CN102133506A - Polyamide composite nanofiltration membrane - Google Patents
Polyamide composite nanofiltration membrane Download PDFInfo
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- CN102133506A CN102133506A CN2011100489118A CN201110048911A CN102133506A CN 102133506 A CN102133506 A CN 102133506A CN 2011100489118 A CN2011100489118 A CN 2011100489118A CN 201110048911 A CN201110048911 A CN 201110048911A CN 102133506 A CN102133506 A CN 102133506A
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Abstract
The invention relates to a polymer separation membrane, in particular to a high-performance polyamide composite membrane. In the invention, an ultra-thin active separating layer is compounded on a porous supporting membrane through interfacial polycondensation between an aqueous solution containing aliphatic macromolecular polyamine and an organic solution containing a dyadic aromatic reaction monomer; the aliphatic macromolecular polyamine is polyvinylamine; the dyadic aromatic reaction monomer is phthaloyl chloride or paraphthaloyl chloride or 2,4-toluene diisocyanate; and the thickness of the active separating layer is 0.02-0.5 mum. The invention has the advantage that a novel high-performance composite nanofiltration membrane which is made of raw materials easy to obtain and has low cost and excellent preferential segregation performance is provided. The high-performance composite nanofiltration membrane provided by the invention has multiple purposes and a simple manufacturing method.
Description
Technical field
The present invention relates to a kind of polymeric membrane for separation, specifically be meant a kind of high performance polyamide composite film.
Technical background
NF membrane is a kind of novel diffusion barrier of aperture between reverse osmosis membrane and milipore filter, because how electrically charged it have on nano level membrane aperture, the film, allow low organic matter and the multivalent ion of alite that divide, have unique separating property, higher separation accuracy by holding back higher molecular weight.Compare with other diffusion barrier, NF membrane has that membrane flux is bigger, the process infiltration forces down, selects isolating ions, operating pressure power low, system to require characteristics such as low.At present, the NF membrane technology be widely used in water softening and brackish water desalination, drink water purifying, feed separation purifying and concentrate, wastewater treatment and fields such as middle water reuse, cleaner production, obtained good economic and social benefit.But the development of NF membrane at present also is not very ripe, is mainly reflected in: the needs that the manufacturing cost of NF membrane is higher relatively, the NF membrane performance can't satisfy practical application.Thereby it is very crucial and necessary to applying of NF membrane technology to develop high performance nanofiltration film.
Composite nanometer filtering film is that one deck ultrathin functional layer is deposited to suitable micropore support membrane surface, aperture, and depositional mode mainly contains surface-coated, interfacial polycondensation and in-situ polymerization etc.Composite membrane has many advantages than asymmetric membrane: it can make every layer to reach optimum performance by optimization.Ultrathin functional layer can be optimized to desirable selection permeability, and support membrane can reach best intensity and pressure tightness.In addition, composite membrane can make the material that is difficult to form asymmetric membrane form ultrathin membrane, as because solvent limitation and crosslinking polymer can form composite membrane by in-situ polymerization or interfacial polycondensation.To the ultra-thin active separating layer material requirements good hydrophilic property of composite nanometer filtering film, and its mechanical stability, heat endurance and hydrolytic stability are all fine.At present, business-like composite nanometer filtering film all is on the polysulfones porous support membrane, is prepared from by the interfacial polycondensation between polyamine and the polynary acyl chlorides.
Fibiger etc. adopt interfacial polymerization technology to prepare composite nanometer filtering film in US Patent 4,769,148 in 1987.Water is the aqueous solution that contains piperazine function monomer and wetting agent, and organic facies contains the crosslinking agent pyromellitic trimethylsilyl chloride, obtains the composite nanometer filtering film of ultrathin functional layer for poly-piperazine amide.The chemical structural formula of its active separating layer can be expressed as:
Cadotte etc. adopt interfacial polymerization technology and strong acid treatment method to prepare composite nanometer filtering film in US Patent 4,812,270 in 1989.Water is the aqueous solution that contains m-phenylene diamine (MPD) function monomer and wetting agent, organic facies contains the crosslinking agent pyromellitic trimethylsilyl chloride, obtain the compound ultrathin functional layer of Wholly aromatic polyamide through interfacial polymerization, with strong acid the polyamide functional layer is handled then, with the removal efficiency reinforcing agent film is modified to handle at last and wait until the composite nanometer filtering film that is applicable to water softening.The chemical structural formula of the active separating layer of composite nanometer filtering film is as follows:
Hodgdon etc. adopt interface polycondensation to prepare composite nanometer filtering film in US Patent 5,152,901 in 1992.Water is the aqueous solution of bridged piperazine derivatives class polyamine and wetting agent, and it is pyromellitic trimethylsilyl chloride and m-phthaloyl chloride mixture that organic facies contains crosslinking agent, and the ultrathin functional layer of the composite membrane NF membrane that obtains is poly-piperazine amide.The chemical structural formula of its active separating layer can be expressed as::
Lawrence etc. adopt interfacial polymerization to prepare composite nanometer filtering film in US Patent 5,693,227 in 1997.Water is the aqueous solution that contains piperazine function monomer and wetting agent, and organic facies contains crosslinking agent 5-isocyanates isophthaloyl chlorine, and porous support membrane is a polysulphone super-filter membrane, and the ultrathin functional layer of the composite nanometer filtering film that obtains is poly-piperazine amide-polyureas.The concrete chemical structural formula of active separating layer can be expressed as:
In addition, US Patent 6,123,804, US Patent 6,464,873, US Patent6,536,605, patent such as US Patent 6,878,278 also is to adopt the interface polymerization reaction between polyamine and the polynary acyl chlorides to prepare composite nanometer filtering film.
But the composite nanometer filtering film of commercially producing at present exists still that kind is single, performance is on the low side, can't satisfy problems such as practical application request.
Thereby preparation novel high-performance composite nanometer filtering film is for increasing the NF membrane kind, improve the NF membrane performance, satisfying application the demand of high-performance NF membrane material is all had crucial meaning.
Summary of the invention
The present invention is directed to deficiency of the prior art, provide a kind of raw material to be easy to get, cheap, select the superior composite nanometer filtering film of separating property.
The present invention is achieved by following technical proposals:
A kind of polyamide composite nanometer filtering film, it is characterized in that, the aqueous solution by the big molecule polyamine of fatty family on the porous support membrane and contain interfacial polycondensation between the organic solution of binary aromatic series reaction monomers is compounded with the ultra-thin active separating layer of one deck, and the chemical structural formula of active separating layer is expressed as:
In the formula, X is:
Porous support membrane wherein is conventional support membrane, and its preparation method, membrane structure are general in the market film, can oneself prepare, also can buy on market in the present invention.
As preferably, above-mentioned polyamide composite nanometer filtering film, the big molecule polyamine of described aliphatic is polyvinylamine (PVAm), its chemical structural formula is as follows:
In the formula: a is the ammonia degree of separating of polyvinylamine, a=vinylamine construction unit number/(vinylamine construction unit number+acrylamide construction unit number).
As preferably, above-mentioned polyamide composite nanometer filtering film, described binary aromatic series reaction monomers is m-phthaloyl chloride (IPC), or paraphthaloyl chloride (TPC), or 2,4-vulcabond toluene (TDI).
As preferably, above-mentioned polyamide composite nanometer filtering film, the described part by weight that is used for the big molecule polyamine of aqueous solution aliphatic of interfacial polycondensation is 0.5-4.0wt%, the part by weight of binary aromatic series reaction monomers is 0.05-0.30wt% in the organic solution.
As preferably, above-mentioned polyamide composite nanometer filtering film, ammonia degree of the separating a of described polyvinylamine is between 0.1-0.9.
As preferably, above-mentioned polyamide composite nanometer filtering film, the molecular weight of described polyvinylamine is between 1000-500000; As better selection, the molecular weight of described polyvinylamine is between 3000-100000.
As preferably, above-mentioned polyamide composite nanometer filtering film, the thickness of described active separating layer is between 0.02-0.5 μ m; As better selection, the thickness of described active separating layer is between 0.05-0.3 μ m.
Polyamide composite nanometer filtering film described in the present invention is a flat sheet membrane, or hollow-fibre membrane, or tubular membrane.
Beneficial effect: the selection separating property of high-performance composite nanometer filtering film of the present invention and permeance property are not less than existing polyamide composite nanometer filtering film, and the preparation method is more simple.
The specific embodiment
Below enforcement of the present invention is specified:
Following examples provide explanation, preparation method and their separating property of high-performance composite nanometer filtering film.Yet these embodiment only provide as an illustration rather than limit the present invention.
Porous support membrane preparation: preparation according to a conventional method, the present invention is the UDEL PS3500 polysulfones with 13.0wt%, the water of 0.25wt% and the surfactant of 0.1wt% are dissolved in N, in the dinethylformamide, be coated with and scrape on polyester non-woven fabric, immerse then in the water to remove and obtain molecular cut off (MWCO) after desolvating and be the polysulfones porous support membrane of 8-10 ten thousand.Wherein surfactant comprises alkyl phenol polyoxy Acetoxon acid esters at least, a kind of in dodecyl sodium sulfate and the alkyl phenol polyoxy Acetoxon hydrochlorate.
The preparation of composite nanometer filtering film: the polysulfones porous support membrane of hygrometric state is immersed in contains in the big molecule polyamine of the aliphatic aqueous solution that acid receives agent 2-8 minute, with squeegee roll extrusion support membrane surface, after taking-up drains the aqueous solution and dries up with nitrogen, carry out the single face interface polymerization reaction with the organic solution that contains binary aromatic series reaction monomers; It is triethylamine that acid wherein receives agent, or NaOH, or sodium carbonate, or tertiary sodium phosphate, and content is 1.0-4.0wt%; The big molecule polyamine of aliphatic wherein is polyvinylamine (PVAm), and content is 0.5-4.0wt%, and ammonia degree of separating is 0.1-0.9, and molecular weight is at 1000-500,000; Binary aromatic series reaction monomers wherein is m-phthaloyl chloride (IPC), or paraphthaloyl chloride (TPC), or 2,4-vulcabond toluene (TDI), content are 0.05-0.30wt%; The used organic solvent of organic solution is Isopar
G, or trifluorotrichloroethane, or n-hexane, or normal heptane, or dodecane; The single face haptoreaction time wherein is 0.5-5 minute.After composite membrane dried in the shade 2-5 minute, handled 5-10 minute down last in 40-50 ℃ water rinsing 20-40 minute again at 50-80 ℃ in air.
The composite nanometer filter membrane separating property is estimated: solute removal efficiency and water flux are two important parameters of evaluating combined film nanofiltration separation performance.By the cross-flow permeability test, sodium chloride removal efficiency, sodium sulphate removal efficiency and the water flux etc. of composite nanometer filtering film are separated performance evaluation.
Solute removal efficiency (R) is defined as: under certain operating condition, and feeding liquid solute concentration (C
f) with penetrating fluid in solute concentration (C
p) poor, again divided by the feeding liquid solute concentration.Concrete computing formula is as follows:
Water flux (F) is defined as: under certain operating condition, see through the volume (V) of the water of elementary membrane area (A) in the unit interval (t), its unit is l/m
2.h.Concrete computing formula is as follows:
The operating condition that composite nanometer filter membrane separating property mensuration adopts among the present invention is: feed liquor is sodium-chloride water solution or the aqueous sodium persulfate solution of 500mg/l, and operating pressure is 1.0MPa, and operating temperature is 25 ℃, and pH value of solution is 6.8.
Embodiment 1-3
UDEL PS3500 polysulfones with 13.0wt%, the polyoxyethylene nonyl phenyl Acetoxon acid esters of the water of 0.25wt% and 0.1wt% is dissolved in N, the N--dimethyl formamide is coated with and scrapes on polyester non-woven fabric, immerses then in the water to remove that to obtain molecular cut off after desolvating be 100,000 polysulfones porous support membrane.
The polysulfones porous support membrane of hygrometric state is immersed in polyvinylamine (molecular weight=28,000 that contain 3.0wt% triethylamine and 3.0wt%; Ammonia degree of separating a=0.53) in the aqueous solution 5 minute, with squeegee roll extrusion support membrane surface, after draining the aqueous solution and the support membrane surface being dried up with nitrogen, (be respectively m-phthaloyl chloride (IPC) with the binary aromatic series reaction monomers that contains of 0.2wt%, or paraphthaloyl chloride (TPC), or 2,4-vulcabond toluene (TDI)) n-heptane solution single face contact carried out interface polymerization reaction 120 seconds.The composite membrane of gained dried in the shade in air 5 minutes, handled 10 minutes down at 60 ℃ again, last rinsing 30 minutes in 40-50 ℃ water.The composite nanometer filtering film of preparation is used sodium-chloride water solution and the aqueous sodium persulfate solution of 500mg/l respectively, 1.0MPa, 25 ℃, pH 6.8 times, and the solute removal efficiency and the water flux of test membrane.These several embodiment investigate in the organic solution binary aromatic series reaction monomers kind to the composite nanometer filtering film Effect on Performance.
Embodiment 4-10
As the embodiment of front, as stated above, adopt polyvinylamine (molecular weight=28,000 that contain 3.0wt% triethylamine and 0.5-4.0wt%; Ammonia degree of separating a=0.53) the aqueous solution contacts with the n-heptane solution single face of the m-phthaloyl chloride (IPC) of 0.18wt% and to carry out preparing in interface polymerization reaction 0.5-5 minute composite nanometer filtering film.These several embodiment investigate the part by weight of policapram in the aqueous solution to the composite nanometer filtering film Effect on Performance.
Embodiment 11-17
As the embodiment of front, as stated above, adopt polyvinylamine (molecular weight=28,000 that contain 4.0wt% tertiary sodium phosphate and 2.4wt%; Ammonia degree of separating a=0.53) the aqueous solution contacts with the hexane solution single face of the paraphthaloyl chloride (TDI) of 0.05-0.30wt% and to carry out interface polymerization reaction and prepared composite nanometer filtering film in 90 seconds.These several embodiment investigate the part by weight of binary aromatic series reaction monomers in the organic phase solution to the composite nanometer filtering film Effect on Performance.
Embodiment 18-27
As the embodiment of front, as stated above, adopting the molecular weight contain 1.0wt% NaOH and 2.8wt% is 1000-500,000, ammonia degree of separating is the aqueous solution of the polyvinylamine of 0.1-0.9, and with the Isopar of the paraphthaloyl chloride (TPC) of 0.15wt%
GThe formulations prepared from solutions composite nanometer filtering film.These several embodiment are ammonia degree of separating of investigating polyvinylamine with molecular weight to the composite nanometer filtering film Effect on Performance.
Claims (9)
1. polyamide composite nanometer filtering film, it is characterized in that, at the aqueous solution by the big molecule polyamine of fatty family on the porous support membrane and contain interfacial polycondensation between the organic solution of binary aromatic series reaction monomers, the active separating layer of compound one deck, the chemical structural formula of active separating layer is expressed as:
In the formula, X is:
Described organic solution is: Isopar
G, or trifluorotrichloroethane, or n-hexane, or normal heptane, or dodecane.
2. a kind of polyamide composite nanometer filtering film according to claim 1 is characterized in that, the big molecule polyamine of described aliphatic is a polyvinylamine, and its chemical structural formula is as follows:
In the formula: a is the ammonia degree of separating of polyvinylamine, a=vinylamine construction unit number/(vinylamine construction unit number+acrylamide construction unit number).
3. a kind of polyamide composite nanometer filtering film according to claim 2 is characterized in that, ammonia degree of the separating a of described polyvinylamine is between 0.1-0.9; The molecular weight of described polyvinylamine is between 1000-500000.
4. a kind of polyamide composite nanometer filtering film according to claim 3 is characterized in that the molecular weight of described polyvinylamine is between 3000-100000.
5. a kind of polyamide composite nanometer filtering film according to claim 1 is characterized in that, described binary aromatic series reaction monomers is a m-phthaloyl chloride, or paraphthaloyl chloride, or 2,4-vulcabond toluene.
6. a kind of polyamide composite nanometer filtering film according to claim 1, it is characterized in that, the part by weight of the big molecule polyamine of aliphatic is 0.5-4.0wt% in the described aqueous solution, and the part by weight of binary aromatic series reaction monomers is 0.05-0.30wt% in the organic solution.
7. a kind of polyamide composite nanometer filtering film according to claim 1, the thickness that it is characterized in that described active separating layer is between 0.02-0.5 μ m.
8. a kind of polyamide composite nanometer filtering film according to claim 7, the thickness that it is characterized in that described active separating layer is between 0.05-0.3 μ m.
9. a kind of polyamide composite nanometer filtering film according to claim 1 is characterized in that described polyamide composite nanometer filtering film is a flat sheet membrane, or hollow-fibre membrane, or tubular membrane.
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Cited By (5)
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| CN102350227A (en) * | 2011-09-09 | 2012-02-15 | 杭州水处理技术研究开发中心有限公司 | Preparation method of fluorion selective nanofiltration membrane |
| CN104117296A (en) * | 2014-08-06 | 2014-10-29 | 哈尔滨工业大学 | Polyamide composite nanofiltration membrane with main chain containing ether oxygen structure, and preparation method thereof |
| CN104640619A (en) * | 2012-08-20 | 2015-05-20 | 尤尼吉可株式会社 | Porous polyamide hollow fiber membrane having very small pore diameter, and method for producing same |
| CN105617875A (en) * | 2014-11-03 | 2016-06-01 | 株洲时代新材料科技股份有限公司 | High-throughput hollow fiber composite nanofiltration membrane, and preparation method thereof |
| CN115364684A (en) * | 2022-10-25 | 2022-11-22 | 天津大学 | High-flux positively-charged nanofiltration membrane and preparation method thereof |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102350227A (en) * | 2011-09-09 | 2012-02-15 | 杭州水处理技术研究开发中心有限公司 | Preparation method of fluorion selective nanofiltration membrane |
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| CN104640619A (en) * | 2012-08-20 | 2015-05-20 | 尤尼吉可株式会社 | Porous polyamide hollow fiber membrane having very small pore diameter, and method for producing same |
| CN104640619B (en) * | 2012-08-20 | 2018-05-01 | 尤尼吉可株式会社 | Fine pore size stephanoporate polyamide hollow-fibre membrane and its manufacture method |
| CN104117296A (en) * | 2014-08-06 | 2014-10-29 | 哈尔滨工业大学 | Polyamide composite nanofiltration membrane with main chain containing ether oxygen structure, and preparation method thereof |
| CN104117296B (en) * | 2014-08-06 | 2016-08-24 | 哈尔滨工业大学 | A kind of preparation method of the main chain polyamide composite nanofiltration membrane containing ether oxide structure |
| CN105617875A (en) * | 2014-11-03 | 2016-06-01 | 株洲时代新材料科技股份有限公司 | High-throughput hollow fiber composite nanofiltration membrane, and preparation method thereof |
| CN115364684A (en) * | 2022-10-25 | 2022-11-22 | 天津大学 | High-flux positively-charged nanofiltration membrane and preparation method thereof |
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Effective date of registration: 20211103 Address after: 313100 Industrial Zone, Si an town, Changxing County, Huzhou, Zhejiang Patentee after: Zhejiang Yimo New Material Technology Co.,Ltd. Address before: 310018 Xiasha Higher Education Zone, Hangzhou, Zhejiang, Jianggan District Patentee before: ZHEJIANG SCI-TECH University |