CN104525000B - A kind of preparation method of high selectivity polyvinyl alcohol nanofiltration membrane - Google Patents
A kind of preparation method of high selectivity polyvinyl alcohol nanofiltration membrane Download PDFInfo
- Publication number
- CN104525000B CN104525000B CN201410794979.4A CN201410794979A CN104525000B CN 104525000 B CN104525000 B CN 104525000B CN 201410794979 A CN201410794979 A CN 201410794979A CN 104525000 B CN104525000 B CN 104525000B
- Authority
- CN
- China
- Prior art keywords
- polyvinyl alcohol
- preparation
- membrane
- aqueous solution
- glutaraldehyde
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a kind of preparation method of polymeric membrane, specifically refer to a kind of hydrophily good, selectively good, rejection is higher, the preparation method of the polyvinyl alcohol nanofiltration membrane that water flux is higher. The present invention is by polysulfones counterdie is first applied with the polyvinyl alcohol water solution that mass concentration is 0.1%-1%, dry in the shade, the mixed aqueous solution that the ammonium alcohol polyvinyl phosphate that is 0.1%-1% by concentration again and qualities of glycerin content are 0.1%-0.5% applies, dry in the shade, then the aqueous solution of polyvinyl alcohol and glutaraldehyde is applied, wherein the mass concentration of polyvinyl alcohol is 1%-3%, and the mass concentration of glutaraldehyde is 0.1-0.5%; In 100 DEG C of baking ovens, process 1min-10min again, prepared by composite membrane. Advantage of the present invention is that preparation technology is simple, the NF membrane obtaining with respect to existing NF membrane to Na2SO4And MgCl2There are higher ion-selective permeability and higher water flux.
Description
Technical field
The present invention relates to a kind of preparation method of polymeric membrane, specifically refer to a kind of hydrophily good, selectiveWell, rejection is higher, the preparation method of the polyvinyl alcohol nanofiltration membrane that water flux is higher.
Background technology
Because having highly hydrophilic, good resistance tocrocking and filming performance, polyvinyl alcohol (PVA) becomes moreGet over one of hydrophilic film material of extensive use, especially have more suction as utilized thin film composite membranes compacted zone membrane materialGravitation. PVA has the performance of anti-Organic Pollution and resistance to chlorine, and these two performances are that current business polyamide is anti-The ultimate challenge that permeable membrane faces, the flux of PVA film is less simultaneously, has limited its large-scale application, instituteA new direction in recent years with the flux that improves PVA reverse osmosis membrane or NF membrane. Due in PVA chainHydroxyl is more active, is very easy to react with the compound that contains the functional groups such as carboxyl, aldehyde radical, hydroxyl, is dividingBetween son, form covalent bond, reaction generates cross-linked network shape structure, thereby reduces the swellbility of film in water. AsMorancho etc. utilize sulfonation succinic acid to make crosslinking agent, and crosslinked PVA prepares PEM for FC, examinesExamined the impact of content of crosslinking agent on film heat endurance and mechanical property (MoranchoJM, SallaJM,CadenatoA，etal.Thermalanalysisofenhancedpoly(vinylalcohol)-basedproton-conductingmembranescrosslinkedwithsulfonationagentsfordirectmethanolfuelcells[J].J.Appl.Polym.Sci.，2012，124：57-65.)。Lin etc. adopt solution coating/particle leaching legal system for PVA/PAN composite membrane, carry out with glutaraldehyde as cross linkerCrosslinked, for separating of caprolactam/aqueous systems (LinWH, LiQ, ZhuTR.Studyofsolventcasting/particulateleachingtechniquemembranesinpervaporationfordehydrationofcaprolactam[J].J.Ind.Eng.Chem.，2012，18：941-947.)。Zhang etc. first react and prepare polyvinyl alcohol of acetalization with PVA with acetaldehyde, and then inversion of phases masking uses glutaraldehydeBe cross-linked, the milipore filter obtaining to the rejection of BSA also can reach more than 95% (ZhangYZ, LiHQ,LiH，etal.Preparationandcharacterizationofmodifiedpolyvinylalcoholultrafiltrationmembranes[J].Desalination，2006，192：214-223.)。
In general, the preparation of NF membrane completes by twice coating, if Fibiger etc. is at 1987 USPatent4, the water that NF membrane employing is prepared in 769,148 median surface polymerizations is the aqueous solution of piperazine and wetting agent,Crosslinking agent is pyromellitic trimethylsilyl chloride, adopts secondary cladding process to prepare NF membrane. Lawrence etc. were at the US of 1997Patent5, adopts interface polycondensation taking 5-isocyanates isophthaloyl chlorine as crosslinking agent in 693,227, exists with piperazineReaction preparation NF membrane on polysulfones support membrane, use be also twice painting method.
Glutaraldehyde has stronger crosslinked action to polyvinyl alcohol, and the reactivity of glutaraldehyde is higher, higherUnder treatment temperature, within the relatively short time, just can occur crosslinked with polyvinyl alcohol. On counterdie, first apply lowThe poly-vinyl alcohol solution of concentration, has increased the hydrophily of film greatly, after drying in the shade, and coated polyvinyl alcohol phosphorusAcid ammonium glycerine water solution can make polyethylene ammonium phosphate be penetrated into preferably in the middle of polyvinyl alcohol, the effect of glycerineBe moisturizing, make ammonium alcohol polyvinyl phosphate have the longer time to be penetrated in the middle of polyvinyl alcohol, what finally apply is poly-Vinyl alcohol glutaraldehyde solution has formed the cross linking membrane of one deck densification on film surface, can make ammonium alcohol polyvinyl phosphateCan be by " be stranded ", prevent that ammonium alcohol polyvinyl phosphate runs off inside. Like this, ammonium alcohol polyvinyl phosphate is just as " folderLayer " be equally clipped between the polyvinyl alcohol of twice coating, can increase the water flux of film, and its electronegativity is certainlyDetermine the NF membrane of preparation thus and there is higher ion-selective permeability.
But in twice coating preparation process, also there is certain deficiency in preparation-obtained film in performance,Especially select the technical indicator such as permeability, water flux. For this reason, technical staff wishes by certain technology handHow section, improve better and select permeability, raising water flux? and also many for the research of NF membrane,So improving on existing film basis neither an easy thing, especially present membrane materialMany, in the situation that in process conditions, controllable parameter is a lot, feasible technical scheme of How to choose, is onePart needs a large amount of creative works.
Summary of the invention
For better solution deficiency of the prior art, technical staff is by the research to many materials, existingOn the basis of technology, realize issue-resolutions such as selecting permeability, water flux. Because glutaraldehyde is to polyethyleneAlcohol has stronger crosslinked action, and the reactivity of glutaraldehyde is higher, under higher treatment temperature, relativelyIn the shorter time, just can occur crosslinked with polyvinyl alcohol. The polyvinyl alcohol that first applies low concentration on counterdie is moltenLiquid, has increased the hydrophily of film greatly, after drying in the shade, and coated ammonium alcohol polyvinyl phosphate glycerine water solution energyEnough make polyethylene ammonium phosphate be penetrated into preferably in the middle of polyvinyl alcohol, the effect of glycerine is moisturizing, makes poly-secondEnol phosphate ammonium has the longer time to be penetrated in the middle of polyvinyl alcohol, the polyvinyl alcohol glutaraldehyde solution finally applyingForm the cross linking membrane of one deck densification on film surface, can make the ammonium alcohol polyvinyl phosphate can be by " be stranded " innerFace, prevents that ammonium alcohol polyvinyl phosphate runs off. Like this, ammonium alcohol polyvinyl phosphate is clipped in two just as " interlayer "Between the polyvinyl alcohol of inferior coating, can increase the water flux of film, and its electronegativity determines preparation thusNF membrane has higher ion-selective permeability. In addition, also carried out a large amount of examinations for the selection of membrane materialTest, determine as the selection of the molecular weight to base film material, the selection of material solubility, although this concentration is wherein seenLike difference not too, but really not little for the impact of microcosmic membrane structure, can by the mensuration to SpecificationsTo draw, improvement of the present invention has obtained good effect.
The present invention is achieved by following technical proposals:
A preparation method for high selectivity polyvinyl alcohol nanofiltration membrane, is characterized in that, comprises the following steps:Polysulfones counterdie is first applied with the polyvinyl alcohol water solution that mass concentration is 0.1%-1%, dry in the shade, then by denseThe ammonium alcohol polyvinyl phosphate that degree is 0.1%-1% and the mixed aqueous solution that qualities of glycerin content is 0.1%-0.5% are coated withCover, dry in the shade, then the aqueous solution of polyvinyl alcohol and glutaraldehyde is applied, wherein the mass concentration of polyvinyl alcohol is1%-3%, the mass concentration of glutaraldehyde is 0.1-0.5%; In 100 DEG C of baking ovens, process 1min-10min again, multipleClosing film preparation completes; The molecular cut off of wherein said polysulfones counterdie is 2-3 ten thousand.
Effective group expression described in the present invention is as follows:
As preferably, the degree of hydrolysis of the polyvinyl alcohol described in above-mentioned a kind of preparation method is 85-89%, molecular weightFor 100000-150000.
As preferably, the polyvinyl alcohol water solution described in above-mentioned a kind of preparation method is through vacuum defoamation processingSolution. Can effectively remove like this impact on film of bubble wherein.
As preferably, the ammonium alcohol polyvinyl phosphate described in above-mentioned a kind of preparation method be purity be 99.9% pointAnalyse pure material.
As preferably, the ammonium alcohol polyvinyl phosphate mixed solution described in above-mentioned a kind of preparation method is for first configuringThe aqueous solution, and then mix with glycerine.
As preferably, in the aqueous solution of the polyvinyl alcohol described in above-mentioned a kind of preparation method and glutaraldehyde, add rareSulfuric acid or watery hydrochloric acid are as crosslinking agent, and wherein the degree of hydrolysis of polyvinyl alcohol is 98-99%, and molecular weight is150000-200000。
As preferably, the crosslinking agent described in above-mentioned a kind of preparation method is watery hydrochloric acid.
Beneficial effect: preparation technology of the present invention is simple, preparation-obtained NF membrane is with respect to existing nanofiltrationFilm is to Na2SO4And MgCl2There are higher ion-selective permeability and higher water flux. Use the coating side of three timesMethod is rare, and general NF membrane is higher to bivalent ions rejection, and utilizes this patent method systemStandby NF membrane, not only preparation method's novelty, and dianion and bivalent cation are had to good selectionProperty.
Detailed description of the invention
Below in conjunction with example, the present invention will be further described, but protection scope of the present invention is not limited to this.
Embodiment 1
The polyvinyl alcohol water solution of preparation 0.3%, deaeration is for subsequent use. The polyvinyl alcohol phosphoric acid that preparation concentration is 0.4%Ammonium and glycerol content are 0.3% mixed aqueous solution, for subsequent use. Preparation polyvinyl alcohol concentration is 2%, and glutaraldehyde is denseDegree is 0.3% mixed aqueous solution, and adds the hydrochloric acid of certain content, for subsequent use. Polysulfones counterdie is first used to concentrationBe that 0.3% polyvinyl alcohol applies, dry in the shade, then the ammonium alcohol polyvinyl phosphate and the glycerol content that are 0.4% by concentrationBeing that 0.3% mixed aqueous solution applies, drying in the shade, is finally 2% by the polyvinyl alcohol concentration of adding certain hydrochloric acid,Glutaraldehyde concentration is 0.3% mixed aqueous solution coating, in 100 DEG C of baking ovens, processes 3min, composite membrane preparationComplete. High selectivity polyvinyl alcohol nanofiltration membrane is to 1000ppmNa2SO4Be trapped in 78%, water flux is 135LMH,To 1000ppmMgCl2Rejection be 5%, water flux is 155LMH.
Embodiment 2
The polyvinyl alcohol water solution of preparation 0.3%, deaeration is for subsequent use. The polyvinyl alcohol phosphoric acid that preparation concentration is 0.5%Ammonium and glycerol content are 0.5% mixed aqueous solution, for subsequent use. Preparation polyvinyl alcohol concentration is 2%, and glutaraldehyde is denseDegree is 0.3% mixed aqueous solution, and adds the hydrochloric acid of certain content, for subsequent use. Polysulfones counterdie is first used to concentrationBe that 0.3% polyvinyl alcohol applies, dry in the shade, then the ammonium alcohol polyvinyl phosphate and the glycerol content that are 0.5% by concentrationBeing that 0.5% mixed aqueous solution applies, drying in the shade, is finally 2% by the polyvinyl alcohol concentration of adding certain hydrochloric acid,Glutaraldehyde concentration is 0.3% mixed aqueous solution coating, in 100 DEG C of baking ovens, processes 4min, composite membrane preparationComplete. High selectivity polyvinyl alcohol nanofiltration membrane is to 1000ppmNa2SO4Be trapped in 83%, water flux is 138LMH,To 1000ppmMgCl2Rejection be 6%, water flux is 157LMH.
Embodiment 3
The polyvinyl alcohol water solution of preparation 0.5%, deaeration is for subsequent use. The polyvinyl alcohol phosphoric acid that preparation concentration is 0.4%Ammonium and glycerol content are 0.3% mixed aqueous solution, for subsequent use. Preparation polyvinyl alcohol concentration is 2%, and glutaraldehyde is denseDegree is 0.3% mixed aqueous solution, and adds the hydrochloric acid of certain content, for subsequent use. Polysulfones counterdie is first used to concentrationBe that 0.5% polyvinyl alcohol applies, dry in the shade, then the ammonium alcohol polyvinyl phosphate and the glycerol content that are 0.4% by concentrationBeing that 0.3% mixed aqueous solution applies, drying in the shade, is finally 2% by the polyvinyl alcohol concentration of adding certain hydrochloric acid,Glutaraldehyde concentration is 0.3% mixed aqueous solution coating, in 100 DEG C of baking ovens, processes 3min, composite membrane preparationComplete. High selectivity polyvinyl alcohol nanofiltration membrane is to 1000ppmNa2SO4Be trapped in 80%, water flux is 121LMH,To 1000ppmMgCl2Rejection be 8%, water flux is 148LMH.
Embodiment 4
The polyvinyl alcohol water solution of preparation 0.3%, deaeration is for subsequent use. The polyvinyl alcohol phosphoric acid that preparation concentration is 0.4%Ammonium and glycerol content are 0.3% mixed aqueous solution, for subsequent use. Preparation polyvinyl alcohol concentration is 3%, and glutaraldehyde is denseDegree is 0.3% mixed aqueous solution, and adds the hydrochloric acid of certain content, for subsequent use. Polysulfones counterdie is first used to concentrationBe that 0.3% polyvinyl alcohol applies, dry in the shade, then the ammonium alcohol polyvinyl phosphate and the glycerol content that are 0.4% by concentrationBeing that 0.3% mixed aqueous solution applies, drying in the shade, is finally 3% by the polyvinyl alcohol concentration of adding certain hydrochloric acid,Glutaraldehyde concentration is 0.3% mixed aqueous solution coating, in 100 DEG C of baking ovens, processes 3min, composite membrane preparationComplete. High selectivity polyvinyl alcohol nanofiltration membrane is to 1000ppmNa2SO4Be trapped in 88%, water flux is 137LMH,To 1000ppmMgCl2Rejection be 9%, water flux is 159LMH.
Embodiment 5
The polyvinyl alcohol water solution of preparation 0.3%, deaeration is for subsequent use. The polyvinyl alcohol phosphoric acid that preparation concentration is 0.4%Ammonium and glycerol content are 0.3% mixed aqueous solution, for subsequent use. Preparation polyvinyl alcohol concentration is 2%, and glutaraldehyde is denseDegree is 0.5% mixed aqueous solution, and adds the hydrochloric acid of certain content, for subsequent use. Polysulfones counterdie is first used to concentrationBe that 0.3% polyvinyl alcohol applies, dry in the shade, then the ammonium alcohol polyvinyl phosphate and the glycerol content that are 0.4% by concentrationBeing that 0.3% mixed aqueous solution applies, drying in the shade, is finally 2% by the polyvinyl alcohol concentration of adding certain hydrochloric acid,Glutaraldehyde concentration is 0.5% mixed aqueous solution coating, in 100 DEG C of baking ovens, processes 3min, composite membrane preparationComplete. High selectivity polyvinyl alcohol nanofiltration membrane is to 1000ppmNa2SO4Be trapped in 90%, water flux is 135LMH,To 1000ppmMgCl2Rejection be 5%, water flux is 155LMH.
Embodiment 6
The polyvinyl alcohol water solution of preparation 0.3%, deaeration is for subsequent use. The ammonium alcohol polyvinyl phosphate that preparation concentration is 0.4%With the mixed aqueous solution that glycerol content is 0.3%, for subsequent use. Preparation polyvinyl alcohol concentration is 2%, and glutaraldehyde concentration is0.3% mixed aqueous solution, and add the hydrochloric acid of certain content, for subsequent use. Be first 0.3% by concentration by polysulfones counterdiePolyvinyl alcohol apply, dry in the shade, then the ammonium alcohol polyvinyl phosphate that is 0.4% by concentration and glycerol content are 0.3%Mixed aqueous solution apply, dry in the shade, be finally 2% by adding the polyvinyl alcohol concentration of certain hydrochloric acid, glutaraldehyde is denseDegree is 0.3% mixed aqueous solution coating, in 100 DEG C of baking ovens, processes 5min, prepared by composite membrane. Gao XuanSelect property polyethylene alcohol NF membrane to 1000ppmNa2SO4Be trapped in 73%, water flux is 118LMH, right1000ppmMgCl2Rejection be 9%, water flux is 130LMH.
Claims (7)
1. a preparation method for high selectivity polyvinyl alcohol nanofiltration membrane, is characterized in that, comprises the following steps:
Polysulfones counterdie is first applied with the polyvinyl alcohol water solution that mass concentration is 0.1%-1%, dry in the shade, thenThe mixing water that the ammonium alcohol polyvinyl phosphate that is 0.1%-1% by mass concentration and qualities of glycerin content are 0.1%-0.5%Solution applies, and dries in the shade, and then the aqueous solution of polyvinyl alcohol and glutaraldehyde is applied to the wherein quality of polyvinyl alcoholConcentration is 1%-3%, and the mass concentration of glutaraldehyde is 0.1-0.5%; In 100 DEG C of baking ovens, process again1min-10min, prepared by composite membrane; The molecular cut off of wherein said polysulfones counterdie is 2-3 ten thousand.
2. a kind of preparation method according to claim 1, is characterized in that, the water of described polyvinyl alcoholXie Du is 85-89%, and molecular weight is 100000-150000.
3. a kind of preparation method according to claim 1, is characterized in that, described polyvinyl alcohol waterSolution is the solution through vacuum defoamation processing.
4. a kind of preparation method according to claim 1, is characterized in that, described polyvinyl alcohol phosphorusAcid ammonium is that purity is 99.9% analysis pure material.
5. a kind of preparation method according to claim 1, is characterized in that, described polyvinyl alcohol phosphorusAcid ammonium mixed solution is for first configuring the aqueous solution, and then mixes with glycerine.
6. a kind of preparation method according to claim 1, is characterized in that, described polyvinyl alcohol andIn the aqueous solution of glutaraldehyde, add dilute sulfuric acid or watery hydrochloric acid as crosslinking agent, wherein the degree of hydrolysis of polyvinyl alcohol is98-99%, molecular weight is 150000-200000.
7. a kind of preparation method according to claim 6, is characterized in that, described crosslinking agent is rareHydrochloric acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410794979.4A CN104525000B (en) | 2014-12-18 | 2014-12-18 | A kind of preparation method of high selectivity polyvinyl alcohol nanofiltration membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410794979.4A CN104525000B (en) | 2014-12-18 | 2014-12-18 | A kind of preparation method of high selectivity polyvinyl alcohol nanofiltration membrane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104525000A CN104525000A (en) | 2015-04-22 |
| CN104525000B true CN104525000B (en) | 2016-05-25 |
Family
ID=52840733
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410794979.4A Active CN104525000B (en) | 2014-12-18 | 2014-12-18 | A kind of preparation method of high selectivity polyvinyl alcohol nanofiltration membrane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104525000B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105214519A (en) * | 2015-10-27 | 2016-01-06 | 北京碧水源膜科技有限公司 | The preparation method of polyvinyl alcohol composite nanometer filtering film |
| CN105561799B (en) * | 2015-12-19 | 2018-01-09 | 山东招金膜天股份有限公司 | A kind of preparation method of positively charged nanofiltration membranes |
| CN106621841B (en) * | 2016-12-30 | 2020-09-18 | 北京碧水源膜科技有限公司 | Preparation method of positively charged nanofiltration membrane |
| CN113289498B (en) * | 2021-05-10 | 2022-05-10 | 蓝星（杭州）膜工业有限公司 | Positively charged nanofiltration membrane and preparation method thereof |
| CN114870658A (en) * | 2022-05-25 | 2022-08-09 | 哈尔滨工业大学 | Preparation method of polyamide nanofiltration membrane with polyaldehyde crosslinked polyvinyl alcohol as intermediate layer |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101934201A (en) * | 2009-06-29 | 2011-01-05 | 北京时代沃顿科技有限公司 | High-selectivity composite nanofiltration membrane and preparation method thereof |
| CN101732998B (en) * | 2010-01-25 | 2012-03-07 | 杭州水处理技术研究开发中心有限公司 | Preparation method for cross-linking polyvinyl alcohol furfural nanofiltration membrane |
| CN102125811B (en) * | 2011-01-10 | 2012-09-05 | 杭州水处理技术研究开发中心有限公司 | Method for preparing polyvinyl alcohol-chitosan nano filtration membrane |
-
2014
- 2014-12-18 CN CN201410794979.4A patent/CN104525000B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN104525000A (en) | 2015-04-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104525000B (en) | A kind of preparation method of high selectivity polyvinyl alcohol nanofiltration membrane | |
| CN103446899B (en) | Organic and inorganic surface chemically-crosslinked alginate-based hybrid hydrogel filter membrane, and preparation method thereof | |
| CN103736400B (en) | A kind of preparation method of graphene oxide composite nano filter membrane | |
| CN104772043B (en) | Sodium alginate-graphite phase carbon nitride nano-sheet hybridized composite membrane as well as preparation and application of composite membrane | |
| CN105148741B (en) | A kind of preparation method of inorganic nano-hybrid lotus positive electrical polyelectrolyte complex compound infiltrating and vaporizing membrane | |
| CN104607063B (en) | PVDF permanently hydrophilic ultrafiltration membrane and modification method thereof | |
| CN103331108B (en) | Polymer pervaporation membrane prepared by dialysis method after membrane formation and preparation method of polymer pervaporation membrane | |
| CN106890570A (en) | A kind of preparation method of the hollow fiber nanofiltration membrane of graphene oxide doped | |
| CN105617882A (en) | Chitosan modified graphene oxide nano composite positive osmotic membrane and preparation method thereof | |
| CN103706264A (en) | Layer-by-layer self-assembling oxidized graphene nano-filtration membrane and preparation method thereof | |
| CN105289321B (en) | A kind of composite nanometer filtering film and preparation method thereof | |
| CN105233705A (en) | Polyvinylidene fluoride/polydopamine modified nanometer kaolin hollow fiber composite film preparation method | |
| CN109012188B (en) | Preparation method of high-flux polytetrafluoroethylene composite nanofiltration membrane | |
| CN104362277A (en) | Composite separator with multilayered structure and preparation method of separator | |
| EP1024886A1 (en) | A manufacturing method of composite membrane having hydrophilic coating layer on hydrophobic support membrane | |
| CN108246130B (en) | GO/SiO2Preparation method of modified nano composite film | |
| CN105214502A (en) | A kind of Nano Silver/Graphene/polyvinyl alcohol mixing matrix membrane and preparation method thereof | |
| CN104607056A (en) | Hollow fiber compound nanofiltration membrane and preparation method thereof | |
| Hyeon et al. | Composite membranes based on sulfonated poly (ether ether ketone) and SiO 2 for a vanadium redox flow battery | |
| CN102580585A (en) | Preparation method of pollution-resistant low-pressure nanofiltration membrane | |
| CN102274693A (en) | Method for preparing organic pervaporation membrane | |
| CN102743981A (en) | Preparation and application of sodium alginate pervaporation hybrid membrane | |
| CN108837714A (en) | A kind of poly-dopamine/manganese dioxide composite membrane and preparation method thereof | |
| CN104801206A (en) | Modified guanidyl film, and preparation and application thereof | |
| CN114984769A (en) | Fluoropolymer hollow fiber hydrophobic porous membrane and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |