CN1631499A - Novel compound nanometer filtering membrane of polyamide and its preparing method - Google Patents
Novel compound nanometer filtering membrane of polyamide and its preparing method Download PDFInfo
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- CN1631499A CN1631499A CN 200410068154 CN200410068154A CN1631499A CN 1631499 A CN1631499 A CN 1631499A CN 200410068154 CN200410068154 CN 200410068154 CN 200410068154 A CN200410068154 A CN 200410068154A CN 1631499 A CN1631499 A CN 1631499A
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Abstract
The invention unfurls a new kind of compounding film and its producing method. The invention use this way to produce the film, which has the good effect for water-off and salt-off rate. The invention use the high numerator material of close water and steady through the reaction at the film of many holes, then the high thin function film is made over. The invention's craft is easy, the craft condition is easy to operate, so it decrease the cost, benefiting to the large using of the high numerator compounding materials. The invention can be largely used in the liquid separating, particularly in the water solution separating, such as softening the high hard water, handling the wasted water.
Description
Technical field
The invention belongs to a kind of novel compound nanometer filtering membrane of polyamide and preparation method thereof.
Background technology
Nano filtering composite membrane 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 cutting out.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.Salt rejection rate and water flux are two important parameters estimating Nano filtering composite membrane, and salt rejection rate R is defined as: under certain operating condition, and feeding liquid salinity (c
f) with penetrating fluid in salinity (c
p) poor, again divided by the feeding liquid salinity.
Water flux is defined as: under certain operating condition, see through the volume of the water of elementary membrane area in the unit interval, its unit is l/m
2.h.
The operating condition that adopts among the present invention is: the sodium-chloride water solution of 500ppm, and the aqueous sodium persulfate solution of 500ppm, the magnesium sulfate solution of 500ppm, operating pressure are 105psi, operating temperature is 25 ℃.
Polyamide has acid amides functional group (CO-NH-), good hydrophilic property, and its mechanical stability, heat endurance and hydrolytic stability are all fine, are applicable to nanofiltration process.On the polysulfones support membrane, become the composite membrane kind of present combination property optimum by the NF membrane of the compound one deck aromatic polyamides of interfacial polycondensation ultrathin functional layer gained.
At present, a lot of Nano filtering composite membranes all adopt piperazine or derivatives thereof and polynary acyl chlorides to be prepared from the polysulfones support membrane by interfacial polymerization.As the US Patent4 in 1987 such as: Fibiger etc., it is the aqueous solution of piperazine and wetting agent that 769,148 median surface polymerizations prepare the water that NF membrane adopts, and crosslinking agent is a pyromellitic trimethylsilyl chloride.The chemical structural formula of polyamide can be expressed as in its compound ultrathin functional layer:
Lawrence etc. are at US Patent5 in 1997, and adopting interface polycondensation in 693,227 is crosslinking agent with 5-isocyanates isophthaloyl chlorine, with piperazine prepared in reaction NF membrane on the polysulfones support membrane.Hodgdon etc. adopt interface polycondensation in US Patent 5,152,901 in 1992 be crosslinking agent with pyromellitic trimethylsilyl chloride and m-phthaloyl chloride, with bridged piperazine derivatives class polyamine prepared in reaction NF membrane on the polysulfones support membrane.
Summary of the invention
The objective of the invention is to prepare a kind of novel reverse osmosis composite membrane, the composite membrane ultrathin functional layer (CO-NH-), also contains the amido formate functional group (OCO-NH-) except containing the acid amides functional group.The chemical structural formula of ultrathin functional layer aromatic polyamides can be expressed as:
X is-OCO-NH-in the formula; Y corresponds to-OH; Z is-COOH.
Involved in the present invention is a kind of novel compound nanometer filtering membrane of polyamide, is by polyamine and the compound one deck aromatic polyamides of the polynary acyl chlorides interfacial polycondensation of modified aromatic thin layer on porous support membrane.
Above-mentioned novel compound nanometer filtering membrane of polyamide, described polyamine are 1, the 4-cyclohexanediamine.
Above-mentioned novel compound nanometer filtering membrane of polyamide, described aromatic polycarboxylic acyl chlorides comprises 5-oxygen formyl chloride-isophthaloyl chlorine at least, in the m-phthaloyl chloride one.
Above-mentioned novel compound nanometer filtering membrane of polyamide, the part by weight of described polyamine and the polynary acyl chlorides of modified aromatic was from 0.1: 1 to 40: 1.
Above-mentioned novel compound nanometer filtering membrane of polyamide, described support membrane is the UDEL P3500 polysulfones with 16%, and 0.3% water and 0.1% surfactant are dissolved in N, the N-dimethylacetylamide, be coated with and scrape on polyester non-woven fabric, immerse gel in the water then and remove and obtain after desolvating; 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 method of above-mentioned novel compound nanometer filtering membrane of polyamide, be that the polysulfones support membrane directly is immersed in the polyamines solution, behind squeegee roll extrusion support membrane surface, carry out the single face interface polymerization reaction with the modified multicomponent solution of acid chloride, the interface polymerization reaction that generates polyamide active layer only carries out on polysulfones support membrane surface, composite membrane dried in the shade in air 1～3 minute, and again through heat treatment, rinsing obtains Nano filtering composite membrane.
The preparation method of above-mentioned novel compound nanometer filtering membrane of polyamide, described heat treatment is to handle 3-10 minute down at 40-70 ℃.
The preparation method of above-mentioned novel compound nanometer filtering membrane of polyamide, described rinsing comprised for two steps, and the first step is to be in 15% the aqueous solution rinsing 10-40 minute at 30-60 ℃ methyl alcohol part by weight, and second step was in 30-60 ℃ water rinsing 10-40 minute.
The preparation method of above-mentioned novel compound nanometer filtering membrane of polyamide, the used organic solvent of described modified multicomponent solution of acid chloride is a trifluorotrichloroethane, n-hexane, a kind of in the heptane.
This novel compound nanometer filtering membrane of polyamide also can be prepared into hollow-fibre membrane.
The specific embodiment
Following examples provide the explanation of nanofiltration composite membrane and their desalting performance.Yet these embodiment only provide as an illustration rather than limit the present invention.
Embodiment 1-9 is with 16% UDEL P3500 polysulfones, 0.3% water and 0.1% polyoxyethylene nonyl phenyl Acetoxon acid esters are dissolved in N, and dinethylformamide is coated with and scrapes on polyester non-woven fabric, immerse then in the water to remove and obtain the support membrane that molecular cut off is 2-3 ten thousand after desolvating, hygrometric state is preserved standby.
The polysulfones support membrane single face of hygrometric state is immersed in 2,4-cyclohexanediamine part by weight is 0.1%, in the aqueous solution of NaOH part by weight 0.25% 2 minutes, after extracting with squeegee roll extrusion support membrane surface, be that 0.1% cyclohexane solution single face contacts and carries out interface polymerization reaction 20-40 second with 5-oxygen formyl chloride-isophthaloyl chlorine part by weight.Composite membrane dried in the shade in air 2 minutes, handled 3-10 minute down through 40-70 ℃ again.Then carry out two step rinsings again: the first step is to be in 15% the aqueous solution rinsing 10-40 minute at 30-60 ℃ methyl alcohol part by weight, and second step was in 30-60 ℃ water rinsing 10-40 minute.The composite membrane of preparation is kept in the water, and at the saline solution of 500ppm, operating pressure is 105psi, and operating temperature is its desalting performance of test under 25 ℃ the condition.
Embodiment reaction time (s) salt type flux (l/m
2.h) salt rejection rate (%)
1 20 sodium chloride 41.6 59.7
2 20 sodium sulphate 40.8 92.1
3 20 magnesium sulfate 41.2 87.2
4 30 sodium chloride 39.8 62.1
5 30 sodium sulphate 37.8 92.5
6 30 magnesium sulfate 38.0 85.2
7 40 sodium chloride 38.6 65.0
8 40 sodium sulphate 39.1 93.6
9 40 magnesium sulfate 38.9 88.2
Embodiment 10-18 is as the embodiment of front, as stated above, adopt 2,4-cyclohexanediamine part by weight is 0.1%, the aqueous solution of NaOH part by weight 0.25%, 5-oxygen formyl chloride-isophthaloyl chlorine part by weight be 0.075% and m-phthaloyl chloride chlorine part by weight be that 0.025% cyclohexane solution prepares Nano filtering composite membrane.These several embodiment investigate to add the influence of m-phthaloyl chloride to film properties.
Embodiment reaction time (s) salt type flux (l/m
2.h) salt rejection rate (%)
10 20 sodium chloride 52.9 51.9
11 20 sodium sulphate 51.9 80.1
12 20 magnesium sulfate 53.4 75.8
13 30 sodium chloride 48.7 54.0
14 30 sodium sulphate 46.3 80.4
15 30 magnesium sulfate 43.6 74.0
16 40 sodium chloride 47.3 56.5
17 40 sodium sulphate 48.9 81.3
18 40 magnesium sulfate 48.6 76.6
Claims (10)
1. a novel compound nanometer filtering membrane of polyamide is characterized in that, on the porous support membrane by polyamine and the compound one deck aromatic polyamides of the polynary acyl chlorides interfacial polycondensation of modified aromatic thin layer.
2. novel compound nanometer filtering membrane of polyamide as claimed in claim 1 is characterized in that, described polyamine is 1, the 4-cyclohexanediamine.
3. novel compound nanometer filtering membrane of polyamide as claimed in claim 1 is characterized in that, described aromatic polycarboxylic acyl chlorides comprises 5-oxygen formyl chloride-isophthaloyl chlorine at least, in the m-phthaloyl chloride one.
4. novel compound nanometer filtering membrane of polyamide as claimed in claim 1 is characterized in that, the part by weight of described polyamine and the polynary acyl chlorides of modified aromatic was from 0.1: 1 to 40: 1.
5. novel compound nanometer filtering membrane of polyamide as claimed in claim 1, it is characterized in that, described support membrane is the UDEL P3500 polysulfones with 16%, 0.3% water and 0.1% surfactant are dissolved in N, N-monomethyl acetamide, be coated with and scrape on polyester non-woven fabric, immerse gel in the water then and remove and obtain after desolvating; 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.
6. the preparation method of a novel compound nanometer filtering membrane of polyamide, it is characterized in that, the polysulfones support membrane directly is immersed in the polyamines solution, behind squeegee roll extrusion support membrane surface, carry out the single face interface polymerization reaction with the modified multicomponent solution of acid chloride, the interface polymerization reaction that generates polyamide active layer only carries out on polysulfones support membrane surface, and composite membrane dried in the shade in air 1～3 minute, through heat treatment, rinsing obtains Nano filtering composite membrane again.
7. the preparation method of novel compound nanometer filtering membrane of polyamide as claimed in claim 6 is characterized in that, described heat treatment is to handle 3-10 minute down at 40-70 ℃.
8. the preparation method of novel compound nanometer filtering membrane of polyamide as claimed in claim 6, it is characterized in that, described rinsing comprised for two steps, and the first step is to be in 15% the aqueous solution rinsing 10-40 minute at 30-60 ℃ methyl alcohol part by weight, and second step was in 30-60 ℃ water rinsing 10-40 minute.
9. the preparation method of novel compound nanometer filtering membrane of polyamide as claimed in claim 6 is characterized in that, the used organic solvent of modified multicomponent solution of acid chloride is a trifluorotrichloroethane, n-hexane, a kind of in the heptane.
10. this novel compound nanometer filtering membrane of polyamide also can be prepared into hollow-fibre membrane.
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Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100402133C (en) * | 2005-11-09 | 2008-07-16 | 华东理工大学 | Preparation method of polymer hollow fiber composite nano filtering membrane |
| CN101829508A (en) * | 2010-05-11 | 2010-09-15 | 杭州水处理技术研究开发中心有限公司 | Novel polyamide nanofiltration membrane and preparation method thereof |
| CN101502763B (en) * | 2009-02-10 | 2011-06-22 | 杭州水处理技术研究开发中心有限公司 | Novel biological contamination-resistant ultrathin compound film and preparation method thereof |
| CN102120149A (en) * | 2011-01-30 | 2011-07-13 | 杭州方然滤膜技术有限公司 | Method for preparing acid-proof polysulfonamide nanofiltration composite film |
| CN102133506A (en) * | 2011-02-28 | 2011-07-27 | 浙江理工大学 | Polyamide composite nanofiltration membrane |
| CN102151499A (en) * | 2011-02-28 | 2011-08-17 | 浙江理工大学 | Polyamide composite nanofiltration membrane and preparation method thereof |
| CN102210981A (en) * | 2011-06-10 | 2011-10-12 | 南京帝膜净水材料开发有限公司 | Method for preparing polyamide reverse osmosis composite membrane |
| CN102219673A (en) * | 2011-05-06 | 2011-10-19 | 中国科学院长春应用化学研究所 | Positive charged composite nanofiltration membrane and preparation method thereof |
| CN101254419B (en) * | 2007-12-13 | 2011-12-14 | 复旦大学 | Crosslinked hyperbranched polyalcohol composite nano filter membrance and method of preparing the same |
| CN103464011A (en) * | 2013-09-21 | 2013-12-25 | 淮海工学院 | Aroma polyamide composite membrane with surface containing salicylaldehyde and quaternary ammonium salt and preparing method of aroma polyamide composite membrane |
| CN103464010A (en) * | 2013-09-21 | 2013-12-25 | 淮海工学院 | Anti-staining high-stability aromatic polyamide composite membrane and preparation method thereof |
| CN105536555A (en) * | 2010-12-21 | 2016-05-04 | 通用电气公司 | Polymeric matrices formed from monomers comprising a protected amine group |
| CN106999870A (en) * | 2016-06-30 | 2017-08-01 | 中国石油大学(华东) | The molecule of polysulfonamide nanofiltration or reverse osmosis composite membrane process for assembly preparing layer by layer |
| CN107096401A (en) * | 2016-02-23 | 2017-08-29 | 内蒙古天环境技术有限公司 | A kind of high-k Nano filtering composite membrane and preparation method thereof |
| CN109789378A (en) * | 2016-10-28 | 2019-05-21 | 日东电工株式会社 | Composite semipermeable membrane and spiral separation membrane element |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100402133C (en) * | 2005-11-09 | 2008-07-16 | 华东理工大学 | Preparation method of polymer hollow fiber composite nano filtering membrane |
| CN101254419B (en) * | 2007-12-13 | 2011-12-14 | 复旦大学 | Crosslinked hyperbranched polyalcohol composite nano filter membrance and method of preparing the same |
| CN101502763B (en) * | 2009-02-10 | 2011-06-22 | 杭州水处理技术研究开发中心有限公司 | Novel biological contamination-resistant ultrathin compound film and preparation method thereof |
| CN101829508A (en) * | 2010-05-11 | 2010-09-15 | 杭州水处理技术研究开发中心有限公司 | Novel polyamide nanofiltration membrane and preparation method thereof |
| CN105536555B (en) * | 2010-12-21 | 2019-05-07 | Bl 科技公司 | The PA membrane generated by the monomer of the amine groups containing protection through interfacial polymerization |
| CN105536555A (en) * | 2010-12-21 | 2016-05-04 | 通用电气公司 | Polymeric matrices formed from monomers comprising a protected amine group |
| CN102120149A (en) * | 2011-01-30 | 2011-07-13 | 杭州方然滤膜技术有限公司 | Method for preparing acid-proof polysulfonamide nanofiltration composite film |
| CN102120149B (en) * | 2011-01-30 | 2014-03-12 | 杭州方然滤膜技术有限公司 | Method for preparing acid-proof polysulfonamide nanofiltration composite film |
| CN102151499A (en) * | 2011-02-28 | 2011-08-17 | 浙江理工大学 | Polyamide composite nanofiltration membrane and preparation method thereof |
| CN102133506B (en) * | 2011-02-28 | 2013-01-09 | 浙江理工大学 | Polyamide composite nanofiltration membrane |
| CN102133506A (en) * | 2011-02-28 | 2011-07-27 | 浙江理工大学 | Polyamide composite nanofiltration membrane |
| CN102219673A (en) * | 2011-05-06 | 2011-10-19 | 中国科学院长春应用化学研究所 | Positive charged composite nanofiltration membrane and preparation method thereof |
| CN102210981A (en) * | 2011-06-10 | 2011-10-12 | 南京帝膜净水材料开发有限公司 | Method for preparing polyamide reverse osmosis composite membrane |
| CN103464010A (en) * | 2013-09-21 | 2013-12-25 | 淮海工学院 | Anti-staining high-stability aromatic polyamide composite membrane and preparation method thereof |
| CN103464010B (en) * | 2013-09-21 | 2015-04-15 | 淮海工学院 | Anti-staining high-stability aromatic polyamide composite membrane and preparation method thereof |
| CN103464011B (en) * | 2013-09-21 | 2015-04-15 | 淮海工学院 | Aroma polyamide composite membrane with surface containing salicylaldehyde and quaternary ammonium salt and preparing method of aroma polyamide composite membrane |
| CN103464011A (en) * | 2013-09-21 | 2013-12-25 | 淮海工学院 | Aroma polyamide composite membrane with surface containing salicylaldehyde and quaternary ammonium salt and preparing method of aroma polyamide composite membrane |
| CN107096401A (en) * | 2016-02-23 | 2017-08-29 | 内蒙古天环境技术有限公司 | A kind of high-k Nano filtering composite membrane and preparation method thereof |
| CN107096401B (en) * | 2016-02-23 | 2021-11-26 | 内蒙古天一环境技术有限公司 | High-dielectric-constant nanofiltration composite membrane and preparation method thereof |
| CN106999870A (en) * | 2016-06-30 | 2017-08-01 | 中国石油大学(华东) | The molecule of polysulfonamide nanofiltration or reverse osmosis composite membrane process for assembly preparing layer by layer |
| CN109789378A (en) * | 2016-10-28 | 2019-05-21 | 日东电工株式会社 | Composite semipermeable membrane and spiral separation membrane element |
| US11207645B2 (en) | 2016-10-28 | 2021-12-28 | Nitto Denko Corporation | Composite semipermeable membrane and spiral wound separation membrane element |
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