CN103055715B - Composite nanofiltration membrane and preparation method thereof - Google Patents
Composite nanofiltration membrane and preparation method thereof Download PDFInfo
- Publication number
- CN103055715B CN103055715B CN201310041836.1A CN201310041836A CN103055715B CN 103055715 B CN103055715 B CN 103055715B CN 201310041836 A CN201310041836 A CN 201310041836A CN 103055715 B CN103055715 B CN 103055715B
- Authority
- CN
- China
- Prior art keywords
- solution
- film
- layer
- membrane
- preparation
- 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)
Abstract
The invention discloses a composite nanofiltration membrane and a preparation method thereof, and belongs to the technical field of nanofiltration membranes. The composite nanofiltration membrane is characterized by comprising a three-layer structure that the lowest layer is a polyester non-woven fabric base membrane, the middle layer is a chlorinated polyvinyl chloride support layer and the top layer is an aromatic polyamide ultrathin separation layer. Compared with the prior art, the composite nanofiltration membrane is simple in formula, convenient to carry out technological operation, and easy to carry out industrial production. By adopting the technology disclosed by the invention, the prepared composite nanofiltration membrane has good chemical stability and anti-fouling performance; the reject rate on magnesium sulfate is greater than 97%, and the reject rate on sodium chloride is greater than 85%.
Description
Technical field
The invention belongs to technical field of membrane separation, specifically, the present invention relates to a kind of composite nanometer filtering film and preparation method thereof, it contains three-decker: orlop is polyester non-woven fabric basement membrane, and middle one deck is chliorinated polyvinyl chloride supporting layer, and the superiors are aromatic polyamides ultra-thin parting absciss layers, formula of the present invention is simple, technological operation is convenient, and being easy to suitability for industrialized production, is a kind of composite nanometer filtering film that can be applicable to life, chemical industry, biology, environmental protection, medicine and other fields.
Background technology
Membrane separation technique is as the optimization technique of 21 century water treatment, with conventional water treatment Technical comparing, have that energy consumption is low, separative efficiency is high, technique is simple, without the need to adding additive, not affecting the advantages such as health, therefore the field such as to prepare at the process of seawater and brackish water desalination, dirty water and waste water and recovery, ultra-pure water to be widely used, and demonstrate vast potential for future development.
Membrane separating process mainly contains micro-filtration (MF), ultrafiltration (UF), nanofiltration (NF) and counter-infiltration (RO).NF membrane is the pressure-actuated Novel separation film of one between reverse osmosis membrane and milipore filter, it can retain organic molecule and most of inorganic salts be passed through, the separation of different valence state ion can be realized, the very little same amino acid of relative molecular mass difference and same proteinoid can be separated, and high relative molecular weight can be realized be separated with the organic of low relative molecular weight, due to cut-off region (the cutoff scope 200 ~ 1000Da of its acumen, and its aperture is in nanoscale), in petrochemical industry, biochemical and medical, food, papermaking, be used widely in the fields such as textile printing and dyeing and water treatment procedure.The eighties in 20th century, U.S.'s Filmtec companies develops the NF membrane of the models such as NF-40, NF-50, NF-70.At present, Nanofiltration-membrane technique is state-of-the-art separation and filtering technique in the world, and due to extensive market, the numerous and confused organizational strength in countries in the world is put in the exploitation of Nanofiltration-membrane technique.The kind of NF membrane constantly increases, and performance improves constantly.Its development trend is exploitation heat-resisting, acid and alkali-resistance, resistance to oxidation, resistance to free chlorine, high water flux, high rejection, resistant to pollution high-performance NF membrane.Membrane material has cellulose acetate, aromatic polyamides, sulfonated polyether sulfone etc.From the engineering of water treatment example of nanofiltration successful operation at home and abroad, its separating property is good, and stable effluent quality is reliable, and energy consumption low, there is good Technical Economy.
Although the domestic development of NF membrane is in recent years very fast, successively researched and developed multiple NF membrane, major part is all also in the laboratory research development phase, not yet commercialization.The chemical stability of film and resistance tocrocking are all poor.Wherein crucial be also the selection of membrane material and preparation technology immature.
Summary of the invention
The object of the present invention is to provide and be a kind ofly easy to the stable performance of suitability for industrialized production, resistant to pollution composite nanometer filtering film and preparation method thereof.
Technical characteristic of the present invention is: this composite nanometer filtering film forms by three layers, orlop is non-woven fabrics basement membrane, and middle one deck is chliorinated polyvinyl chloride supporting layer, and the superiors are aromatic polyamides ultra-thin parting absciss layers, technical scheme of the present invention is made up of formula and preparation technology
Technical characteristic of the present invention is: provide a kind of hollow fiber compound nanofiltration membrane, and it comprises basement membrane, supporting layer and separating layer,
Basement membrane is matured product-polyester non-woven fabric
The milipore filter of the feature of supporting layer formula to be a kind of with chliorinated polyvinyl chloride be base material, containing (by weight percentage):
High molecular polymer-chliorinated polyvinyl chloride (CPVC): 12% ~ 15%,
Solvent-dimethyl formamide (DMF): 75 ~ 80%,
Additive-calcium chloride (CaCl
2): 2 ~ 8%,
The feature of separating layer is a kind of high crosslinked aromatic polyamides separating layer, and its forming process is the crosslinked of solution A and solution B,
The formula of solution A contains (by weight percentage):
High molecular polymer-m-phenylene diamine (MPD): 0.05% ~ 2%,
Solvent-water: 97 ~ 99.95%,
Additive-neopelex: 0.02 ~ 2%,
The formula of solution B contains (by weight percentage):
High molecular polymer-pyromellitic trimethylsilyl chloride: 0.05 ~ 2.5%,
Solvent-n-hexane: 97.5 ~ 99.95%,
The supporting layer that hollow fiber compound nanofiltration membrane of the present invention comprises, the feature of its preparation technology is a kind of sol-gel phase separation method preparation method, contains following steps with this:
Step 1, after high molecular polymer, solvent and additive are weighed by the proportioning of described formula, mixing;
Step 2, the mixed liquor of step 1 is stirred and is warming up to 70-80 ° of C gradually, stir at this temperature, high molecular polymer, solvent and additive are fully dissolved becomes uniform colloidal sol;
Step 3, the colloidal sol that step 2 is obtained is placed in centrifugal degasser degassed, and is cooled to 60-65 ° of about C, is incubated 24 hours;
Step 4, by colloidal sol obtained for step 3 with Flat Membrane knifing machine even application on non-woven fabrics base material.Coated film THICKNESS CONTROL is at about 20 ~ 120 μm;
Step 5, the Flat Membrane after film is immersed in water-bath carries out gel, and bath temperature controls between 20 ~ 25 ° of C;
Step 6, tests after film forming, the process such as dehydration, makes supporting layer.
The ultra-thin parting absciss layer of hollow fiber compound nanofiltration membrane of the present invention, the feature of its preparation technology is a kind of interfacial polymerization preparation method, containing following steps:
Step 1: by described formulated solution A and solution B;
Step 2, is immersed in solution A by the above-mentioned basement membrane being coated with supporting layer, and solution A temperature controls at 0 ~ 30 ° of C, soaks and takes out after 1 ~ 60 second, remove unnecessary solution A;
Step 3: the film processed through step 2 applies solution B through Flat Membrane coating machine, and solution B temperature controls at 0 ~ 30 ° of C;
Step 4: the film processed through step 3 is immersed in pure water, and water temperature controls at 20 ~ 60 ° of C, soak time 1 ~ 20 hour;
Step 5: the film processed through step 4 at the air drying of 20 ~ 30 °,
Step 6: the film processed through step 5 heats under 50 ~ 90 ° of C, the composite nanometer filtering film of obtained three-decker of the present invention.
The test of film: (1) Adlerika, with the MgSO of 2000ppm
4solution, test pressure 0.5MPa, probe temperature 25 ° of C; (2) sodium chloride solution, by the NaCl solution of 2000ppm, test pressure 0.5MPa, probe temperature 25 ° of C.
Compared with prior art, formula of the present invention is simple, and technological operation is convenient, is easy to suitability for industrialized production.Adopt the technology of the present invention, obtained composite nanometer filtering film has good chemical stability and resistance tocrocking, is greater than 97%, is greater than 85% to sodium chloride rejection to magnesium sulfate rejection rate.
Detailed description of the invention
Help to understand the present invention better according to following embodiment, instead of the present invention described in detail in restriction claims.
Embodiment 1, the preparation process of the present embodiment is as follows:
(1) configure supporting layer preparation liquid, take chliorinated polyvinyl chloride 120g(12%), solvent DMF 800g(80%), additive calcium chloride 80g(8%) and, preparation 1000g preparation liquid;
(2) mixed liquor stirs and is warming up to 75 ° of C gradually, makes uniform colloidal sol;
(3) after degassed, cool to 60 ° of C and be incubated 24 hours;
(4) be coated on non-woven fabrics base material with Flat Membrane knifing machine by film, coating layer thickness is 0.2mm, is immersed in gel film forming in the water-bath of 25 ° of C;
(5) above-mentioned film is for subsequent use through checking, dewatering;
(6) configure solution A, 1000g, takes m-phenylene diamine (MPD) 10g(1%), water 970g(97%), neopelex 20g(2%) and, above-mentioned substance mixing and stirring obtained solution A;
(7) configure solution B, 1000g, takes pyromellitic trimethylsilyl chloride 20g(2%), n-hexane 980g(98%), above-mentioned substance mixing and stirring obtained solution B;
(8) film made through step 7 is immersed in solution A, solution A temperature 25 ° of C, soaks 30 seconds, removes unnecessary solution A;
(9) above-mentioned film is through Flat Membrane coating machine coating solution B, solution B temperature 25 ° of C;
(10) above-mentioned film is immersed in pure water, water temperature 40 ° of C, soak time 10 hours;
(11) above-mentioned film is at the air drying of 25 ° of C;
(12) above-mentioned film heats under 60 ° of C, and obtained the present invention has the composite nanometer filtering film of three-decker.
Embodiment 2, the preparation process of the present embodiment is as follows:
(1) configure supporting layer preparation liquid, take chliorinated polyvinyl chloride 150g(15%), solvent DMF 790g(79%), additive calcium chloride 60g(6%) and, preparation 1000g preparation liquid;
(2) mixed liquor stirs and is warming up to 75 ° of C gradually, makes uniform colloidal sol;
(3) after degassed, cool to 60 ° of C and be incubated 24 hours;
(4) be coated on non-woven fabrics base material with Flat Membrane knifing machine by film, coating layer thickness is 0.2mm, is immersed in gel film forming in the water-bath of 25 ° of C;
(5) above-mentioned film is for subsequent use through checking, dewatering;
(6) configure solution A, 1000g, takes m-phenylene diamine (MPD) 15g(1.5%), water 970g(97%), neopelex 15g(1.5%) and, above-mentioned substance mixing and stirring obtained solution A;
(7) configure solution B, 1000g, takes pyromellitic trimethylsilyl chloride 18g(1.8%), n-hexane 980g(99.2%), above-mentioned substance mixing and stirring obtained solution B;
(8) film made through step 7 is immersed in solution A, solution A temperature 25 ° of C, soaks 30 seconds, removes unnecessary solution A;
(9) above-mentioned film is through Flat Membrane coating machine coating solution B, solution B temperature 25 ° of C;
(10) above-mentioned film is immersed in pure water, water temperature 40 ° of C, soak time 10 hours;
(11) above-mentioned film is at the air drying of 25 ° of C;
(12) above-mentioned film heats under 60 ° of C, and obtained the present invention has the composite nanometer filtering film of three-decker.
The performance test of composite nanometer filtering film
The composite nanometer filtering film obtained to above-described embodiment carries out performance test, (1) Adlerika, with the MgSO of 2000ppm
4solution, test pressure 0.5MPa, probe temperature 25 ° of C; (2) sodium chloride solution, by the NaCl solution of 2000ppm, test pressure 0.5MPa, probe temperature 25 ° of C.
The composite nanometer filtering film of embodiment 1 is 97.5% to the rejection of magnesium sulfate after tested, and water flux is 46.2L/m
2.h, be 86.2% to the rejection of sodium chloride, water flux is 46.5L/m
2.h; The composite nanometer filtering film of embodiment 2 is 97.8% to the rejection of magnesium sulfate, and water flux is 45.9L/m
2.h, be 85.8% to the rejection of sodium chloride, water flux is 45.8L/m
2.h.
Claims (1)
1. the preparation method of a composite nanometer filtering film, it is characterized in that, containing three-decker: orlop is polyester non-woven fabric basement membrane, middle one deck is the chliorinated polyvinyl chloride supporting layer prepared by sol-gel phase separation method, and the superiors are the aromatic polyamides ultra-thin parting absciss layers prepared by interfacial polymerization;
The milipore filter of feature of its formula of described supporting layer to be a kind of with chliorinated polyvinyl chloride be base material, contains, by weight percentage:
High molecular polymer-chliorinated polyvinyl chloride (CPVC): 12% ~ 15%,
Solvent-dimethyl formamide (DMF): 75 ~ 80%,
Additive-calcium chloride (CaCl
2): 2 ~ 8%, chliorinated polyvinyl chloride, dimethyl formamide and calcium chloride three components sum are 100%;
Feature of its formula of described separating layer is a kind of high crosslinked aromatic polyamides separating layer, its forming process be solution A and solution B be cross-linked to form aromatic polyamides separating layer,
The formula of solution A contains, by weight percentage:
High molecular polymer-m-phenylene diamine (MPD): 0.05% ~ 2%,
Solvent-water: 97 ~ 99.95%,
Additive-neopelex: 0.02 ~ 2%, m-phenylene diamine (MPD), water and neopelex three components sum are 100%;
The formula of solution B contains, by weight percentage:
High molecular polymer-pyromellitic trimethylsilyl chloride: 0.05 ~ 2.5%,
Solvent-n-hexane: 97.5 ~ 99.95%;
Prepare the method for composite nanometer filtering film successively containing following steps:
The preparation of middle support layer
Step 1, after high molecular polymer, solvent and additive being weighed by described proportioning by supporting layer formula, mixing;
Step 2, the mixed liquor of step 1 is stirred and is warming up to 70-80 ° of C gradually, stir at this temperature, high molecular polymer, solvent and additive are fully dissolved becomes uniform colloidal sol;
Step 3, the colloidal sol that step 2 is obtained is placed in centrifugal degasser degassed, and is cooled to 60-65 ° of C, is incubated 24 hours;
Step 4, colloidal sol step 3 obtained is with Flat Membrane knifing machine even application on non-woven fabrics base material, and coated film THICKNESS CONTROL is at 20 ~ 120 μm;
Step 5, the Flat Membrane after film is immersed in water-bath carries out gel, and bath temperature controls between 20 ~ 25 ° of C;
Step 6, tests after film forming, processed, makes supporting layer;
The preparation of ultra-thin parting absciss layer
Step a: by separating layer formulated solution A and solution B;
Step b, is immersed in solution A by the basement membrane being coated with supporting layer, and solution A temperature controls at 0 ~ 30 ° of C, soaks and takes out after 1 ~ 60 second, remove unnecessary solution A;
Step c: the film through step b process applies solution B through Flat Membrane coating machine, and solution B temperature controls at 0 ~ 30 ° of C;
Steps d: the film through step c process is immersed in pure water, water temperature controls at 20 ~ 60 ° of C, soak time 1 ~ 20 hour;
Step e: through the film of steps d process at the air drying of 20 ~ 30 °,
Step f: the film through step e process heats under 50 ~ 90 ° of C, the composite nanometer filtering film of obtained three-decker of the present invention.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310041836.1A CN103055715B (en) | 2013-02-04 | 2013-02-04 | Composite nanofiltration membrane and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310041836.1A CN103055715B (en) | 2013-02-04 | 2013-02-04 | Composite nanofiltration membrane and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103055715A CN103055715A (en) | 2013-04-24 |
| CN103055715B true CN103055715B (en) | 2015-01-28 |
Family
ID=48098784
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310041836.1A Active CN103055715B (en) | 2013-02-04 | 2013-02-04 | Composite nanofiltration membrane and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103055715B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104190265A (en) * | 2014-08-31 | 2014-12-10 | 浙江大学 | Low-pressure high-flux chlorine-containing polymer nanofiltration membrane with stable separation layer and preparation method thereof |
| CN105289335B (en) * | 2015-11-30 | 2018-01-30 | 天津工业大学 | A kind of high-throughout compound membrane preparation method |
| CN108452689A (en) * | 2017-03-06 | 2018-08-28 | 青岛致用新材料科技有限公司 | Highly selective full alicyclic polyamide NF membrane of one kind and preparation method thereof |
| CN107158971A (en) * | 2017-06-09 | 2017-09-15 | 浙江睿升环保科技有限公司 | A kind of preparation method of composite nanometer filtering film |
| CN107899437A (en) * | 2017-11-21 | 2018-04-13 | 贵阳时代沃顿科技有限公司 | A kind of high-performance water-oil separationg film based on interfacial polymerization and preparation method thereof |
| CN112604512A (en) * | 2020-11-16 | 2021-04-06 | 广西中科鼎新产业技术研究院有限公司 | Acid-resistant ultrafiltration membrane material and preparation method thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2517782A4 (en) * | 2009-12-24 | 2017-01-04 | Toray Industries, Inc. | Composite semipermeable membrane and method for producing same |
| CN102139187B (en) * | 2010-01-28 | 2013-04-10 | 中国科学院化学研究所 | Hyperfiltration membrane or nanofiltration membrane with multi-layered composite structure and preparation method thereof |
| CN102380257B (en) * | 2010-09-02 | 2013-11-06 | 财团法人工业技术研究院 | Filtration material for desalination |
| CN102580556B (en) * | 2012-03-06 | 2015-04-29 | 北京科泰兴达高新技术有限公司 | Antipollution flat membrane and method for producing same |
-
2013
- 2013-02-04 CN CN201310041836.1A patent/CN103055715B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN103055715A (en) | 2013-04-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103055715B (en) | Composite nanofiltration membrane and preparation method thereof | |
| CN110314559A (en) | A kind of preparation method of interfacial polymerization composite membrane | |
| CN105435653B (en) | A kind of composite nanometer filtering film to divalent ion removing with high selectivity and preparation method thereof | |
| WO2018120476A1 (en) | Supramolecular composite nano-filtration membrane and preparation method therefor and use thereof | |
| Wang et al. | Polybenzimidazole nanofiltration hollow fiber for cephalexin separation | |
| CN110917907B (en) | High-flux reverse osmosis membrane and preparation method and application thereof | |
| Liu et al. | Highly improved organic solvent reverse osmosis (OSRO) membrane for organic liquid mixture separation by simple heat treatment | |
| CN107029555A (en) | A kind of solvent resistant NF membrane and preparation method thereof | |
| CN110339724B (en) | Composite polyamide membrane with salt concentration responsiveness and preparation method and application thereof | |
| CN110215852A (en) | Composite semipermeable membrane | |
| WO2006038409A1 (en) | Process for producing semipermeable composite membrane | |
| WO2013129610A1 (en) | Complex semi-permeable membrane | |
| Semiz | Removal of reactive black 5 from wastewater by membrane filtration | |
| CN107486041B (en) | Ultra-low pressure composite reverse osmosis membrane and preparation method thereof | |
| Wei et al. | One-step fabrication of recyclable polyimide nanofiltration membranes with high selectivity and performance stability by a phase inversion-based process | |
| CN105709616B (en) | A kind of preparation method of organic solvent-resistant ultrafiltration membrane, prepared film and its application | |
| KR20100078822A (en) | Manufacturing method for polyamide-based reverse osmosis membrane and polyamide-based reverse osmosis membrane manufactured thereby | |
| CN103111191B (en) | Preparation method of high-flux composite polyamide reverse osmosis membrane | |
| CN110354682A (en) | A kind of stable against biological contamination reverse osmosis membrane and its preparation method and application | |
| CN109173753A (en) | Casting solution, ultrafiltration membrane, reverse osmosis composite membrane or Nano filtering composite membrane | |
| CN109692579A (en) | Reverse osmosis membrane and its preparation method and application | |
| Ghodsi et al. | Controlling the morphology of PVDF hollow fiber membranes by promotion of liquid–liquid phase separation | |
| CN105939777B (en) | Spiral separation membrane element | |
| Hosseini et al. | Exploring the characteristics, performance, and modification of Matrimid for development of thin‐film composite and thin‐film nanocomposite reverse osmosis membranes | |
| JP2013223861A (en) | Composite diaphragm |
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 | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: A composite nanofiltration membrane and its preparation method Effective date of registration: 20210317 Granted publication date: 20150128 Pledgee: Bank of Inner Mongolia Co., Ltd. Xilingol Taipusiqi sub branch Pledgor: BEIJING CRYSTEC TECHNOLOGIES Co.,Ltd. Registration number: Y2021150000023 |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| PC01 | Cancellation of the registration of the contract for pledge of patent right |
Date of cancellation: 20220324 Granted publication date: 20150128 Pledgee: Bank of Inner Mongolia Co.,Ltd. Xilingol Taipusiqi sub branch Pledgor: Beijing Crystec Technologies Co.,Ltd. Registration number: Y2021150000023 |
|
| PC01 | Cancellation of the registration of the contract for pledge of patent right |