kind of organic-inorganic hybrid films preparation method |
| CN109966935A (en) * | 2019-04-10 | 2019-07-05 | 重庆工程职业技术学院 | A kind of ethyl cellulose-organic-silicon hybridization film and preparation method thereof |
| CN110294853A (en) * | 2019-06-28 | 2019-10-01 | 陕西科技大学 | A kind of HEC/PVA interpenetrating networks film and preparation method thereof |
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| CN114432905A (en) * | 2022-02-13 | 2022-05-06 | 北京化工大学 | Non-asbestos alkaline electrolyzed water composite diaphragm and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1481928A (en) * | 2003-07-29 | 2004-03-17 | 复旦大学 | hydrophilic organic-inorganic compounded pervaporation separating film and method for making the same |
| US20080295691A1 (en) * | 2007-06-01 | 2008-12-04 | Chunqing Liu | Uv cross-linked polymer functionalized molecular sieve/polymer mixed matrix membranes |
| CN101698138A (en) * | 2009-10-29 | 2010-04-28 | 浙江大学 | Method for preparing high-performance polyelectrolyte-silicon dioxide nanocomposite pervaporation membrane |
| CN102743981A (en) * | 2012-07-18 | 2012-10-24 | 盐城工学院 | Preparation and application of sodium alginate pervaporation hybrid membrane |
-
2013
- 2013-01-03 CN CN201310000118XA patent/CN103028331A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1481928A (en) * | 2003-07-29 | 2004-03-17 | 复旦大学 | hydrophilic organic-inorganic compounded pervaporation separating film and method for making the same |
| US20080295691A1 (en) * | 2007-06-01 | 2008-12-04 | Chunqing Liu | Uv cross-linked polymer functionalized molecular sieve/polymer mixed matrix membranes |
| CN101698138A (en) * | 2009-10-29 | 2010-04-28 | 浙江大学 | Method for preparing high-performance polyelectrolyte-silicon dioxide nanocomposite pervaporation membrane |
| CN102743981A (en) * | 2012-07-18 | 2012-10-24 | 盐城工学院 | Preparation and application of sodium alginate pervaporation hybrid membrane |
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| CN103446899A (en) * | 2013-09-13 | 2013-12-18 | 天津工业大学 | Organic and inorganic surface chemically-crosslinked alginate-based hybrid hydrogel filter membrane, and preparation method thereof |
| CN103446899B (en) * | 2013-09-13 | 2015-05-06 | 天津工业大学 | Organic and inorganic surface chemically-crosslinked alginate-based hybrid hydrogel filter membrane, and preparation method thereof |
| CN103752184A (en) * | 2014-01-23 | 2014-04-30 | 成都新柯力化工科技有限公司 | Inorganic-organic composite ultrafiltration membrane and preparation method thereof |
| CN103752184B (en) * | 2014-01-23 | 2015-08-12 | 成都新柯力化工科技有限公司 | Milipore filter of a kind of inorganic-organic hybrid and preparation method thereof |
| CN104707488A (en) * | 2015-04-03 | 2015-06-17 | 深圳市诚德来实业有限公司 | Hollow fiber composite membrane and preparation method thereof |
| CN108889142A (en) * | 2018-06-15 | 2018-11-27 | 长春工业大学 | A kind of polyvinyl alcohol-hydroxyethyl cellulose/polyacrylonitrile gas dehumidification membrane preparation method |
| CN109847592A (en) * | 2019-01-04 | 2019-06-07 | 广州汉至蓝能源与环境技术有限公司 | A kind of organic-inorganic hybrid films preparation method |
| CN109966935A (en) * | 2019-04-10 | 2019-07-05 | 重庆工程职业技术学院 | A kind of ethyl cellulose-organic-silicon hybridization film and preparation method thereof |
| CN110294853A (en) * | 2019-06-28 | 2019-10-01 | 陕西科技大学 | A kind of HEC/PVA interpenetrating networks film and preparation method thereof |
| CN110294853B (en) * | 2019-06-28 | 2022-04-08 | 陕西科技大学 | HEC/PVA interpenetrating network film and preparation method thereof |
| CN110903509A (en) * | 2019-11-18 | 2020-03-24 | 江苏大学 | Preparation method of molecularly imprinted nanocomposite membrane for selectively separating atrazine |
| CN110903509B (en) * | 2019-11-18 | 2022-03-22 | 江苏大学 | Preparation method of molecularly imprinted nanocomposite membrane for selectively separating atrazine |
| CN114432905A (en) * | 2022-02-13 | 2022-05-06 | 北京化工大学 | Non-asbestos alkaline electrolyzed water composite diaphragm and preparation method thereof |
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Application publication date: 20130410 |