CN101733024B - Positively charged composite nanofiltration membrane and preparation method thereof - Google Patents
Positively charged composite nanofiltration membrane and preparation method thereof Download PDFInfo
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- CN101733024B CN101733024B CN2010100395347A CN201010039534A CN101733024B CN 101733024 B CN101733024 B CN 101733024B CN 2010100395347 A CN2010100395347 A CN 2010100395347A CN 201010039534 A CN201010039534 A CN 201010039534A CN 101733024 B CN101733024 B CN 101733024B
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Abstract
The invention discloses a positively charged composite nanofiltration membrane and a preparation method thereof. The positively charged composite nanofiltration membrane consists of a porous support layer and polymer containing two functional groups, namely cations and hydroxyl; and the preparation process comprises the following steps: firstly, obtaining the polymer through free radical copolymerization reaction; secondly, preparing the polymer and a crosslinking agent into aqueous solution with certain concentration; and thirdly, coating the aqueous solution on the support layer, and crosslinking to obtain the composite membrane. The nanofiltration membrane prepared by the method has water flux of between 15 and 30L.m-2.h-1 under the operating pressure of 0.6MPa, has high retention ratio of bivalent cations which can reach 94.3 percent maximally, and has the retention ratio of monovalent cations lower than 60 percent. The prepared positively charged composite nanofiltration membrane has good separation performance; and the method for preparing the membrane is simple and feasible, low in cost and suitable for industrial production.
Description
Technical field
The invention belongs to the NF membrane separation field, relate in particular to a kind of Positively charged composite nanofiltration membrane and preparation method thereof.
Background technology
In recent years, membrane separation technique relies on its advantage energy-conservation, efficient, environmental protection, has obtained development rapidly in separating substances purifying field.Wherein, nanofiltration has become the focus of membrane separation technique research as a kind of novel pressure drive membrane separation process.The aperture of NF membrane and molecular cut off are between reverse osmosis membrane and the milipore filter, mainly are to realize by aperture sieving actoion and Coulomb repulsion effect to the separation of material.Generally speaking, NF membrane has higher rejection to multivalent salts ion and molecular weight greater than 200 organic matter, and very low to the rejection of monovalent salt ion and low-molecular-weight organic matter, thereby can realize the Selective Separation to material.Owing to the separating effect that NF membrane has this uniqueness, the Separation ﹠ Purification of material in water softening, wastewater treatment, bio-pharmaceuticals, the field of petrochemical industry have been widely used in.
At present, most of commercialization NF membrane are composite membrane, form by surface functional layer and bottom support layer, divide according to membrane preparation method, mainly contain two big classes such as poly-(ether) sulfone SPESf/ SPSf of cellulose acetate CA, sulfonation that polyamide PA film that interfacial polymerization makes and phase inversion make, sulfonated polyether-ether-ketone SPEEK film.The polyamide nanofiltration membrane chlorine resistance that interfacial polymerization obtains is poor, and oxidation easily takes place cortex.Employing phase inversions such as Buonomenna have prepared the PEEKWC NF membrane (Reactive﹠amp of the lotus positive electricity of polyetheretherketone; Functional Polymers 69 (2009) 259-263).But when adopting this kind method system film, its preparation process is comparatively complicated, and the structure and the performance of film are restive.Yet, the surface-coated method only needs functional polymer solution directly is coated on membrane surface as a kind of simple film-forming method, carries out the immobilization processing and gets final product, and the structure of gained composite membrane and performance are easy to regulation and control, now more and more this method are used for the preparation of composite nanometer filtering film.
Existing NF membrane major part is that bear is electrical, and in practical application area, it is that lotus is electropositive that many situations need film, as the processing of the recovery of high volence metal ion, electroplating wastewater, contain the processing of radioactive metal ion waste water etc.The functional polymer material of now having developed that can be used for the positively charged nanofiltration film preparation is also very limited, adopt this simple film-forming method of surface-coated, the report of preparation positively charged nanofiltration membranes only has following several: the polyphenylene oxide PPO after with the bromo processing such as Xu, with the polyamine is crosslinking agent, has made the NF membrane (Journal of Membrane Science 215 (2003) 25-32) of lotus positive electricity by the crosslinked method of in-situ chemical.Gao etc. have reported the method for a series of employing chemical crosslinkings, with positively charged nanofiltration membranes (Separation and Purification Technology 58 (2008) 393-399 of shitosan and the preparation of derivative class bioabsorbable polymer material thereof; Desalination 233 (2008) 147-1 56 and Desalination 239 (2009) 38-45).Along with the expansion day by day in application of membrane separation technology field, market is also more and more to the demand of the NF membrane of lotus positive electricity, is badly in need of developing a series of novel material of preparing, and adopts easy film-forming method, produces the NF membrane of the good lotus positive electricity of separating property.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art, a kind of Positively charged composite nanofiltration membrane and preparation method thereof is provided.
Positively charged composite nanofiltration membrane and preparation method thereof comprises following steps:
1) monomer that contains tertiary amine group of 2～5 mass parts and the hydroxyalkyl acrylate monomer of 1 mass parts are added in the entry, be made into the aqueous solution that mass percent concentration is 10～30wt%, feed nitrogen, adding mass percent concentration is water soluble oxidized-reduction initator of 1～3wt%, carries out polymerisation in solution under 35～50 ℃, and polymerization time is 8～24 hours, with acetone with polymer precipitation, repeatedly after the washing, get cationic copolymer, standby after the vacuum drying;
2) the above-mentioned cationic copolymer of 1～2.5 mass parts is added in the entry dissolve, add the polyaldehyde of 0.1～0.45 mass parts, adding inorganic acid regulator solution pH value again is 2～4, stirs 3 hours under 20～30 ℃ temperature, left standstill 8～12 hours, and obtained the solution of homogeneous transparent;
3) under the relative air humidity condition of 20～30 ℃ temperature and 50～60%, above-mentioned solution evenly is coated on the supporting layer, again it was positioned in the baking oven of 40～60 ℃ of temperature 2～4 hours, obtain Positively charged composite nanofiltration membrane.
The monomer that contains tertiary amine group described in the step 1) is methacrylic acid-N, N-dimethylaminoethyl, methacrylic acid-N, N-lignocaine methyl esters or methacrylic acid-N, N-dimethylamino methyl esters.Hydroxyalkyl acrylate monomer described in the step 1) is in hydroxy-ethyl acrylate, hydroxyethyl methacrylate or the hydroxy propyl methacrylate.Oxidant in the described oxidation-reduction initiator of step 1) is ammonium persulfate or potassium peroxydisulfate, and the reducing agent in the described oxidation-reduction initiator is a sodium hydrogensulfite, and the mass ratio of Oxidizing and Reducing Agents is 1: 1.Step 2) polyaldehyde described in is glyoxal or glutaraldehyde.Step 2) inorganic acid described in is sulfuric acid or hydrochloric acid.Supporting layer described in the step 3) is polysulfones flat plate ultrafiltration membrane or polyacrylonitrile flat plate ultrafiltration membrane.
The present invention is by adjusting the kind and the ratio of monomer in the copolymer, and the separating property difference of gained NF membrane is to divalent salts MgCl
2Higher rejection is arranged, can be up to 80～95%, and lower to the rejection of monovalent salt NaCl, generally be lower than 60%, water flux is 15～30 L.m
-2.h
-1, can be applicable to water softening, wastewater treatment, different field such as the recovery of metal have broad application prospects.
The present invention is as the copolymer of film function of surface layer material, be that monomer and the hydroxyalkyl acrylate monomer that contains tertiary amine group adopts solution polymerization process to make, the charge of material, hydrophilic and hydrophobic can easier be realized by composition and the proportioning of adjusting polymer monomers; Simultaneously, used monomer conveniently is easy to get, and is cheap, and solvent for use is a water, clean environment firendly, and preparation process is simple and safe.The preparation of composite membrane adopts simple coating, the crosslinked processing of heat cure to get final product, and filming technology is simple, cost is low, has the favorable industrial practicality.
Description of drawings
Fig. 1 is the stereoscan photograph on the surface of Positively charged composite nanofiltration membrane of the present invention;
Fig. 2 is the stereoscan photograph in the cross section of Positively charged composite nanofiltration membrane of the present invention.
The specific embodiment
Provide embodiments of the invention below, but the present invention is not subjected to the restriction of embodiment:
Embodiment 1:
Methacrylic acid-N with 2 mass parts, the hydroxy-ethyl acrylate of N-dimethylaminoethyl and 1 mass parts adds in the entry, be made into the aqueous solution that mass percent concentration is 10wt%, feed nitrogen, adding mass percent concentration is water soluble oxidized-reduction initator K of 1wt%
2S
2O
8And NaHSO
3(1: 1) carries out polymerisation in solution under 35 ℃, polymerization time is 24 hours, with polymer precipitation, repeatedly after the washing, gets cationic copolymer with acetone, and is standby after the vacuum drying; The copolymer of 1 mass parts and the glutaraldehyde of 0.1 mass parts are added to the water, add sulfuric acid again, transferring the pH value of solution value is 2; Under 20 ℃ temperature, stirred 3 hours, left standstill 8 hours, obtain the solution of homogeneous transparent; Under the relative air humidity condition of 20 ℃ temperature and 50%, above-mentioned solution evenly is coated on the polysulphone super-filter membrane, more coated composite membrane is placed baking oven, 40 ℃ of following crosslinking curings 4 hours, obtain Positively charged composite nanofiltration membrane.Positively charged composite nanofiltration membrane is at 25 ℃, under the 0.6MPa pressure, for 1g.L
-1NaCl and MgCl
2The separating resulting of solution is: the rejection to NaCl is 48.5%, and water flux is 21.5L.m
-2.h
-1To MgCl
2Rejection be 84.7%, water flux is 20.8L.m
-2.h
-1
Embodiment 2:
Methacrylic acid-N with 5 mass parts, the hydroxy-ethyl acrylate of N-dimethylaminoethyl and 1 mass parts adds in the entry, be made into the aqueous solution that mass percent concentration is 30wt%, feed nitrogen, adding mass percent concentration is water soluble oxidized-reduction initator K of 3wt%
2S
2O
8And NaHSO
3(1: 1) carries out polymerisation in solution under 50 ℃, polymerization time is 8 hours, with polymer precipitation, repeatedly after the washing, gets cationic copolymer with acetone, and is standby after the vacuum drying; The copolymer of 2.5 mass parts and the glutaraldehyde of 0.45 mass parts are added to the water, add sulfuric acid again, transferring the pH value of solution value is 4; Under 30 ℃ temperature, stirred 3 hours, left standstill 12 hours, obtain the solution of homogeneous transparent; Under the relative air humidity condition of 30 ℃ temperature and 60%, above-mentioned solution evenly is coated on the polysulphone super-filter membrane, more coated composite membrane is placed baking oven, 60 ℃ of following crosslinking curings 2 hours, obtain Positively charged composite nanofiltration membrane.Positively charged composite nanofiltration membrane is at 25 ℃, under the 0.6MPa pressure, for 1g.L
-1NaCl and MgCl
2The separating resulting of solution is: the rejection to NaCl is 53.8%, and water flux is 17.6L.m
-2.h
-1To MgCl
2Rejection be 82.2%, water flux is 1 6.5L.m
-2.h
-1
Embodiment 3:
Methacrylic acid-N with 3 mass parts, the hydroxy-ethyl acrylate of N-dimethylaminoethyl and 1 mass parts adds in the entry, be made into the aqueous solution that mass percent concentration is 15wt%, feed nitrogen, adding mass percent concentration is water soluble oxidized-reduction initator K of 2wt%
2S
2O
8And NaHSO
3(1: 1) carries out polymerisation in solution under 45 ℃, polymerization time is 12 hours, with polymer precipitation, repeatedly after the washing, gets cationic copolymer with acetone, and is standby after the vacuum drying; The copolymer of 1 mass parts and the glutaraldehyde of 0.19 mass parts are added to the water, add hydrochloric acid again, transferring the pH value of solution value is 3; Under 25 ℃ temperature, stirred 3 hours, left standstill 8 hours, obtain the solution of homogeneous transparent; Under the relative air humidity condition of 25 ℃ temperature and 55%, above-mentioned solution evenly is coated on the polysulphone super-filter membrane, more coated composite membrane is placed baking oven, 60 ℃ of following crosslinking curings 2 hours, obtain Positively charged composite nanofiltration membrane.Positively charged composite nanofiltration membrane is at 25 ℃, under the 0.6MPa pressure, for 1g.L
-1NaCl and MgCl
2The separating resulting of solution is: the rejection to NaCl is 49.8%, and water flux is 22.8L.m
-2.h
-1To MgCl
2Rejection be 85.5%, water flux is 21.6L.m
-2.h
-1
Embodiment 4:
Methacrylic acid-N with 3 mass parts, the hydroxy-ethyl acrylate of N-dimethylaminoethyl and 1 mass parts adds in the entry, be made into the aqueous solution that mass percent concentration is 15wt%, feed nitrogen, adding mass percent concentration is water soluble oxidized-reduction initator K of 2wt%
2S
2O
8And NaHSO
3(1: 1) carries out polymerisation in solution under 45 ℃, polymerization time is 12 hours, with polymer precipitation, repeatedly after the washing, gets cationic copolymer with acetone, and is standby after the vacuum drying; The copolymer of 1.5 mass parts and the glutaraldehyde of 0.19 mass parts are added to the water, add sulfuric acid again, transferring the pH value of solution value is 3; Under 25 ℃ temperature, stirred 3 hours, left standstill 8 hours, obtain the solution of homogeneous transparent; Under the relative air humidity condition of 25 ℃ temperature and 55%, above-mentioned solution evenly is coated on the polysulphone super-filter membrane, more coated composite membrane is placed baking oven, 50 ℃ of following crosslinking curings 2 hours, obtain Positively charged composite nanofiltration membrane.Positively charged composite nanofiltration membrane is at 25 ℃, under the 0.6MPa pressure, for 1g.L
-1NaCl and MgCl
2The separating resulting of solution is: the rejection to NaCl is 52.2%, and water flux is 25.8L.m
-2.h
-1To MgCl
2Rejection be 89.6%, water flux is 24.1 L.m
-2.h
-1
Embodiment 5:
Methacrylic acid-N with 3 mass parts, the hydroxy-ethyl acrylate of N-dimethylaminoethyl and 1 mass parts adds in the entry, be made into the aqueous solution that mass percent concentration is 15wt%, feed nitrogen, adding mass percent concentration is water soluble oxidized-reduction initator K of 2wt%
2S
2O
8And NaHSO
3(1: 1) carries out polymerisation in solution under 45 ℃, polymerization time is 12 hours, with polymer precipitation, repeatedly after the washing, gets cationic copolymer with acetone, and is standby after the vacuum drying; The copolymer of 2.5 mass parts and the glutaraldehyde of 0.19 mass parts are added to the water, add sulfuric acid again, transferring the pH value of solution value is 3; Under 25 ℃ temperature, stirred 3 hours, left standstill 8 hours, obtain the solution of homogeneous transparent; Under the relative air humidity condition of 25 ℃ temperature and 55%, above-mentioned solution evenly is coated on the polysulphone super-filter membrane, more coated composite membrane is placed baking oven, 50 ℃ of following crosslinking curings 3 hours, obtain Positively charged composite nanofiltration membrane.Positively charged composite nanofiltration membrane is at 25 ℃, under the 0.6MPa pressure, for 1g.L
-1NaCl and MgCl
2The separating resulting of solution is: the rejection to NaCl is 53.1%, and water flux is 22.3L.m
-2.h
-1To MgCl
2Rejection be 92.2%, water flux is 20.6L.m
-2.h
-1
Embodiment 6:
Methacrylic acid-N with 3 mass parts, the hydroxy-ethyl acrylate of N-dimethylaminoethyl and 1 mass parts adds in the entry, be made into the aqueous solution that mass percent concentration is 15wt%, feed nitrogen, adding mass percent concentration is water soluble oxidized-reduction initator K of 2wt%
2S
2O
8And NaHSO
3(1: 1) carries out polymerisation in solution under 45 ℃, polymerization time is 12 hours, with polymer precipitation, repeatedly after the washing, gets cationic copolymer with acetone, and is standby after the vacuum drying; The copolymer of 1.5 mass parts and the glutaraldehyde of 0.3 mass parts are added to the water, add sulfuric acid again, transferring the pH value of solution value is 3; Under 25 ℃ temperature, stirred 3 hours, left standstill 8 hours, obtain the solution of homogeneous transparent; Under the relative air humidity condition of 25 ℃ temperature and 55%, above-mentioned solution evenly is coated on the polysulphone super-filter membrane, more coated composite membrane is placed baking oven, 50 ℃ of following crosslinking curings 3 hours, obtain Positively charged composite nanofiltration membrane.Positively charged composite nanofiltration membrane is at 25 ℃, under the 0.6MPa pressure, for 1g.L
-1NaCl and MgCl
2The separating resulting of solution is: the rejection to NaCl is 60.7%, and water flux is 20.6L.m
-2.h
-1To MgCl
2Rejection be 94.3%, water flux is 19.1L.m
-2.h
-1
Embodiment 7:
Methacrylic acid-N with 3 mass parts, the hydroxy-ethyl acrylate of N-dimethylaminoethyl and 1 mass parts adds in the entry, be made into the aqueous solution that mass percent concentration is 15wt%, feed nitrogen, adding mass percent concentration is water soluble oxidized-reduction initator K of 2wt%
2S
2O
8And NaHSO
3(1: 1) carries out polymerisation in solution under 45 ℃, polymerization time is 12 hours, with polymer precipitation, repeatedly after the washing, gets cationic copolymer with acetone, and is standby after the vacuum drying; The copolymer of 1.5 mass parts and the glutaraldehyde of 0.45 mass parts are added to the water, add sulfuric acid again, transferring the pH value of solution value is 3; Under 25 ℃ temperature, stirred 3 hours, left standstill 8 hours, obtain the solution of homogeneous transparent; Under the relative air humidity condition of 25 ℃ temperature and 55%, above-mentioned solution evenly is coated on the polysulphone super-filter membrane, more coated composite membrane is placed baking oven, 50 ℃ of following crosslinking curings 3 hours, obtain Positively charged composite nanofiltration membrane.Positively charged composite nanofiltration membrane is at 25 ℃, under the 0.6MPa pressure, for 1g.L
-1NaCl and MgCl
2The separating resulting of solution is: the rejection to NaCl is 64.4%, and water flux is 16.2L.m
-2.h
-1To MgCl
2Rejection be 92.7%, water flux is 15.3L.m
-2.h
-1
Embodiment 8:
Methacrylic acid-N with 3 mass parts, the hydroxy-ethyl acrylate of N-dimethylaminoethyl and 1 mass parts adds in the entry, be made into the aqueous solution that mass percent concentration is 15wt%, feed nitrogen, adding mass percent concentration is water soluble oxidized-reduction initator K of 2wt%
2S
2O
8And NaHSO
3(1: 1) carries out polymerisation in solution under 45 ℃, polymerization time is 12 hours, with polymer precipitation, repeatedly after the washing, gets cationic copolymer with acetone, and is standby after the vacuum drying; The copolymer of 2 mass parts and the glutaraldehyde of 0.37 mass parts are added to the water, add sulfuric acid again, transferring the pH value of solution value is 3; Under 25 ℃ temperature, stirred 3 hours, left standstill 8 hours, obtain the solution of homogeneous transparent; Under the relative air humidity condition of 25 ℃ temperature and 55%, above-mentioned solution evenly is coated on the polysulphone super-filter membrane, more coated composite membrane is placed baking oven, 50 ℃ of following crosslinking curings 3 hours, obtain Positively charged composite nanofiltration membrane.Positively charged composite nanofiltration membrane is at 25 ℃, under the 0.6MPa pressure, for 1g.L
-1NaCl and MgCl
2The separating resulting of solution is: the rejection to NaCl is 56.8%, and water flux is 16.7L.m
-2.h
-1To MgCl
2Rejection be 88.6%, water flux is 1 5.5L.m
-2.h
-1
Claims (5)
1. the preparation method of a Positively charged composite nanofiltration membrane is characterized in that its step is as follows:
1) monomer that contains tertiary amine group of 2～5 mass parts and the hydroxyalkyl acrylate monomer of 1 mass parts are added in the entry, be made into the aqueous solution that mass percent concentration is 10～30wt%, feed nitrogen, adding mass percent concentration is water soluble oxidized-reduction initator of 1～3wt%, carries out polymerisation in solution under 35～50 ℃, and polymerization time is 8～24 hours, with acetone with polymer precipitation, repeatedly after the washing, get cationic copolymer, standby after the vacuum drying;
2) the above-mentioned cationic copolymer of 1～2.5 mass parts is added in the entry dissolve, add the polyaldehyde of 0.1～0.45 mass parts, adding inorganic acid regulator solution pH value again is 2～4, stirs 3 hours under 20～30 ℃ temperature, left standstill 8～12 hours, and obtained the solution of homogeneous transparent;
3) under the relative air humidity condition of 20～30 ℃ temperature and 50～60%, above-mentioned solution evenly is coated on the supporting layer, again it was positioned in the baking oven of 40～60 ℃ of temperature 2～4 hours, obtain Positively charged composite nanofiltration membrane;
The described monomer that contains tertiary amine group is methacrylic acid-N, N-dimethylaminoethyl, methacrylic acid-N, N-lignocaine methyl esters or methacrylic acid-N, N-dimethylamino methyl esters, described hydroxyalkyl acrylate monomer is hydroxy-ethyl acrylate, hydroxyethyl methacrylate or hydroxy propyl methacrylate.
2. the preparation method of a kind of Positively charged composite nanofiltration membrane according to claim 1, it is characterized in that the oxidant in the described oxidation-reduction initiator of step 1) is ammonium persulfate or potassium peroxydisulfate, reducing agent in the described oxidation-reduction initiator is a sodium hydrogensulfite, and the mass ratio of Oxidizing and Reducing Agents is 1: 1.
3. the preparation method of a kind of Positively charged composite nanofiltration membrane according to claim 1 is characterized in that step 2) described in polyaldehyde be glyoxal or glutaraldehyde.
4. the preparation method of a kind of Positively charged composite nanofiltration membrane according to claim 1 is characterized in that step 2) described in inorganic acid be sulfuric acid or hydrochloric acid.
5. the preparation method of a kind of Positively charged composite nanofiltration membrane according to claim 1 is characterized in that the supporting layer described in the step 3) is polysulfones flat plate ultrafiltration membrane or polyacrylonitrile flat plate ultrafiltration membrane.
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| CN102294176B (en) * | 2011-08-17 | 2013-06-26 | 浙江大学 | High permeability nanofiltration membrane containing zwitterion and preparation method thereof |
| CN103285742B (en) * | 2013-06-26 | 2014-09-03 | 浙江大学 | Preparation method of quaternary ammonium salt type cationic polymer modified chitosan nanofiltration membrane |
| CN103451850B (en) * | 2013-08-16 | 2015-12-09 | 西安理工大学 | The preparation method of lotus positive electroceramics micro nanometer fiber film |
| CN104190265A (en) * | 2014-08-31 | 2014-12-10 | 浙江大学 | Low-pressure high-flux chlorine-containing polymer nanofiltration membrane with stable separation layer and preparation method thereof |
| CN106422811A (en) * | 2015-08-11 | 2017-02-22 | 贵阳时代沃顿科技有限公司 | Novel polyelectrolyte nanofiltration membrane and preparation method thereof |
| CN106582326B (en) * | 2015-10-20 | 2019-07-19 | 中国石油化工股份有限公司 | A kind of antibacterial composite nanometer filtering film and its preparation method and application |
| CN110548398B (en) * | 2018-06-04 | 2021-11-26 | 宁波蓝盾新材料科技有限公司 | Crosslinking type zwitterion group modified forward osmosis membrane and preparation method thereof |
| CN109925882A (en) * | 2019-04-16 | 2019-06-25 | 德蓝水技术股份有限公司 | A kind of hollow fiber compound nanofiltration membrane and preparation method thereof |
| CN111569676B (en) * | 2020-06-02 | 2021-07-27 | 四川大学 | Ultrafiltration membrane, nanofiltration membrane, preparation method thereof and ultrafiltration-nanofiltration reversible conversion method |
| CN112755810B (en) * | 2020-12-18 | 2023-05-12 | 中化(宁波)润沃膜科技有限公司 | Positively charged composite nanofiltration membrane and preparation method thereof |
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