CN102974228B - Nanofiltration membrane with nanometer hybridized desalination layer - Google Patents
Nanofiltration membrane with nanometer hybridized desalination layer Download PDFInfo
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Abstract
The invention discloses a nanofiltration membrane with a nanometer hybridized desalination layer. The desalination layer formed through interphase hybridization of an inorganic nanoparticle with a particle size of 1 to 1000 nm and polyamide or polyimide is arranged on a porous supporting layer of the membrane. A preparation method for the nanofiltration membrane mainly comprises the following steps: pre-dispersion of the nanoparticle, preparation of a solution A, preparation of a solution B, interfacial polymerization, surface polishing and roller squeezing, rinsing with deionized water, moisture retention with glycerin and drying, wherein air drying and sulfonation can be carried out after surface polishing and roller squeezing. According to the invention, nanometer hybridization effects of a high polymer nano-material in the nanofiltration membrane are made full use of, so hydrophilic performance, antioxidation performance and anti-pollution performance of the nanofiltration membrane are improved, and the nanofiltration membrane has the advantages of low pollution, great flux and a high removal rate. The preparation method is scientific and reasonable, enables the nanometer composite nanofiltration membrane with a specific nanoparticle and polyamide hybridized desalination layer to be prepared and has higher ion selectivity, low pollution capability and temperature stability.
Description
Technical field
The present invention relates to and a kind of there is NF membrane of nano hybridization desalination layer and preparation method thereof, belong to Nanofiltration-membrane technique field.
Background technology
Nanofiltration is a kind of pressure-driven membrane separating process between counter-infiltration and ultrafiltration, NF membrane is the functional pellicle of one allowing solvent molecule or some low molecular weight solutes or low price ion permeable, be a kind of special and up-and-coming diffusion barrier kind, be nanoscale because of its surface apertures and the material of nanoscale (0.001 micron) can be retained and gain the name; It retains organic molecular weight and is approximately about 150-500, and the ability retaining dissolubility salt is between 2%-98%, to the desalination of monovalent anion salting liquid lower than high-valence anion salting liquid.Since the eighties, in succession developed various NF membrane and assembly in the world, wherein the overwhelming majority is composite nanofiltration membrane, and its surface is mostly electronegative.By the composition of composite nanometer filtering film ultra-thin composite layer, NF membrane can be divided into aromatic polyamides class composite nanometer filtering film, poly-croak carboxamide dihydrochloride class composite nanometer filtering film, poly-(ether) sulfone class composite nanometer filtering film of sulfonation and mixed type composite nanometer filtering film.NF membrane due to its operating pressure low, compared with low pressure reverse osmosis, energy 15% can be economized under same application occasion, simultaneously, it has higher hauling-out rate to the organic matter that divalence or multivalent ion and molecular weight are greater than 200, therefore application is more and more wider, as solution decolouring and organics removal (TOC), remove first three alkyl halide of chlorination (THM) predecessor (humic acid and fulvic acid) in drinking water, seawater removes sulfate, demineralized water and TDS content in reduction solution, remove the nitrate in underground water, radioactive substance and selenium, food, concentrated and the desalination of material in pharmaceuticals industry, waste water (liquid) process etc.
Along with the raising of expanding economy and social life level, nanofiltration by improve application water quality, water softening, dyestuff, pigment, medicine and Bio-engineering Products etc. purification to be separated with concentrated, the profit degree of depth and to print and dye, weave, obtain applying more and more widely in waste water (liquid) desolventing technology etc. in chemical industry and pharmaceuticals industry, bring fabulous Social and economic benef@.The quality of NF membrane is the key point ensureing nanofiltration effect.Because common NF membrane flux pollutes greatly, easily, therefore rely on the flux of strict controlling diaphragm to reduce the loss of NF membrane in actual applications; Again because it has higher removal efficiency and lower to monovalent ion removal efficiency to divalent ion, thus the formula of research NF membrane and preparation method more beneficial important in reality production with the desalting ability improving compound desalination layer.
CN101934201A discloses a kind of high-selectivity composite nanofiltration membrane and preparation method thereof, comprise nonwoven layer and high-molecular porous supporting layer, porous support layer has the polyamide surface layer that one deck or bilayer polyamine and/or polyhydric alcohol amine and polynary acyl chloride reaction are made, interfacial polymerization is utilized to form one deck or double-layer polyamide surface layer, add the thickness on NF membrane top layer, make film surface flatness, hydrolytic resistance, resistance to oxidation and scoring resistance, stain resistance is improved, and film surface can electronegative or positive charge, thus make this composite nanometer filtering film have the function desalination layer of high selectivity.But along with the changes in demand in the progress of social productive forces and production application, the ion selectivity of the function desalination layer of the composite nanometer filtering film of the program, low stain ability and temperature stability are not ideal enough.
Summary of the invention
The invention provides and a kind of there is NF membrane of nano hybridization desalination layer and preparation method thereof, solve the ion selectivity of the functional desalination layer of high-selectivity composite nanofiltration membrane of the prior art, low stain ability and the dissatisfactory problem of temperature stability.
It is of the present invention that to have NF membrane of nano hybridization desalination layer and preparation method thereof as described below.
There is a NF membrane for nano hybridization desalination layer, comprise nonwoven layer and porous support layer, it is characterized in that: on porous support layer, have one deck to be the desalination layer that the inorganic nano-particle of 1 ~ 1000nm and polyamide or the alternate hydridization of polyimides are formed by particle diameter; The formation of nano hybridization polyamide or polyimides desalination layer is prepared from through interfacial reaction on porous support by the aqueous phase solution containing amine monomers and the organic phase solution containing acyl chlorides monomer; The ratio of nano particle in the hydridization desalination layer formed by interracial contact is 1 ~ 10wt%; Described porous support layer is polysulfones, any one or several in polyether sulfone, Kynoar, PPSU, modification PPSU and polyvinyl chloride to be separated formation through conventional non-solvent inducing solutions.
Preparation has the preparation method of the NF membrane of nano hybridization desalination layer as claimed in claim 1, mainly comprises the following steps:
(1) nano particle is pre-dispersed: inorganic or organic nano particle are scattered in solution A and/or B solution solvent used, again the pre-dispersed 0.5 ~ 24h of high-power ultrasonic is carried out to above-mentioned solvent, described nano particle and corresponding solution A unmixing, with corresponding B solution unmixing.
(2) solution A is prepared: after the nano particle Monodispersed of step (1) is in water, add amine monomers and pH adjustment reagent successively, stir, dissolve after completely, gained solution A adopts ultrasonic continuation process 1 ~ 5h, the pH scope of adjustment solution A is 6 ~ 12, is preferably 7 ~ 10, is more preferably 8 ~ 9;
(3) prepare B solution: after the nano particle Monodispersed of step (1) is in B solution organic solvent used, adds acyl chlorides monomer successively, stir, dissolve after completely, gained B solution adopts ultrasonic continuation process 30 ~ 100min.
(4) interface polymerization reaction and the process of surface finish squeezing roller: porous support layer is put into solution A, time of contact is 1 ~ 200s, after draining surface water drops, put into B solution again to contact, time of contact is 1 ~ 300s, takes out and obtain nascent nano combined NF membrane, then the process of surface finish squeezing roller is adopted, squeezing roller pressure is 0 ~ 5MPa, is preferably 0.2 ~ 3MPa, is more preferably 0.2 ~ 1MPa.
(5) NF membrane of step (4) gained is adopted that temperature is 20 ~ 80 DEG C, bath raio is 1:(5 ~ 100) deionized water carry out rinsing 5 ~ 10min, and to be immersed in concentration be 0.5 ~ 20wt%, temperature is 1 ~ 40min in the glycerite of 15 ~ 80 ° of C, carries out moisturizing process;
Inorganic nano-particle in described step (1) is any one or several in zeolite L TA, aluminium oxide, titanium oxide, alunite, silica, alumina, beidellite, hydroxyl aluminium alum, ice crystal, halloysite, new alum, ransomite, imvite, apjohnite, hydrocalumite, kaolin, nontronite, kalinite, calcite, saponite, mellite, graphite, CNT, chalcoalumite, iron oxide, zinc oxide, nm of gold, kaolinite, hydroxyapatite and anauxite.
Nano particle diameter in described step (1) is 1 ~ 1000nm, is preferably 1 ~ 500nm, is preferably 5 ~ 200nm, is more preferably 10 ~ 100nm; The concentration of nano particle in solution A or B solution is 0.005 ~ 50wt%, is preferably 0.005 ~ 30wt%, is more preferably 0.01 ~ 20wt%.
The solvent that in described step (1), solution A is used is selected from any one or several in cyclohexane, hexane, heptane, octane, naphtha, ISOPAR-E, ISOPAR-L, ISOPAR-G and mineral oil.
Amine monomers in described step (2) is piperazine, or m-phenylene diamine (MPD) and/or p-phenylenediamine (PPD);
When amine monomers is piperazine, its concentration is 0.01 ~ 5wt%, and optimization concentration is 0.05 ~ 2wt%;
When amine monomers be p-phenylenediamine (PPD) and/or m-phenylene diamine (MPD) time, its integrated concentration is 0.5 ~ 6wt%, be preferably 1wt% ~ 4wt%.
Acyl chlorides monomer in described step (3) is any one or several in o-phthaloyl chloride, paraphthaloyl chloride, m-phthaloyl chloride, connection phenyl-diformyl, pyromellitic trimethylsilyl chloride, benzene-disulfo-chloride, fourth three acyl chlorides, succinyl chloride, penta 3 acyl chlorides, glutaryl chlorine, cyclohexane diacid chloride, cyclohexane three acyl chlorides, cyclohexane four acyl chlorides, oxolane diacid chloride, oxolane four acyl chlorides, cyclopropane three acyl chlorides, cyclobutane diacid chloride, cyclobutane four acyl chlorides, pentamethylene diacid chloride.
When acyl chlorides monomer is pyromellitic trimethylsilyl chloride, its concentration is 0.1 ~ 5wt%, is preferably 0.5 ~ 3wt%;
When acyl chlorides monomer is any one or several in other acyl chlorides monomers, its integrated concentration is 0.01 ~ 2wt%, is preferably 0.03 ~ 1.5wt%.
After surface finish squeezing roller process in described step (4) terminates, adopt the organic phase solvent on air-dry mode process removal diaphragm, wind speed range is 0.1m/s ~ 20m/s, is preferably 1 ~ 5m/s; Temperature is 15 ~ 60 DEG C, is preferably 30 ~ 50 DEG C.
After described air-dry process terminates, concentrated sulfuric acid aqueous solution is adopted to carry out sulfonation process to the nano combined NF membrane surface after removing organic phase solvent, wherein, sulfuric acid concentration is 10 ~ 80wt%, be preferably 20 ~ 50wt%, sulfuric acid solution temperature is 15 ~ 70 DEG C, and be preferably 40 ~ 60 DEG C, the sulfonation processing time is 1 ~ 120min.
After moisturizing process in described step (5) terminates, adopt drying mode process, bake out temperature is 20 ~ 120 DEG C, and drying time is 2 ~ 60min.
Compared with prior art, the inorganic nano-particle with certain particle diameter and surface characteristic is introduced in NF membrane desalination layer by interfacial polymerization by the present invention, form the hybrid structure between inorganic nano-particle and polyamide, make this NF membrane desalination layer have some advantage function of inorganic material and organic material concurrently.Existence as hydrophilic inorganic nano particle can effectively promote NF membrane to one, bivalent ions removal efficiency, improve the resistance to temperature stability of desalination layer and anti-organic contamination energy, the existence of polyamide then effectively can lock nano particle, and provides enough free volume to keep the performance of low-pressure high-throughput.
Technical scheme of the present invention, in the preparation process of dry type NF membrane, introduces the mode of physical impact, arranges nascent NF membrane surface, can obtain better flux performance through the NF membrane arranged.For promoting this film further for ion effective selectivity and clearance, introduce more surface band electric group by sulfonation technology.
Beneficial effect of the present invention: the nano hybridization effect having given full play to high molecule nano material in NF membrane, improves hydrophilicity, anti-oxidant and antifouling property, possesses the effect of low stain, large flux, high removal efficiency; Its preparation method is scientific and reasonable, has prepared the nano combined NF membrane with specific nano particle and polyamide hybrid desalination layer, and it has higher ion selectivity, low stain ability and temperature stability.Use the NF membrane with nano hybridization desalination layer obtained by preparation method of the present invention, under the test condition of the 2000ppmNaCl aqueous solution, 70psi operating pressure, temperature 25 DEG C, pH value 6.5-7.5, NaCl removal efficiency is at 60-95%, and water flux is at 30-50GPD; At 2000ppmMgSO
4under aqueous solution test condition, MgSO
4removal efficiency is more than 98%, and water flux is at 24-50GPD.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph (SEM figure) of the nano combined desalination layer of NF membrane of the present invention.
Detailed description of the invention
In order to deepen to understand the present invention, below in conjunction with embodiment and accompanying drawing, the present invention is described in further detail, and this embodiment only for explaining the present invention, does not form limiting the scope of the present invention.
Embodiment 1
A kind of NF membrane with nano hybridization desalination layer of the present invention, mainly prepare according to the following steps:
(1) nano particle is pre-dispersed: get 100g titanium dioxide nano-particle (particle diameter is 60nm) and be scattered in 1900g deionized water, adopt high-power ultrasonic to carry out ultrasonic disperse process after stirring, and namely obtains nano titania dispersion liquid after ultrasonic 6h;
(2) solution A preparation: 11g Piperazine anhydrous is dissolved in be mixed with a diphenylamines concentration in the described nano titania dispersion liquid of 989g step (1) be the solution of 1.1wt%, stir, dissolve completely, appropriate pH is adopted to regulate reagent NaOH, mixed solution is carried out stirring and dissolving, adjustment final solution pH is i.e. obtained solution A after 12, and gained solution A adopts ultrasonic continuations to process 1h.The concentration of nano particle in solution A is 50wt%.
(3) B solution preparation: be dissolved in by 23.4g pyromellitic trimethylsilyl chloride in 976.6g ethyl cyclohexane and be mixed with the solution that concentration is 2.3wt%, stir, dissolves completely, obtains B solution, and gained B solution adopts ultrasonic continuation process 30min.The concentration of nano particle in B solution is 50wt%.
(4) polysulfone porous supporting layer is soaked 30s in solution A, time of contact is 50s, taking-up drains to film surface without the obvious globule, then contact 20s with B solution, time of contact is 50s, adopts polishing pressure roller to carry out roller process rapidly after being taken out by diaphragm, squeezing roller pressure is 0.2MPa, its rear film at room temperature air-dry removal remains ethyl cyclohexane, and wind speed range is 0.1m/s, and temperature is 15 ° of C.
(5) by nanofiltration diaphragm concentration be 80wt%, temperature is soak 10min in the sulfuric acid solution of 15 DEG C, afterwards with temperature be 20 DEG C, bath raio is the residual acid of the washed with de-ionized water removing of 1:30, then concentration be 5wt%, temperature is soak 2min in the glycerite of 15 DEG C.
(6) in 80 DEG C of baking ovens, dry 10min, in dry type diaphragm, final moisture content is lower than 0.5wt%.
Embodiment 2
(1) nano particle is pre-dispersed: get 100g titanium dioxide nano-particle (particle diameter is 500nm) and be scattered in 1900g deionized water, adopt high-power ultrasonic to carry out ultrasonic disperse process after stirring, and namely obtains nano titania dispersion liquid after ultrasonic 6h;
(2) solution A preparation: 11g Piperazine anhydrous is dissolved in the described nano titania dispersion liquid of 989g step (1) that to be mixed with diphenylamines and a diphenylamines integrated concentration be the solution of 0.5wt%, stir, dissolve completely, adding appropriate pH regulates reagent NaOH adjustment final solution pH to be after 11, i.e. obtained solution A, gained solution A adopts ultrasonic continuation process 5h.The concentration of nano particle in solution A is 50wt%.
(3) B solution preparation: be dissolved in by 23.4g pyromellitic trimethylsilyl chloride in 976.6g ethyl cyclohexane and be mixed with the solution that concentration is 5wt%, stir, dissolves completely, obtains B solution, and gained B solution adopts ultrasonic continuation process 100min.The concentration of nano particle in B solution is 50wt%.
(4) polysulfone porous supporting layer is soaked in solution A, time of contact is 1s, taking-up drains to film surface without the obvious globule, then with B solution soak, time of contact is 1s, and adopt polishing pressure roller to carry out roller process rapidly after being taken out by diaphragm, squeezing roller pressure is 5MPa, its rear film at room temperature air-dry removal remains ethyl cyclohexane, and wind speed is 0.1m/s; Temperature is 60 DEG C.
(5) be 10wt% by nanofiltration diaphragm in concentration, temperature is the sulfuric acid solution of 70 DEG C, soaks 120min in sulfuric acid solution, the acid that the washed with de-ionized water removing that rear temperature is 80 DEG C, bath raio is 1:5 is residual, then be 0.5wt% in concentration, temperature is soak 1min in the glycerite of 80 DEG C.
(6) in 120 DEG C of baking ovens, dry 2min, in dry type diaphragm, final moisture content is lower than 0.5wt%.
Embodiment 3
(1) nano particle is pre-dispersed: get 100g titanium dioxide nano-particle (particle diameter is 200nm) and be scattered in 1900g deionized water, adopt high-power ultrasonic to carry out ultrasonic disperse process after stirring, and namely obtains nano titania dispersion liquid after ultrasonic 6h;
(2) solution A preparation: 11g Piperazine anhydrous is dissolved in the described nano titania dispersion liquid of 989g step (1) and is mixed with the solution that piperazine concentration is 1.5wt%, stir, dissolve completely, adding appropriate pH regulates reagent NaOH adjustment final solution pH to be after 11, i.e. obtained solution A, gained solution A adopts ultrasonic continuation process 2h.The concentration of nano particle in solution A is 20wt%.
(3) B solution preparation: be dissolved in by 23.4g pyromellitic trimethylsilyl chloride in 976.6g ethyl cyclohexane and be mixed with the solution that concentration is 3wt%, stir, dissolves completely, obtains B solution, and gained B solution adopts ultrasonic continuation process 40min.The concentration of nano particle in B solution is 20wt%.
(4) polysulfone porous supporting layer is soaked in solution A, time of contact is 150s, taking-up drains to film surface without the obvious globule, then with B solution soak, time of contact is 200s, and adopt polishing pressure roller to carry out roller process rapidly after being taken out by diaphragm, squeezing roller pressure is 1MPa, its rear film at room temperature air-dry removal remains ethyl cyclohexane, and wind speed is 5m/s; Temperature is 40 DEG C.
(5) be 50wt% by nanofiltration diaphragm in concentration, temperature is the sulfuric acid solution of 40 DEG C, soaks 40min in sulfuric acid solution, the acid that the washed with de-ionized water removing that rear temperature is 40 DEG C, bath raio is 1:80 is residual, then be 15wt% in concentration, temperature is soak 10min in the glycerite of 30 DEG C.
(6) in 50 DEG C of baking ovens, dry 40min, in dry type diaphragm, final moisture content is lower than 0.5wt%.
Embodiment 4
(1) nano particle is pre-dispersed: get 100g titanium dioxide nano-particle (particle diameter is 10nm) and be scattered in 1900g deionized water, adopt high-power ultrasonic to carry out ultrasonic disperse process after stirring, and namely obtains nano titania dispersion liquid after ultrasonic 6h;
(2) solution A preparation: 11g Piperazine anhydrous is dissolved in the described nano titania dispersion liquid of 989g step (1) and is mixed with the solution that p-phenylenediamine (PPD) concentration is 1wt%, stir, dissolve completely, adding appropriate pH regulates reagent NaOH adjustment final solution pH to be after 11, i.e. obtained solution A, gained solution A adopts ultrasonic continuation process 2h.The concentration of nano particle in solution A is 10wt%.
(3) B solution preparation: be dissolved in by 23.4g pyromellitic trimethylsilyl chloride in 976.6g ethyl cyclohexane and be mixed with the solution that concentration is 0.5wt%, stir, dissolves completely, obtains B solution, and gained B solution adopts ultrasonic continuation process 80min.The concentration of nano particle in B solution is 10wt%.
(4) polysulfone porous supporting layer is soaked in solution A, time of contact is 100s, taking-up drains to film surface without the obvious globule, then with B solution soak, time of contact is 100s, and adopt polishing pressure roller to carry out roller process rapidly after being taken out by diaphragm, squeezing roller pressure is 2MPa, its rear film at room temperature air-dry removal remains ethyl cyclohexane, and wind speed is 10m/s; Temperature is 30 DEG C.
(5) be 20wt% by nanofiltration diaphragm in concentration, temperature is the sulfuric acid solution of 60 DEG C, soaks 80min in sulfuric acid solution, the acid that the washed with de-ionized water removing that rear temperature is 60 DEG C, bath raio is 1:50 is residual, then be 5wt% in concentration, temperature is soak 30min in the glycerite of 60 DEG C.
(6) in 90 DEG C of baking ovens, dry 20min, in dry type diaphragm, final moisture content is lower than 0.5wt%.
Embodiment 5
(1) nano particle is pre-dispersed: get 100g titanium dioxide nano-particle (particle diameter is 100nm) and be scattered in 1900g deionized water, adopt high-power ultrasonic to carry out ultrasonic disperse process after stirring, and namely obtains nano titania dispersion liquid after ultrasonic 6h;
(2) solution A preparation: 11g Piperazine anhydrous is dissolved in the described nano titania dispersion liquid of 989g step (1) and is mixed with the solution that piperazine concentration is 2wt%, stir, dissolve completely, add appropriate pH and regulate reagent NaOH, adjustment final solution pH is after 11, i.e. obtained solution A, gained solution A adopts ultrasonic continuation process 1 ~ 5h.The concentration of nano particle in solution A is 10wt%.
(3) B solution preparation: be dissolved in by 23.4g pyromellitic trimethylsilyl chloride in 976.6g ethyl cyclohexane and be mixed with the solution that concentration is 2wt%, stir, dissolves completely, obtains B solution, and gained B solution adopts ultrasonic continuation process 60min.The concentration of nano particle in B solution is 10wt%.
(4) polysulfone porous supporting layer is soaked in solution A, time of contact is 200s, taking-up drains to film surface without the obvious globule, then with B solution soak, time of contact is 300s, and adopt polishing pressure roller to carry out roller process rapidly after being taken out by diaphragm, squeezing roller pressure is 0.6MPa, its rear film at room temperature air-dry removal remains ethyl cyclohexane, and wind speed is 2.5m/s; Temperature is 40 DEG C.
(5) be 35wt% by nanofiltration diaphragm in concentration, temperature is the sulfuric acid solution of 50 DEG C, soaks 60min in sulfuric acid solution, the acid that the washed with de-ionized water removing that rear temperature is 50 DEG C, bath raio is 1:100 is residual, then be 10wt% in concentration, temperature is soak 20min in the glycerite of 40 DEG C.
(6) in 70 DEG C of baking ovens, dry 30in, in dry type diaphragm, final moisture content is lower than 0.5wt%.
Get the dry type NF membrane with nano combined desalination layer of the embodiment of the present invention 1 ~ 5 gained as test example, then prepare common NF membrane according to the following steps as a comparison case:
(1) solution A preparation: be dissolved in by 11g Piperazine anhydrous in 989g water and be mixed with the solution that concentration is 1.1wt%, abundant stirring and dissolving is complete, then adds 1g NaOH and 20gN in this solution, N-dimethylformamide (DMF) stirring and dissolving i.e. obtained solution A.
(2) B solution preparation: be dissolved in by 23.4g pyromellitic trimethylsilyl chloride in 976.6g ethyl cyclohexane and be mixed with the solution that concentration is 2.3wt%, dissolves completely and namely obtains B solution.
(3) polysulfone porous supporting layer is soaked 30s in solution A, take out and drain film surface to without the obvious globule, then contact 20s with B solution, by the at room temperature surperficial ethyl cyclohexane of air-dry removal after diaphragm taking-up.
(4) nanofiltration diaphragm prepared by (3) step is soaked 10min in 80 ° of C citric acids, afterwards with the acid that washed with de-ionized water removing is residual, then in the normal temperature glycerite of 5wt%, soak 2min, soak diaphragm in 80 ° of C baking ovens, dry obtained common composite nanometer filtering film.
Get test example NF membrane and comparative example NF membrane, test at diaphragm monitor station, be under the test condition of 70psi, temperature 25 DEG C, pH value 6.5-7.5 at operating pressure, obtain 2000ppm NaCl aqueous solution water flux (GFD) and NaCl removal efficiency, and 2000ppm MgSO4 aqueous solution water flux (GFD) and MgSO4 removal efficiency, the results are shown in Table 1.
Table 1 nanometer filtering film water flux and removal efficiency
(according to the statement of beneficial effect, have modified wherein two MgSO
4water flux value be more than 24.）
As shown in table 1, relative to the common NF membrane of comparative example, NF membrane of the present invention has higher NaCl aqueous solution water flux and NaCl removal efficiency.Under same experimental enviroment and condition, the present invention has the more outstanding performance of the common NF membrane compared in comparative example, possesses higher MgSO4 aqueous solution water flux and MgSO4 removal efficiency.
Electron-microscope scanning is carried out to the desalination layer with the dry type NF membrane of nano combined desalination layer of the present invention, the SEM that obtains figure as shown in Figure 1, have nano particle polyamide hybrid structure desalination layer surface compact and evenly.
Claims (10)
1. there is a NF membrane for nano hybridization desalination layer, comprise nonwoven layer and porous support layer, porous support layer has one deck be the desalination layer that the inorganic nano-particle of 1 ~ 1000nm and polyamide or the alternate hydridization of polyimides are formed by particle diameter; The formation of nano hybridization polyamide or polyimides desalination layer is prepared from through interfacial reaction on porous support by the aqueous phase solution containing amine monomers and the organic phase solution containing acyl chlorides monomer; The ratio of nano particle in the hydridization desalination layer formed by interracial contact is 1 ~ 10wt%; Described porous support layer is polysulfones, any one or several in polyether sulfone, Kynoar, PPSU, modification PPSU and polyvinyl chloride to be separated formation through conventional non-solvent inducing solutions, it is characterized in that: under the test condition of the 2000ppmNaCl aqueous solution, 70psi operating pressure, temperature 25 DEG C, pH value 6.5-7.5, NaCl removal efficiency is at 60-95%, and water flux is at 30-50GPD; Under 2000ppmMgSO4 aqueous solution test condition, MgSO4 removal efficiency is more than 98%, and water flux is at 24-50GPD.
2. there is the preparation method of the NF membrane of nano hybridization desalination layer as claimed in claim 1, it is characterized in that: mainly comprise the following steps:
(1) nano particle is pre-dispersed: inorganic or organic nano particle are scattered in solution A and/or B solution solvent used, again the pre-dispersed 0.5 ~ 24h of high-power ultrasonic is carried out to above-mentioned solvent, described nano particle and corresponding solution A unmixing, with corresponding B solution unmixing;
(2) solution A is prepared: after the nano particle Monodispersed of step (1) is in water, add amine monomers and pH adjustment reagent successively, stir, dissolve after completely, gained solution A adopts ultrasonic continuation process 1 ~ 5h, and the pH scope of adjustment solution A is 6 ~ 12;
(3) prepare B solution: after the nano particle Monodispersed of step (1) is in B solution organic solvent used, adds acyl chlorides monomer successively, stir, dissolve completely, gained B solution adopts ultrasonic continuation process 30 ~ 100min;
(4) interface polymerization reaction and the process of surface finish squeezing roller: porous support layer is put into solution A, time of contact is 1 ~ 200s, after draining surface water drops, put into B solution again to contact, time of contact is 1 ~ 300s, take out and obtain nascent nano combined NF membrane, then adopt the process of surface finish squeezing roller, squeezing roller pressure is 0 ~ 5MPa;
(5) NF membrane of step (4) gained is adopted that temperature is 20 ~ 80 DEG C, bath raio is 1:(5 ~ 100) deionized water carry out rinsing 5 ~ 10min, and to be immersed in concentration be 0.5 ~ 20wt%, temperature is 1 ~ 40min in the glycerite of 15 ~ 80 DEG C, carries out moisturizing process;
Inorganic nano-particle in described step (1) is zeolite L TA, aluminium oxide, titanium oxide, alunite, silica, alumina, beidellite, hydroxyl aluminium alum, ice crystal, halloysite, new alum, ransomite, imvite, apjohnite, hydrocalumite, kaolin, nontronite, kalinite, calcite, saponite, mellite, graphite, CNT, chalcoalumite, iron oxide, zinc oxide, nm of gold, kaolinite, any one or several in hydroxyapatite and anauxite,
The concentration of nano particle in described step (1) in solution A or B solution is 0.005 ~ 50wt%; Nano particle diameter is 1 ~ 1000nm;
Amine monomers in described step (2) is piperazine, or m-phenylene diamine (MPD) and/or p-phenylenediamine (PPD);
When amine monomers is piperazine, its concentration is 0.01 ~ 5wt%;
When amine monomers be p-phenylenediamine (PPD) and/or m-phenylene diamine (MPD) time, its integrated concentration is 0.5 ~ 6wt%;
Acyl chlorides monomer in described step (3) is any one or several in o-phthaloyl chloride, paraphthaloyl chloride, m-phthaloyl chloride, connection phenyl-diformyl, pyromellitic trimethylsilyl chloride, benzene-disulfo-chloride, fourth three acyl chlorides, succinyl chloride, penta 3 acyl chlorides, glutaryl chlorine, cyclohexane diacid chloride, cyclohexane three acyl chlorides, cyclohexane four acyl chlorides, oxolane diacid chloride, oxolane four acyl chlorides, cyclopropane three acyl chlorides, cyclobutane diacid chloride, cyclobutane four acyl chlorides, pentamethylene diacid chloride;
When acyl chlorides monomer is pyromellitic trimethylsilyl chloride, its concentration is 0.1 ~ 5wt%;
When acyl chlorides monomer is any one or several in other acyl chlorides monomers, its integrated concentration is 0.01 ~ 2wt%.
3. the preparation method with the NF membrane of nano hybridization desalination layer according to claim 2, it is characterized in that: after the surface finish squeezing roller process in described step (4) terminates, adopt the organic phase solvent on air-dry mode process removal diaphragm, wind speed range is 0.1m/s ~ 20m/s; Temperature is 15 ~ 60 DEG C.
4. the preparation method with the NF membrane of nano hybridization desalination layer according to claim 3, it is characterized in that: after described air-dry process terminates, concentrated sulfuric acid aqueous solution is adopted to carry out sulfonation process to the nano combined NF membrane surface after removing organic phase solvent, wherein, sulfuric acid concentration is 10 ~ 80wt%, sulfuric acid solution temperature is 15 ~ 70 DEG C, and the sulfonation processing time is 1 ~ 120min.
5. the preparation method with the NF membrane of nano hybridization desalination layer according to claim 2, it is characterized in that: after the moisturizing process in described step (5) terminates, adopt drying mode process, bake out temperature is 20 ~ 120 DEG C, and drying time is 2 ~ 60min.
6. the preparation method with the NF membrane of nano hybridization desalination layer according to claim 2, is characterized in that: the pH value of described adjustment solution A is 7 ~ 10; Described squeezing roller pressure is 0.2 ~ 3MPa; The concentration of nano particle in described step (1) in solution A or B solution is for being 0.005 ~ 30wt%; The particle diameter of described nano particle is 1-500nm; Described when amine monomers is piperazine, its concentration is 0.05 ~ 2wt%; Described when amine monomers be p-phenylenediamine (PPD) and/or m-phenylene diamine (MPD) time, its integrated concentration is 1wt% ~ 4wt%; Described when acyl chlorides monomer is pyromellitic trimethylsilyl chloride, its concentration is 0.5 ~ 3wt%; Described when acyl chlorides monomer is any one or several in other acyl chlorides monomers, its integrated concentration is 0.03 ~ 1.5wt%.
7. the preparation method with the NF membrane of nano hybridization desalination layer according to claim 2, is characterized in that: the pH value of described adjustment solution A is 8 ~ 9; Described squeezing roller pressure is 0.2 ~ 1MPa; The concentration of nano particle in described step (1) in solution A or B solution is for being 0.01 ~ 20wt%; The particle diameter of described nano particle is 5 ~ 200nm.
8. the preparation method with the NF membrane of nano hybridization desalination layer according to claim 2, is characterized in that: the particle diameter of described nano particle is 10 ~ 100nm.
9. the preparation method with the NF membrane of nano hybridization desalination layer according to claim 2, it is characterized in that: after the surface finish squeezing roller process in described step (4) terminates, adopt the organic phase solvent on air-dry mode process removal diaphragm, wind speed range is 1m/s ~ 5m/s; Temperature is 30 ~ 50 DEG C.
10. the preparation method with the NF membrane of nano hybridization desalination layer according to claim 3, it is characterized in that: after described air-dry process terminates, concentrated sulfuric acid aqueous solution is adopted to carry out sulfonation process to the nano combined NF membrane surface after removing organic phase solvent, wherein, sulfuric acid concentration is 20 ~ 50wt%, and sulfuric acid solution temperature is 40 ~ 60 DEG C.
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