CN100395010C - Polyamide reverse osmose membrane and production thereof - Google Patents
Polyamide reverse osmose membrane and production thereof Download PDFInfo
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- CN100395010C CN100395010C CNB2006100233149A CN200610023314A CN100395010C CN 100395010 C CN100395010 C CN 100395010C CN B2006100233149 A CNB2006100233149 A CN B2006100233149A CN 200610023314 A CN200610023314 A CN 200610023314A CN 100395010 C CN100395010 C CN 100395010C
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Abstract
The present invention provides a method for preparing a polyamide reverse osmosis membrane with a special selective separation property, which comprises the steps that a water solution of lentine and 2, 4-diamino benzenesulfonic acid is provided, and the weight ratio of the lentine to the 2, 4-diamino benzenesulfonic acid is 3: 1 to 10: 1; a porous carrier is dipped in the water solution, and a fluid layer is formed on the porous carrier; the single face of the dipped porous carrier with the fluid layer is in contact with organic phase solution with the weight ratio of isophthaloyl dichloride to 1, 3, 5-benzenetricarbonyl chloride of 1: 3 to 1: 10 to carry out an interfacial polymerization reaction. The present invention also provides a reverse osmosis membrane prepared by the method. When the improved polyamide reverse osmosis membrane is used for treating salt water with the NaCl concentration of 50 to 250 g/L, the SO4 <2-> concentration of 5 to 60 g/L and the pH value of 7 to 11 under the operation pressure of 300 to 370 psi and at the temperature of 28 to 32 DEG C, the NaCl removing rate is lower than 8%, and the SO4 <2-> removing rate is higher than 95%. When the improved polyamide reverse osmosis membrane is used for treating NaCl solution with the NaCl concentration of 250 to 2000 mg/L and the pH of 6 to 10 under the operation pressure of 150 to 300 psi and at the temperature of 25 to 32 DEG C, the NaCl removing rate is from 90% to 94%.
Description
Technical field
The present invention relates to the interface synthetic have special selection polyamide reverse osmose membrane separatory and preparation method thereof.
Technical background
People's selective membrane commonly used comes purifying to form the various solution different, that concentration is different, for example adopts NF membrane and reverse osmosis membrane.NF membrane claims loose reverse osmosis membrane again.During nanofiltration membrane treatment different valence state ion solution, because south, road (DONNAN) effect makes NF membrane to the selectivity difference of different ions, thereby different ions is also inequality by the ratio of NF membrane, thereby reaches the purpose that different ions is separated.
But for example handling, NaCl concentration is 50-250g/L, SO
4 2-When concentration was the mixed salt of 5-60g/L, owing to south, the road effect that electric charge produced in the salt solution can't play a major role to Selective Separation, and the pore size of described NF membrane played a major role to Selective Separation.High ion concentration salt solution causes the nanofiltration fenestra to amplify again, and clearance is descended.Therefore general NF membrane is not suitable for the mixed salt that separation has described concentration range.
Reverse osmosis membrane often is applied to resisting the reverse osmosis process of solution self osmotic pressure, and the concentration of its feed brine or seawater is high more, and the reverse osmotic pressure that reverse osmosis membrane must overcome is big more.Reverse osmosis membrane now commonly used is a polyamide reverse osmose membrane, the composite membrane that described reverse osmosis membrane is made up of porous carrier and one deck PA membrane of forming thereon.A main application of reverse osmosis membrane is to be used for processing such as salt solution, seawater, by salt solution or seawater is mandatory through reverse osmosis membrane, filter out the NaCl in salt solution or the seawater or be dissolved in wherein other ion or molecule, thereby reach the purpose of purifying.
But under the operating condition of routine, existing polyamide reverse osmose membrane is 50-250g/L handling NaCl concentration, SO
4 2-When concentration is the salt solution of 5-60g/L, it takes off NaCl and leads greater than 8%, because the osmotic pressure of the mixed salt in the described concentration range is high, so it is minimum that general reverse osmosis membrane is applied in the described mixed salt water yield, the more important thing is, because the Selective Separation characteristic of general reverse osmosis membrane is relatively poor, makes and take off SO
4 2-Rate is low excessively, therefore can't satisfy the needs that are applied to the mixed salt in the described concentration range.Simultaneously, see through contained NaCl and SO in the salt solution of reverse osmosis membrane
4 2-The flow of amount and the salt solution that sees through reverse osmosis membrane very big relation is arranged.
In order to improve the above-mentioned defective of existing reverse osmosis membrane, people attempt to seek the whole bag of tricks and prepare the polyamide reverse osmose membrane with good salt rejection rate.These methods relate to adds various additives or optimizes prior preparation method in the reactant liquor of interfacial polymerization.
US 4,983,291 disclose a kind of on porous carrier the method for interface synthesizing polyamides reverse osmosis membrane, it comprises the steps: it at first is that porous carrier is immersed in the polyamines aqueous solution, and the described as required polyamines aqueous solution also can comprise and the nonreactive polar aprotic solvent of polyamines, polyol or acid acceptor; The unnecessary polyamines aqueous solution on the porous carrier surface of removal through soaking; Subsequently this porous carrier is immersed in the organic solution of many acid chlorides and reacts, form PA membrane with polymerization on described porous carrier; At last the PA membrane that obtains is handled drying with amine salt, amino acid, sulfuric acid, polyacid or the organic acid of hydroxypolycarboxylic acid, acid.
But still there is defective in concentration of treatment in the polyamide reverse osmose membrane after the above-mentioned improvement aspect higher solution, in order further to improve the selection desalination of polyamide reverse osmose membrane, CN 90103937.3 provides a kind of method that improves polyamide reverse osmose membrane salt transmitance, this method comprises with aqueous alkaline metal permanganate solution soaks polyamide reverse osmose membrane, handles once more through the reverse osmosis membrane that soaked above-mentioned with sodium sulfite or hydrogenperoxide steam generator subsequently.Though the salt rejection rate through the reverse osmosis membrane after this method processing improves to some extent, and is still abundant inadequately, under the 300psi operating pressure, under 25-32 ℃, handling NaCl concentration is 50-250g/L, SO
4 2-Concentration is 5-60g/L, when pH is the mixed salt of 7-11, can not reaches and take off NaCl and lead less than 8%, takes off SO
4 2-Rate is greater than 95%.
Therefore, this area still needs to develop reverse osmosis membrane that has particular characteristic and preparation method thereof.
Summary of the invention
The purpose of this invention is to provide reverse osmosis membrane that has particular characteristic and preparation method thereof.
Therefore, the invention provides the preparation method of polyamide reverse osmose membrane, it comprises the steps:
(a) provide m-phenylene diamine (MPD) and 2, the aqueous solution of 4-diamino benzene sulfonic acid, described m-phenylene diamine (MPD) and 2, the weight ratio of 4-diamino benzene sulfonic acid is 3: 1-10: 1;
(b) with described aqueous solution dipping porous carrier, on described porous carrier, form liquid level;
(c) make through the dipping the carrying liqs layer porous carrier with comprise that weight ratio is 1: 3-1: the organic facies single face of 10 m-phthaloyl chloride and pyromellitic trimethylsilyl chloride contacts, and carries out interface polymerization reaction.
The present invention also provides a kind of polyamide reverse osmose membrane, and it comprises porous carrier and the PA membrane of interfacial polymerization on this porous carrier, and described reverse osmosis membrane makes with the following method:
(a) provide m-phenylene diamine (MPD) and 2, the aqueous solution of 4-diamino benzene sulfonic acid, described m-phenylene diamine (MPD) and 2, the weight ratio of 4-diamino benzene sulfonic acid is 3: 1-10: 1;
(b) with described aqueous solution dipping porous carrier, on described porous carrier, form liquid level;
(c) make through the dipping the carrying liqs layer porous carrier with comprise that weight ratio is 1: 3-1: the organic facies single face of 10 m-phthaloyl chloride and pyromellitic trimethylsilyl chloride contacts, and carries out interface polymerization reaction.
The specific embodiment is as follows: the preparation method of polyamide reverse osmose membrane of the present invention comprises provides m-phenylene diamine (MPD) and 2, the step of the aqueous solution of 4-diamino benzene sulfonic acid, described m-phenylene diamine (MPD) and 2, the weight ratio of 4-diamino benzene sulfonic acid is 3: 1-10: 1, be preferably 4: 1-8: 1, more preferably 5: 1.
In embodiments of the present invention, the described m-phenylene diamine (MPD) of aqueous phase and described 2, the concentration sum of 4-diamino benzene sulfonic acid is a 1.0-2.4% weight, is preferably 1.3-2.0% weight.
Be used to prepare described m-phenylene diamine (MPD) and 2, the method for the aqueous solution of 4-diamino benzene sulfonic acid is without particular limitation, and it can be the conventional method of this area.For example, can be so that order to be with m-phenylene diamine (MPD) and 2 arbitrarily, the 4-diamino benzene sulfonic acid is dissolved in and forms the described aqueous solution in the deionized water.
The inventive method also comprises the step with described aqueous solution dipping porous carrier, thereby forms liquid level on described porous carrier.
Porous carrier of the present invention has enough big aperture allows permeate substance, molecule or ion pass through, but the aperture of described porous carrier is not more than the aperture of formed on described porous carrier " bridge formation ".The aperture of described porous carrier is generally less than 0.05 μ m.
The used porous carrier of the present invention is made by polymeric material, and described polymeric material is optional from polysulfones, polyether sulfone, polyimides, polyamide, polypropylene and various halogen polymer.Preferably among the embodiment, described porous carrier is the polysulfones porous carrier in the present invention.
The thickness of described porous carrier can be this area thickness commonly used.In the better embodiment of the present invention, the thickness of the porous carrier that is adopted is 20-60 μ m, is preferably 30-40 μ m.Described porous carrier also can support described porous carrier by nonwoven.
The inventive method also comprise make through the dipping the carrying liqs layer porous carrier with comprise that weight ratio is 1: 3-1: the organic phase solution single face of 10 m-phthaloyl chloride and pyromellitic trimethylsilyl chloride contacts, and carries out the step of interface polymerization reaction.
The organic facies that is applicable to the inventive method comprises that weight ratio is 1: 3-1: 10, be preferably 1: 4-1: and 8, more preferably 1: 5 m-phthaloyl chloride and pyromellitic trimethylsilyl chloride.
Described porous carrier forms liquid level in described aqueous phase solution after, can remove unnecessary aqueous phase solution on the porous carrier of dipping earlier, contact the material polymerization reaction take place in described liquid level and the organic facies again with the organic phase solution single face.
The method that is used to form organic facies is without particular limitation, and they can be the conventional methods of this area.In the better embodiment of the present invention, can m-phthaloyl chloride and pyromellitic trimethylsilyl chloride be added organic solvent with order arbitrarily and form organic facies.
Can remove unnecessary aqueous phase solution on the porous carrier of dipping earlier, contact polymerization reaction take place with the organic phase solution single face more afterwards.
The organic solvent that is used to form described organic phase solution can be an organic solvent arbitrarily, as long as it does not disturb the interfacial polymerization that takes place subsequently.The non-limiting example of appropriate organic solvent has, for example acyclic fat alkane (n-hexane, isooctane etc.), cycloalkane, aromatic hydrocarbon.
Be used to make the porous carrier through dipping without particular limitation with the method that the organic phase solution single face contacts, it can be the conventional method of this area.Described single face contact is meant that any one side of described porous carrier contacts with organic phase solution.
Method of the present invention is carried out at normal temperatures and pressures.
The polyamide reverse osmose membrane that the inventive method forms is made by PA membrane and porous carrier, described PA membrane is to be 3: 1 to 10: 1 m-phenylene diamine (MPD) and 2 by containing weight ratio, the water of 4-diamino benzene sulfonic acid and to contain weight ratio be that the organic facies of 1: 3 to 1: 10 m-phthaloyl chloride and pyromellitic trimethylsilyl chloride is carried out interfacial polymerization and obtained.
In the better embodiment of the present invention, described m-phenylene diamine (MPD) and described 2, the 4-diamino benzene sulfonic acid is a 1.0-3.5% weight in the total concentration of aqueous phase, and described m-phthaloyl chloride and the total concentration of described pyromellitic trimethylsilyl chloride in organic solvent are 0.05-0.25% weight.
The reverse osmosis membrane for preparing with the inventive method under 28-32 ℃, handles that to contain NaCl concentration be 50-250g/L, SO under the 300-370psi operating pressure
4 2-Concentration is 5-60g/L, when pH is the salt solution of 7-11, reaches and takes off NaCl and lead less than 8%, takes off SO
4 2-Rate is greater than 95%.Under the 150-300psi operating pressure, under 25-32 ℃, handling NaCl concentration is 250-2000mg/L, and pH is the NaCl solution of 6-10, and it takes off that NaCl leads is 90-94%.
Method technology of the present invention is simple, easy to operate.Described reverse osmosis membrane performance is good and stable, can be repeatedly used, and the raw material sources that adopted are extensive, and the scope of application is wide, is convenient to enterprise and reduces production costs.
Further specify the present invention below in conjunction with embodiment.
Specific embodiment
For convenience, in following embodiment table, abbreviate m-phenylene diamine (MPD) as MPD, 2, the 4-diamino benzene sulfonic acid abbreviates MPDSA as, and m-phthaloyl chloride abbreviates IPC as, and all benzene trimethyl acyl chlorides abbreviates TMC as, the concentration of organic phase solution abbreviates OC% as, and the concentration of aqueous phase solution is HC%.SO in the embodiment table
4 2-Derive from Na
2SO
4
Embodiment 1
At room temperature, to comprise the liner adhesive-bonded fabric, thickness is that the polysulfones porous carrier of 0.04 μ m is completely infused in and contains m-phenylene diamine (MPD) and 2, the ratio of 4-diamino benzene sulfonic acid is in the aqueous phase solution of 5: 1 (weight), described m-phenylene diamine (MPD) and described 2, the total concentration of 4-diamino benzene sulfonic acid sum in aqueous phase solution is 2.4% weight, after forming liquid level on the described porous carrier, remove aqueous phase solution unnecessary on the described porous carrier, the porous carrier single face that will contain liquid level again is that the hexane solution single face of 1: 5 (weight) contacts with containing m-phthaloyl chloride and the ratio of pyromellitic trimethylsilyl chloride, carry out interface polymerization reaction, described m-phthaloyl chloride and the pyromellitic trimethylsilyl chloride sum total concentration in organic phase solution is 0.15% weight, remove organic phase solution unnecessary on the described porous carrier afterwards, at last that the reverse osmosis membrane that generates is first following dry 5 minutes at 90 ℃, afterwards again 110 ℃ of following vacuum drying 5 minutes, relax rinsing with deionized water behind the cool to room temperature, be placed on its performance of test on the dull and stereotyped test machine afterwards, with NaCl concentration is 750mg/L, the pH value is that 8.0 salt solution is under 225psi pressure, under 28 ℃, by described reverse osmosis membrane, it takes off that NaCl leads is 92.4%; Under 325psi pressure, under 28 ℃, handling NaCl concentration is 200g/L, Na
2SO
4Middle SO
4 2-The concentration of ion is 20g/L, and the pH value is 9.0 mixed salt, and it takes off that NaCl leads is 1.1%, takes off SO
4 2-Rate is 95.5%.
Embodiment 2-13
Among the embodiment 2-13, change m-phenylene diamine (MPD) and 2 in the aqueous phase solution, proportionate relationship between the 4-diamino benzene sulfonic acid, the concentration of aqueous phase solution, proportionate relationship in the organic phase solution between m-phthaloyl chloride and the pyromellitic trimethylsilyl chloride, the concentration of organic phase solution, the operating condition of the performance of the reverse osmosis membrane that the composition of processed saline solution, pH value of solution value and evaluation prepare; The porous carrier that is adopted among the embodiment 4 is for comprising the liner adhesive-bonded fabric, and thickness is the polyamide porous carrier of 0.03 μ m.The porous carrier that is adopted among the embodiment 12 is for comprising the liner adhesive-bonded fabric, and thickness is the polyamide porous carrier of 0.03 μ m; The porous carrier that is adopted among the embodiment 13 is for comprising the liner adhesive-bonded fabric, and thickness is the polypropylene porous carrier of 0.04 μ m, the results are shown in following table.
From table among the embodiment as seen, the polyamide reverse osmose membrane that the present invention prepares under the 300-370psi operating pressure, under 28-32 ℃, is 50-250g/L with NaCl concentration, SO
4 2-Concentration is 5-60g/L, and pH is that the mixed salt of 7-11 is estimated its performance, takes off NaCl and leads less than 8%, takes off SO
4 2-Rate is greater than 95%; Under the 150-300psi operating pressure, under 25-32 ℃, handling NaCl concentration is the low concentration of salt aqueous solution of 250-2000mg/L, and it takes off that NaCl leads is 90-94%.
As seen from the table, owing to m-phenylene diamine (MPD) and 2, the weight ratio of 4-diamino benzene sulfonic acid is 2: 1 among the embodiment 2 and 3; Weight ratio owing to m-phthaloyl chloride and equal benzene trimethyl acyl chlorides among the embodiment 5 and 6 is 1: 11; Because m-phenylene diamine (MPD) and 2, the weight ratio between the 4-diamino benzene sulfonic acid is 11: 1 among the embodiment 9, not within technical scheme provided by the present invention, so when salt solution was estimated its performance described in the employing table, its result did not reach requirement of the present invention.
The technical term that is adopted in the foregoing description only be used for illustrating of the present invention; the present invention is not done any restriction; those skilled in the art is on the basis of the technical scheme that provides of the present invention; any modification or the change made by logic analysis, reasoning or limited test; be conspicuous, be included within protection scope of the present invention.
Claims (11)
1. the preparation method of a polyamide reverse osmose membrane, it comprises the steps:
(a) provide m-phenylene diamine (MPD) and 2, the aqueous solution of 4-diamino benzene sulfonic acid, described m-phenylene diamine (MPD) and 2, the weight ratio of 4-diamino benzene sulfonic acid is 3: 1-10: 1;
(b) with described aqueous solution dipping porous carrier, on described porous carrier, form liquid level;
(c) make through the dipping the carrying liqs layer porous carrier with comprise that weight ratio is 1: 3-1: the organic phase solution single face of 10 m-phthaloyl chloride and pyromellitic trimethylsilyl chloride contacts, and carries out interface polymerization reaction.
2. the method for claim 1 is characterized in that described m-phenylene diamine (MPD) and 2, and the weight ratio of 4-diamino benzene sulfonic acid is 4: 1-8: 1.
3. method as claimed in claim 2 is characterized in that described m-phenylene diamine (MPD) and 2, and the weight ratio of 4-diamino benzene sulfonic acid is 5: 1.
4. as each described method among the claim 1-3, it is characterized in that m-phenylene diamine (MPD) described in the aqueous solution and 2, the concentration sum of 4-diamino benzene sulfonic acid is a 1.0-2.4% weight.
5. method as claimed in claim 4 is characterized in that m-phenylene diamine (MPD) described in the aqueous solution and described 2, and the concentration sum of 4-diamino benzene sulfonic acid is a 1.3-2.0% weight.
6. as each described method among the claim 1-3, it is characterized in that described porous carrier made by polymeric material, described polymeric material is optional from polysulfones, polyether sulfone, polyimides, polyamide, polypropylene and halogen polymer.
7. method as claimed in claim 6 is characterized in that described porous carrier is the polysulfones porous carrier.
8. as each described method among the claim 1-3, the weight ratio that it is characterized in that described m-phthaloyl chloride and pyromellitic trimethylsilyl chloride is 1: 4-1: 8.
9. method as claimed in claim 8, the weight ratio that it is characterized in that described m-phthaloyl chloride and pyromellitic trimethylsilyl chloride is 1: 5.
10. as each described method among the claim 1-3, the aperture that it is characterized in that described porous carrier is less than 0.05 μ m.
11. the polyamide reverse osmose membrane that the described method of claim 1 makes.
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Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100478056C (en) * | 2006-08-25 | 2009-04-15 | 贵阳时代汇通膜科技有限公司 | Oxidation resistant compound reverse osmosis membrane |
| KR100905901B1 (en) * | 2006-09-07 | 2009-07-02 | 웅진코웨이주식회사 | Amine aqueous solution for forming an active layer of polyamide reverse osmosis composite membrane, polyamide reverse osmosis composite membrane prepared thereby, and preparation method thereof |
| CN110508154A (en) * | 2018-05-22 | 2019-11-29 | 中国石油化工股份有限公司 | Nanofiltration membrane and its preparation method and application |
| CN110508162A (en) * | 2018-05-22 | 2019-11-29 | 中国石油化工股份有限公司 | Reverse osmosis membrane and its preparation method and application |
| CN109046025B (en) * | 2018-08-24 | 2020-11-20 | 清华大学 | Nanofiltration membrane for selectively separating trace organic matters and calcium and magnesium ions and preparation method thereof |
| CN110339724B (en) * | 2019-06-26 | 2021-08-03 | 四川大学 | Composite polyamide membrane with salt concentration responsiveness and preparation method and application thereof |
| CN110433666A (en) * | 2019-09-02 | 2019-11-12 | 天津大学 | Antipollution ant-scaling polyamide composite film, raw material, preparation method and application |
| CN110433667B (en) * | 2019-09-02 | 2022-03-22 | 天津大学 | Anti-pollution anti-scaling separation membrane and preparation method thereof |
| CN112892249A (en) * | 2019-12-04 | 2021-06-04 | 时代沃顿科技有限公司 | Polyamide reverse osmosis membrane and preparation method thereof |
| CN111359456B (en) * | 2020-04-13 | 2021-04-23 | 北京化工大学 | Linear-crosslinked multi-component copolymerized polyamide reverse osmosis membrane for seawater desalination and preparation method thereof |
| CN113244794B (en) * | 2021-05-11 | 2022-04-19 | 燕山大学 | Preparation method of nanofiltration membrane for intercepting nitrate and resource utilization of concentrated solution |
| CN113981559B (en) * | 2021-10-26 | 2023-06-23 | 泰和新材集团股份有限公司 | Degradable aromatic polyamide fiber and preparation method thereof |
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| US6368507B1 (en) * | 1998-10-14 | 2002-04-09 | Saekan Industries Incorporation | Composite polyamide reverse osmosis membrane and method of producing the same |
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| US6368507B1 (en) * | 1998-10-14 | 2002-04-09 | Saekan Industries Incorporation | Composite polyamide reverse osmosis membrane and method of producing the same |
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Effective date of registration: 20220907 Address after: No. 475-1, Hope Road, Malu Town, Jiading District, Shanghai, 201801 Patentee after: KAIMO SPECIAL SEPARATION TECHNOLOGY SHANGHAI Co.,Ltd. Address before: 200233 Shanghai City, Yishan Road No. 888 (Leucaena building) room 902 Patentee before: KAIMO FILTRATION TECHNOLOGY SH |