CN1872400A - Method for preparing Nano filtering composite membrane of hollow fiber - Google Patents
Method for preparing Nano filtering composite membrane of hollow fiber Download PDFInfo
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- CN1872400A CN1872400A CN 200510013569 CN200510013569A CN1872400A CN 1872400 A CN1872400 A CN 1872400A CN 200510013569 CN200510013569 CN 200510013569 CN 200510013569 A CN200510013569 A CN 200510013569A CN 1872400 A CN1872400 A CN 1872400A
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Abstract
A process for preparing the nano-filtering composite hollow fiber membrane includes such steps as providing an ultrafiltering (or micron-filtering) hollow fiber membrane, immersing it in the aqueous solution of polymer, and interface polymerizing reaction between the polymer and the cross-linking agent in organic phase to generate a water-insoluble cross-linked barrier layers on its both surface, resulting in a positively charged nano-filtering composite membrane.
Description
Technical field
The present invention relates to-preparation method of kind of diffusion barrier, particularly-preparation method of kind of lotus positive electricity doughnut Nano filtering composite membrane.
Background technology
The filmogen of NF membrane is identical with the reverse osmosis membrane material basically.The membrane material of commercialization NF membrane mainly contains following several: cellulose acetate (CA), SPSF (SPS), sulfonated polyether sulfone (SPES), polyamide (PA) and polyvinyl alcohol (PVA) etc.The NF membrane also commercialization at present of inorganic material preparation.
The preparation technology of NF membrane roughly has following several: phase inversion method, weak solution coating, interfacial polymerization, thermal induction phase inversion, chemic modified method etc., wherein interfacial polymerization is to prepare the most frequently used method of NF membrane.The inorganic material NF membrane generally adopts the sol-gel processing preparation.
NF membrane has 2 characteristics: 1) to the separating property of different organic constituentses, molecular weight is held back (MWCO) scope and is about 200-2000; 2) the film surface charge to the Donnan current potential of different electric charges and like charges, different valence state ion not-sample.The special performance of NF membrane has determined its range of application, is applicable to the separating substances under following several situation: 1) less demanding or do not require to the rejection of monovalention; 2) require to carry out the separation of different valence state ion; 3) less demanding or do not require to the rejection of low-molecular-weight organic matter; 4) need separate with low-molecular-weight organic matter high-molecular-weight organic material.5) predetermined substance is as dyestuff etc., and certain environmental conditions is as separation under the conditions such as temperature, pH value, purification and concentrate etc.
Mostly be the rolling assembly in the nanofiltration membrane component of commercial usefulness greatly, S-NF-70-400, NF270-400, the NF400 of the nanofiltration membrane component Film Tec that adopts tubular type and doughnut formula etc. are also arranged in addition, the ESNAI-4040 of Hydranautics etc., the ESNAl of Hydranautics etc., the SV-320 of Toray etc., the 8040-TS-40-TSA of Trisep etc., the DL8040F of Desal etc., the CA-NF-4040 of the NTR-7410 of Nitto and Hangzhou water treatment centers is a rolled film, and the HNF-130 of Hangzhou water treatment centers is a hollow fiber nanofiltration membrane.At present, the most bear electricity of commercial NF membrane, the NF membrane of lotus positive electricity is a lotus positive electricity as: the UTC-20 of Toray company seldom.
Positively charged membrane can be applicable to the dyestuff desalination of desalinization, heavy metal wastewater thereby, lotus positive electricity and textile waste is handled, compound sugar recoverys of sugar industry, spent lye reuse, different isoelectric point (lsoelectric point, IEP) amino acid whose separation, polypeptide and antibiotic purifying and concentrated, treatment of Organic Wastewater or the like.
Summary of the invention
The objective of the invention is to propose a kind of preparation method of doughnut Nano filtering composite membrane, with hollow fiber ultrafiltration membrane or micro-filtration membrane is basement membrane, behind the aqueous phase solution of the inner surface of basement membrane or outer surface dip-coating composition polymer, the poly-reaction in interface takes place in the bifunctional crosslinking agent in polymer and the organic facies, inner surface or outer surface at basement membrane form water-fast crosslinked barrier layer, thereby prepare the Nano filtering composite membrane of the lotus positive electricity of interior pressure or external pressure.
The present invention relates to a kind of preparation method of doughnut composite nanometer filtering film, with hollow fiber ultrafiltration membrane or micro-filtration membrane is basement membrane, at the surface of basement membrane coating composite material, interface polymerization reaction takes place with the bifunctional crosslinking agent, inner surface or outer surface at basement membrane form water-fast crosslinked barrier layer, and wherein composite material is poly-C
1-C
XThe C that replaces
3-C
YOlefin(e) acid N, N-two C
1-C
ZAmino C
2-C
2ZEster, X≤3, Y≤10, Z≤4 are added with additive sodium acid carbonate or sodium carbonate in the aqueous solution of composite material, and crosslinking agent is two alkylating reagents.
In the preparation method of doughnut composite nanometer filtering film, the water that will contain the composite bed polymer is coated on the basement membrane, dries in the shade under the room temperature, adds the oil phase that contains crosslinking agent then, makes composite membrane after the reaction.
The concentration of composite bed polymer is 1wt%-4wt%, and based on the total concentration of polymer solution, the concentration of additive sodium acid carbonate or sodium carbonate is 0.01-0.2M, and the concentration of crosslinking agent is 0.05-1M.
Description of drawings
Fig. 1 is the interior coating device schematic diagram of press mold in the doughnut;
Fig. 2 is the schematic diagram of interior pressure, external pressure hollow fiber nanofiltration membrane assembly.
Description of reference numerals:
1.PDMAEMA the aqueous solution or pure water 2. Pressure gauges 3. batch cans
4. peristaltic pump 5. hollow fiber film assemblies
The specific embodiment
The hollow fiber nanofiltration membrane lotus positive electricity that the present invention is prepared, this film has higher rejection to divalent salts, and is less to the rejection of monovalent salt.
The used method of the present invention is a composite algorithm, used reaction is interfacial polymerization, used basement membrane is a doughnut, and method of the present invention is that the water that will contain polymer is coated on the basement membrane, approximately after 5-30 minute, excessive solution is toppled over away, dry in the shade under the room temperature, add the oil phase of crosslinking agent then, reaction 1-5hr, the concrete reaction time is decided by the required concrete condition of reaction, thereby makes composite membrane.Polyelectrolyte solution concentrating in absorption of the surface of micropore basal membrane and dry process can cause the inhomogeneities of local concentration to influence the stretching, extension of strand owing to the particularity on surface, the pore size of the cubic network that forms after the generation cross-linking reaction, skewness, thereby the qualification rate of the composite membrane that influence makes, qualification rate is generally: 50-75%, so in being used as the polymer solution of composite bed, add suitable additive, additive is kept as the form of the polymer of the compound barrier layer of preparation even, stable, thereby obtain the composite membrane of high qualification rate, qualification rate is: 90-99%.
Skin-material of the present invention is that composite material is a kind of gel, is polymethylacrylic acid nitrogen base ester class, and general formula is: poly-C
1-C
XThe C that replaces
3-C
YOlefin(e) acid N, N-two C
1-C
ZAmino C
2-C
2ZEster (X≤3, Y≤10, Z≤4) wherein is preferably polymethylacrylic acid N, the N-dimethylaminoethyl.Removing of solvent used the aqueous solution of composite bed polymer usually for convenience.
The basement membrane of composite membrane is existing Hollow Fiber Ultrafiltration or micro-filtration membrane product (polysulfones, Kynoar etc.), can be that molecular cut off is polysulfones, the Kynoar hollow-fibre membrane of 6000-20000.Wherein, the doughnut external diameter of the usefulness of filming outward is 0.15-0.20mm, in be coated with usefulness the doughnut external diameter be 0.25-0.3mm.
Crosslinking agent is two alkylating reagents, as to benzyl dichloride, 1,4 dibromobutane etc., wherein is preferably benzyl dichloride, and the solvent of crosslinking agent is an alkane, as normal heptane, n-hexane etc.The amino of composite bed polymer respectively with two haloalkyl generation quaterisations of crosslinking agent, thereby make crosslinked polymer, and close attachment forms composite membrane on the surface of basement membrane.
Wherein in coating solution, add additive sodium acid carbonate, sodium carbonate etc., play the effects such as configuration of composite bed polymer in the stable preparation process, wherein be preferably sodium acid carbonate.
Concrete operations are: at room temperature, the aqueous solution that has the polymer of additive in the inner surface or the outer surface dip-coating of existing ultrafiltration hollow-fibre membrane (polysulfones, Kynoar), be preferably the polymethylacrylic acid N that is added with sodium acid carbonate, the N-dimethylaminoethyl aqueous solution, polymethylacrylic acid N wherein, the concentration of N-dimethylaminoethyl is: 1wt%-4wt% is a benchmark with the gross weight of solution, and the concentration of sodium acid carbonate is: 0.01-0.2M.After the air part omitted is dried in the air, immerse and carry out the poly-reaction in interface in the certain density cross-linking agent solution, the concentration of crosslinking agent is 0.05-1M, crosslinking time is 1-5hr, takes out the back and cleans with normal heptane, promptly makes Nano filtering composite membrane.
Since the functional layer of product with season amino be crosslinking points, it is the NF membrane of lotus positive electricity that unreacted uncle's amino makes product.
With polymethylacrylic acid N, N-dimethylaminoethyl (PDMAEMA) is effect of the present invention for example further specifies, because PDMAEMA belongs to polyelectrolyte, its aqueous solution shows electropositive, after the dip-coating, in the process that membrane surface is dried in the shade, can be because the configuration of the Different Effects polymer of concentration, and influence cross-linking reaction subsequently, causing prepared cross-linking products network density degree difference, the qualification rate of NF membrane is lower.The present invention adds the additive sodium acid carbonate in PDMAEMA solution, stablized the configuration of polymer, has increased the qualification rate of composite membrane.
The chemical products hollow-fibre membrane that this product is used, composite bed polymer, crosslinking agent can commercially obtain, and wherein basement membrane and composite bed polymer also can make by common method, for example polymethylacrylic acid N, the N-dimethylaminoethyl, can make by polymerisation in bulk, polymerization single polymerization monomer is methacrylic acid N, N-dimethylaminoethyl (chemicals Co., Ltd of Wuxi Sunyu, purity: 99.5%), adopt the method for decompression distillation refining, condition: 62 ℃, 1.04MPa; Initator is an azodiisobutyronitrile; Polymerization temperature is 50 ℃; Polymerization time is a week.
The doughnut Nano filtering composite membrane of the present invention's preparation is 45%-56% to the rejection of 0.5g/LNaCl, to 1g/LMgSO
4Rejection be 80%-98%.It can be used for separating of polyvalent cation and monovalent salt, also can be used for containing the wastewater treatment of high price isotopic ion.Simultaneously, the hollow fiber nanofiltration membrane of the present invention preparation has very high rejection to the dyestuff of lotus positive electricity, can be used for lotus positive electricity dyestuff desalination, concentrate and wastewater treatment.Be that the rejection of rhodamine-B of 497.2 is 70%-96% for example to molecular weight.
Concrete situation is, with diameter is that the outer press mold (film sky, Tianjin film engineering Co., Ltd) of polysulfones, Kynoar doughnut of 0.15-0.20mm is used the pure water rinsing, slightly dry in the air under the room temperature, (contain NaHCO in the solution at the PDMAEMA aqueous solution of its outer surface dip-coating 1wt%-4wt%
3Concentration be 0.01-0.2M), gross weight with polymer is a benchmark, immerse in the n-heptane solution of 0.05-1M to benzyl dichloride behind the 5min-30min under the room temperature and react 0.5-5hr, after product is washed with normal heptane, at glycerine water solution (glycerine: the assembly of making 25cm after soaking water=1: 2～4), it is standby to put into pure water, and measuring the NF membrane product percent of pass is 90%-98%, does not add NaHCO
3The time, product percent of pass is 50%-70%.It is that the rejection of rhodamine-B of 497.2 is 70-86% that the film that makes is used for molecular weight.
Be press mold in the polysulfones, Kynoar doughnut of 0.25-0.3mm with diameter, make the assembly of 30cm length, after the pure water rinsing, utilize following device (Fig. 1) to clean the film inner chamber with pure water once more.Then, the PDMAEMA aqueous solution that adds 1wt%-4wt% in the batch can of this device (contains NaHCO in the solution
3Concentration be 0.01-0.2M), with the flow velocity circulation 5-10min of 10-35ml/hr, the vertical placement slowly purges with nitrogen, and with filter paper unnecessary polymer solution siphoned away.With sealing of assembly, splash into the n-heptane solution of 0.05-1M with dropper after a period of time to benzyl dichloride from the other end, reaction 1hr-5hr, it is standby that product is washed the back with normal heptane.The NF membrane product percent of pass is 90%-99%, does not add NaHCO
3The time, product percent of pass is 50%-70%.Above-mentioned film is 45%-56% to the rejection of 0.5g/L-10g/L NaCl, to 1g/L-4g/LMgSO
4Rejection be 90%-98%.
With diameter is that the outer press mold (film sky, Tianjin film engineering Co., Ltd) of polysulfones, Kynoar doughnut of 0.15-0.20mm is used the pure water rinsing, slightly dry in the air under the room temperature, at the polymethylacrylic acid N of its outer surface dip-coating 1wt%-4wt%, the N-dimethylamino propyl ester aqueous solution (contains NaHCO in the solution
3Concentration be 0.01-0.2M), immerse in the n-heptane solution of 0.05-1M to benzyl dichloride behind the 5min-30min under the room temperature and react 0.5-5hr, after product is washed with normal heptane, at glycerine water solution (glycerine: the assembly of making 30cm after soaking water=1: 2～4), it is standby to put into pure water, measuring the NF membrane product percent of pass is 90%-98%, does not add NaHCO
3The time, product percent of pass is 50%-70%.
Be press mold in the polysulfones, Kynoar doughnut of 0.25-0.3mm with diameter, make the assembly of 30cm length, after the pure water rinsing, utilize following device (Fig. 1) to clean with pure water once more.Then, add the polymethylacrylic acid N of 1wt%-4wt% in the batch can of this device, the N-dimethylamino propyl ester aqueous solution aqueous solution (contains NaHCO in the solution
3Concentration be 0.01-0.2M), with the flow velocity circulation 5-10min of 10-50ml/hr, the vertical placement slowly purges with nitrogen, and with filter paper unnecessary polymer solution siphoned away.With the sealing of assembly one end, the other end splashes into the n-heptane solution of 0.05-1M to benzyl dichloride with dropper after a period of time, reaction 1hr-5hr, and it is standby that product is washed the back with normal heptane.The NF membrane product percent of pass is 90%-99%, does not add NaHCO
3The time, product percent of pass is 50%-70%.
The rejection that above-mentioned film is used for 0.5g/L-10g/L NaCl is 45%-56%, to 1g/L-4g/LMgSO
4Rejection be 90%-98%.
Further specify the present invention with specific embodiment below
Embodiment 1: outer press mold:
With diameter is that the outer press mold (film sky, Tianjin film engineering Co., Ltd) of polysulfone hollow fibre of 0.20mm is used the pure water rinsing, slightly dry in the air under the room temperature, at the polymethylacrylic acid N of its outer surface dip-coating 2% (wt%), the N-dimethylaminoethyl aqueous solution (contains NaHCO in the solution
3Concentration be 0.023M), dry in the air under the room temperature to immerse in the n-heptane solution of 0.069M to benzyl dichloride behind the 10min and react 4hr, product cleans with normal heptane, at glycerine water solution (glycerine: the assembly of making 30cm after soaking water=1: 2～4), it is standby to put into pure water, measuring the NF membrane product percent of pass is 95%, does not add NaHCO
3The time, product percent of pass is 67%.Above-mentioned film is 55% to the rejection of 1g/L NaCl, to 1g/L/LMgSO
4Rejection be 95%.
Embodiment 2: interior press mold:
Be press mold in the polysulfone hollow fibre of 0.25mm with diameter, make the assembly of 30cm length, after the pure water rinsing, utilize following device (Fig. 1) to clean the film inner chamber with pure water once more.Then, add the polymethylacrylic acid N of 1wt% in the batch can of this device, the N-dimethylaminoethyl aqueous solution (contains NaHCO in the solution
3Concentration be 0.023M), with the flow velocity circulation 5min of 25ml/hr, the vertical placement slowly purges with nitrogen, and with filter paper unnecessary polymer solution siphoned away.With sealing of assembly, splash into the n-heptane solution of 0.069M with dropper after a period of time to benzyl dichloride from the other end, reaction 4hr, it is standby that product is washed the back with normal heptane.The NF membrane product percent of pass is 95%, does not add NaHCO
3The time, product percent of pass is 58%.Above-mentioned film is 56% to the rejection of 0.5g/L/L NaCl, to 1g/LMgSO
4Rejection be 95%.
Embodiment 3: outer press mold:
With diameter is that the outer press mold (film sky, Tianjin film engineering Co., Ltd) of polysulfone hollow fibre of 0.20mm is used the pure water rinsing, slightly dry in the air under the room temperature, at the polymethylacrylic acid N of its outer surface dip-coating 2% (wt%), the N-dimethylamino propyl ester aqueous solution (contains NaHCO in the solution
3Concentration be 0.023M), dry in the air under the room temperature to immerse in the n-heptane solution of 0.069M to benzyl dichloride behind the 10min and react 4hr, product cleans with normal heptane, at glycerine water solution (glycerine: the assembly of making 30cm after soaking water=1: 2～4), it is standby to put into pure water, measuring the NF membrane product percent of pass is 95%, does not add NaHCO
3The time, product percent of pass is 67%.Above-mentioned film is 55% to the rejection of 1g/L NaCl, to 1g/L/LMgSO
4Rejection be 95%.
Embodiment 4: interior press mold:
Be press mold in the polysulfone hollow fibre of 0.25mm with diameter, make the assembly of 30cm length, after the pure water rinsing, utilize following device (Fig. 1) to clean the film inner chamber with pure water once more.Then, add the polymethylacrylic acid N of 1wt% in the batch can of this device, the N-dimethylamino propyl ester aqueous solution (contains NaHCO in the solution
3Concentration be 0.023M), with the flow velocity circulation 5min of 25ml/hr, the vertical placement slowly purges with nitrogen, and with filter paper unnecessary polymer solution siphoned away.With sealing of assembly, splash into the n-heptane solution of 0.069M with dropper after a period of time to benzyl dichloride from the other end, reaction 4hr, it is standby that product is washed the back with normal heptane.The NF membrane product percent of pass is 95%, does not add NaHCO
3The time, product percent of pass is 58%.Above-mentioned film is 56% to the rejection of 0.5g/L/L NaCl, to 1g/LMgSO
4Rejection be 95%.
Claims (9)
1. the preparation method of a doughnut composite nanometer filtering film, with hollow fiber ultrafiltration membrane or micro-filtration membrane is basement membrane, inner surface or outer surface coating composite material at basement membrane, composite material and crosslinking agent generation interface polymerization reaction, inner surface or outer surface at basement membrane form water-fast crosslinked barrier layer, and wherein composite material is poly-C
1-C
XThe C that replaces
3-C
YOlefin(e) acid N, N-two C
1-C
ZAmino C
2-C
2ZEster, X≤3, Y≤10, Z≤4 are added with additive sodium acid carbonate or sodium carbonate in the solution of composite material, and crosslinking agent is two alkylating reagents.
2. preparation method according to claim 1 is characterized in that the water that will contain the composite bed polymer is coated on the basement membrane, dries in the shade under the room temperature, adds the oil phase that contains crosslinking agent then, makes composite membrane after the reaction.
3. preparation method according to claim 1 and 2, the concentration that it is characterized in that the composite bed polymer is 1wt%-4wt%, based on the total concentration of polymer solution, the concentration of additive sodium acid carbonate or sodium carbonate is 0.01-0.2M, and the concentration of crosslinking agent is 0.05-1M.
4. preparation method according to claim 1 and 2 is characterized in that the doughnut external diameter of the outer usefulness of filming is 0.15-0.20mm, in be coated with usefulness the doughnut external diameter be 0.25-0.3mm.
5. according to the described preparation method of each claim of claim 1-4, it is characterized in that crosslinking agent is to benzyl dichloride or 1,4 dibromobutane.
6. according to the described preparation method of each claim of claim 1-5, it is characterized in that the composite bed polymer is polymethylacrylic acid N, the N-dimethylaminoethyl.
7. according to the described preparation method of each claim of claim 1-6, it is characterized in that composite bed polymer poly methacrylic acid N, the concentration of N-dimethylaminoethyl is 1wt%-4wt%, and the concentration of additive sodium acid carbonate is 0.01-0.2M, and the concentration of crosslinking agent is 0.05-1M.
8. according to the described preparation method of each claim of claim 1-7, it is characterized in that basement membrane is polysulfones or Kynoar, molecular cut off is 6000-20000.
9. according to the described preparation method of each claim of claim 1-8, it is characterized in that crosslinked before, the water of composite bed polymer was coated on the basement membrane 5-30 minute, crosslinking time is 1-5hr.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102068917A (en) * | 2010-11-17 | 2011-05-25 | 无锡中科光远生物材料有限公司 | Double-layer hollow fiber nano-filtration membrane and preparation method thereof |
| CN102671551A (en) * | 2011-03-18 | 2012-09-19 | 中国科学院大连化学物理研究所 | Electro-conductive micro-filtration membrane and preparation method thereof |
| CN105642129A (en) * | 2014-08-31 | 2016-06-08 | 浙江大学 | Positively charged nano-filtration membrane based on tertiary amine type amphiphilic copolymer and preparation method thereof |
| CN105727752A (en) * | 2016-05-11 | 2016-07-06 | 贵州省材料产业技术研究院 | Preparation method of high-strength anti-pollution antibacterial hollow fiber nanofiltration membrane and product |
| CN109364759A (en) * | 2018-12-21 | 2019-02-22 | 滁州学院 | A kind of calcium lignosulfonate solvent-resistant compound nanofiltration membrane and preparation method thereof |
| CN110935327A (en) * | 2019-12-30 | 2020-03-31 | 碧菲分离膜（大连）有限公司 | Internal pressure formula hollow fiber receives filter membrane production line |
-
2005
- 2005-05-30 CN CN 200510013569 patent/CN1872400A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102068917A (en) * | 2010-11-17 | 2011-05-25 | 无锡中科光远生物材料有限公司 | Double-layer hollow fiber nano-filtration membrane and preparation method thereof |
| CN102671551A (en) * | 2011-03-18 | 2012-09-19 | 中国科学院大连化学物理研究所 | Electro-conductive micro-filtration membrane and preparation method thereof |
| CN102671551B (en) * | 2011-03-18 | 2014-03-05 | 中国科学院大连化学物理研究所 | Electro-conductive micro-filtration membrane and preparation method thereof |
| CN105642129A (en) * | 2014-08-31 | 2016-06-08 | 浙江大学 | Positively charged nano-filtration membrane based on tertiary amine type amphiphilic copolymer and preparation method thereof |
| CN105727752A (en) * | 2016-05-11 | 2016-07-06 | 贵州省材料产业技术研究院 | Preparation method of high-strength anti-pollution antibacterial hollow fiber nanofiltration membrane and product |
| CN105727752B (en) * | 2016-05-11 | 2018-08-14 | 贵州省材料产业技术研究院 | A kind of preparation method and product of high-intensity anti-pollution antibacterial hollow fiber nanofiltration membrane |
| CN109364759A (en) * | 2018-12-21 | 2019-02-22 | 滁州学院 | A kind of calcium lignosulfonate solvent-resistant compound nanofiltration membrane and preparation method thereof |
| CN110935327A (en) * | 2019-12-30 | 2020-03-31 | 碧菲分离膜（大连）有限公司 | Internal pressure formula hollow fiber receives filter membrane production line |
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