CN102824859B - Method for preparing hollow fiber nanofiltration membrane by using thermally induced phase separation/interface cross linking synchronization method - Google Patents
Method for preparing hollow fiber nanofiltration membrane by using thermally induced phase separation/interface cross linking synchronization method Download PDFInfo
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Abstract
The invention discloses a method for preparing a hollow fiber nanofiltration membrane by using a thermally induced phase separation/interface cross linking synchronization method; the preparation method comprises the following steps: 1) mixing polymer, a diluting agent and a cross linking agent to form a homogeneous phase membrane casting solution; 2) extruding the membrane casting solution and core solution, or the membrane casting solution and nitrogen by a ring-shaped spinning head, then conducting the thermally induced phase separation in a cooling bath so as to obtain a hollow primary membrane; 3) soaking the hollow primary membrane in extracting solution containing cross linking pre-polymer, conducting the interface cross linking at the same time with removing diluting agent, thereby obtaining a hollow fiber nanofiltration membrane. According to the method provided by the invention, the preparations of holing and separation layer is finished, and the difficulty point of high require of bonding property between a separation layer and a supporting layer of a combining method in the prior art can be avoided, and meanwhile the thickness and the evenness of the separation layer are easy to control; the simple new method for preparing the hollow fiber nanofiltration membrane with excellent property by using the thermally induced phase separation/interface cross linking synchronization method is provided; and the prepared nanofiltration membrane is little in defect, high in stability and high in controllability.
Description
Technical field
The present invention relates to the preparing technical field of diffusion barrier, be specifically related to the method for be separated/interface-cross-linked synchronous legal system of a kind of thermic for hollow fiber nanofiltration membrane.
Background technology
NF membrane is the Novel separation film growing up phase late 1980s.It has, and operating pressure requirement is low, flux is higher, inorganic salts and molecular weight are had to the features such as higher rejection between 200～1000 organic matter, there is unrivaled advantage separating of organic matter and inorganic matter mixed liquor aspect concentrated, be widely used in that drink water purifying, water for industrial use are softening at present, the field such as concentrated and purifying of composition in wastewater treatment, pharmacy and grocery trade.
Composite algorithm is to use at present at most and the most effective NF membrane preparation method, and it adopts coating process, interfacial polymerization, situ aggregation method, Plasma Polymerization and power forming method etc. to introduce nanofiltration separation layer on porous support membrane surface conventionally.Prepare hydrophilic polyethylene glycol composite nanofiltration membrane as Chinese patent CN100448518C discloses a kind of crosslinked method of coating-electron irradiation that adopts, this preparation method comprises: compound concentration is 1 × 10
-4the polyethylene glycol coating liquor of g/L～3g/L, is coated in prepared polyethylene glycol coating liquor the surface of basement membrane equably, after drying at room temperature polyethylene glycol coat film; Coat film is put into electron accelerator field irradiation, irradiation dose is 5GRY～1 × 10 again
4gRY, exposure time is 1min～10min; Coat film after irradiation is at room temperature placed 12h～24h, obtains polyethylene glycol composite nanofiltration membrane.Polyethylene glycol composite nanofiltration membrane of the present invention adopts polyethylene glycol composite nanofiltration membrane preparation method preparation of the present invention and obtains.This preparation method does not introduce chemical cross-linking agent, does not have organic liquor residual and pollute, and be of value to environmental protection, and component easily purchases, with low cost, is convenient to practical application.This NF membrane has good hydrophily, separation selectivity and water penetration, and resistance to Organic Pollution.Chinese patent application CN 200810059988.3 discloses a kind of take TPO doughnut micropore basal membrane as supporting layer, take polyvinyl alcohol based polymer as transition zone, react the polyamide cortex that the obtains high strength external-compression type Nano filtering composite membrane of hollow fiber as nanofiltration separation layer to be carried out interfacial polycondensation by polyamine solution and polynary acyl halide solution.At present to be mainly with existing membrane material that basement membrane carries out compound for the structure of the hollow fiber nanofiltration membrane composite bed of report, although be better than Flat Membrane aspect antipollution, assembly loadings, but its preparation technology still adopts multiple steps, technical bottleneck has further limited the development of doughnut composite nanometer filtering film.A kind of film-forming process that adopts coating-interfacial polymerization thing is disclosed in Chinese invention patent CN1806901A, dimethylaminoethyl methacrylate-acrylic acid copolymer is coated on to membrane surface, by interface polymerization reaction, coat and basement membrane are cross-linked, thereby make the hydrophobic NF membrane with positive and negative charge simultaneously.A kind of preparation method of polymer hollow fiber composite NF membrane is disclosed in Chinese invention patent CN1785488A, by basement membrane alternately dip-coating in aqueous phase solution and oil-phase solution, make two kinds of dip-coating solution adhere to concurrent biochemical reaction and generate compound separating layer in membrane surface, gained doughnut composite nanometer filtering film is greater than 90% to sodium sulphate rejection.But, the above-mentioned technique part that still comes with some shortcomings: 1. process is loaded down with trivial details; 2. the bad adhesion of supporting layer and composite bed, defect is many; 3. composite bed thickness is difficult to control, and uniformity is not good; 4. be not suitable for hollow fiber nanofiltration membrane, the preparation difficulty of especially interior press mold.Therefore the promotion and application of nanofiltration have greatly been limited.
Summary of the invention
The invention provides a kind of thermic to be separated/interface-cross-linked synchronous legal system is for the method for hollow fiber nanofiltration membrane, and the method is simple, is easy to realize inside and outside pressure type hollow fiber NF membrane, and prepared NF membrane defect is few, stability is high, controllability is strong.
Be separated/interface-cross-linked synchronous legal system of thermic is for a method for hollow fiber nanofiltration membrane, and basic principle is that polymer, diluent and crosslinking agent are mixed, and at high temperature forms homogeneous phase casting solution, and then cooling bringing out is separated at a lower temperature.There is exchange of solvent in the extract that utilization contains crosslinked prepolymer, crosslinked prepolymer forms separating layer in film surface under crosslinking agent effect, makes hollow fiber nanofiltration membrane, specifically comprises the steps: while removing diluent
(1) polymer, diluent and crosslinking agent are mixed, be mixed into homogeneous phase solution at 120 ℃～160 ℃, standing and defoaming, obtains casting solution; Wherein the mass ratio of polymer, diluent and crosslinking agent is 10～40: 60～90: 1～3;
(2) by the casting solution in the casting solution in step (1) and core liquid or step (1) and nitrogen under 120 ℃～160 ℃, 0.1MPa～0.3MPa pressure, speed with 0.5 m/min～20 ms/min is extruded by ring-type spinneret, immerse in the cooling bath of 20 ℃～50 ℃, obtain the nascent film of hollow;
(3) crosslinked prepolymer is mixed with to the extract of 1g/L～15g/L, nascent the hollow in step (2) film is soaked 2 hours～12 hours in the extract of 30 ℃～60 ℃, obtain hollow fiber nanofiltration membrane.
Described polymer can be selected NF membrane basement membrane polymer used etc., preferably the one in Kynoar, polyacrylonitrile, polysulfones, polyether sulfone, cellulose acetate, polyimides, PEI.
The feature of described diluent is that boiling point is more than 180 ℃, energy dissolve polymer heats up, and a kind of or dimethyl sulfone in cyclohexanone, gamma-butyrolacton, propene carbonate, repefral, dibutyl phthalate, dimethyl sulfone and the mixture of 1-METHYLPYRROLIDONE are selected in cooling and polymer generation phase-splitting.In described dimethyl sulfone and the mixture of 1-METHYLPYRROLIDONE, the mass percent of 1-METHYLPYRROLIDONE is preferably greater than 0 and be less than or equal to 50%.
Described core liquid can adopt the conventional core liquid in this area, the solvent of the polymer of specifically selecting boiling point more than 180 ℃ and in can not dissolving casting solution, can select alcoholic solvent or the boiling point ester solvent 180 ℃ or more of boiling point more than 180 ℃, as the one in glycerine, ethylene glycol, BDO, polyethylene glycol, dibutyl phthalate etc.
Described nitrogen plays core liquid.
Described crosslinking agent is selected benzyl dichloride, glutaraldehyde, epoxychloropropane or hexamethylene diisocyanate.
Described cooling bath adopts air.
The feature of described extract is the low boiling point solvent of energy dissolved dilution agent and the mixed solution of crosslinked prepolymer; Therefore, the solvent of described extract is selected the low boiling point solvent of energy dissolved dilution agent, the mixture of preferred water, ethanol or water and ethanol; Described crosslinked prepolymer is selected polymine, polymethylacrylic acid dimethylaminoethyl, sulfated chitosan or sodium cellulose glycolate.
The ring-type spinneret (as shown in Figure 2) that described ring-type spinneret is existing device for spinning, described casting solution adopts the ring-type spinneret of existing device for spinning to extrude.
Tool of the present invention has the following advantages and beneficial effect:
Thermic of the present invention is separated/introduce crosslinked prepolymer when interface-cross-linked same footwork utilization extraction pore, form separating layer with crosslinking agent generation chemical crosslinking in nascent film.The method one step completes the preparation of pore and separating layer, can avoid conventional composite method to require high difficult point to close-burning between separating layer and supporting layer, the thickness of separating layer and uniformity are easy to control simultaneously, and the new method of be separated/interface-cross-linked synchronous legal system of a kind of simple thermic for the hollow fiber nanofiltration membrane of function admirable is provided.
Accompanying drawing explanation
Fig. 1 is the structural representation of existing NF membrane performance evaluation instrument, the wherein flow direction of arrow express liquid;
Fig. 2 is the cross-sectional view of the ring-type spinneret of existing device for spinning.
The specific embodiment
By following examples, the present invention is described in more detail, but described embodiment is not construed as limiting the invention.
Adopt NF membrane performance evaluation instrument to measure water flux and salt rejection, NF membrane performance evaluation instrument is existing instrument, as shown in Figure 1, comprise the feeding liquid storage tank 1 connecting by pipeline successively, feed pump 2, buffer solution storage tank 4, hollow fiber film assembly 6 and flowmeter 9, on pipeline between feed pump 2 and buffering liquid storage tank 4, be connected with the backflow branch road with control valve 3, the outlet access feeding liquid storage tank 1 of this backflow branch road, pipeline between buffer solution storage tank 4 and hollow fiber film assembly 6 is provided with pressure gauge 5, in hollow fiber film assembly 6, be provided with the outlet of hollow-fibre membrane inner chamber diffusate and the outlet of doughnut film outer surface raffinate, the outlet of doughnut film outer surface raffinate and flowmeter 9, feeding liquid storage tank 1 connects by pipeline, on the pipeline between the outlet of doughnut film outer surface raffinate and flowmeter 9, be provided with pressure gauge 7 and control valve 8.
Water or feeding liquid ooze out under feed pump 2 effects from feeding liquid storage tank 1 after buffer solution storage tank 4 enters hollow fiber film assembly 6, can measure water flux and salt rejection.
To select mass ratio be polyacrylonitrile, the dimethyl sulfone of 10: 90: 1 and benzyl dichloride is added in stirred tank and mixed, and is heated to 160 ℃, is stirred well to mixture and is tied to form after homogeneous phase solution, and standing and defoaming, obtains casting solution; Selecting glycerine is core liquid; Casting solution and core liquid, under 160 ℃, 0.2MPa pressure, are extruded by the outer hole of ring-type spinneret with the speed of 3 ms/min, then immersed in the air bath of 30 ℃, obtain the nascent film of hollow.Nascent hollow film is soaked 8 hours in the polyethyleneimine: amine aqueous solution that 40 ℃, polymine concentration are 5g/L, take out, obtain polyacrylonitrile hollow fiber nanofiltration membrane.
Above-mentioned hollow fiber nanofiltration membrane is made after membrane module, adopt NF membrane performance evaluation instrument to measure the water volume that hollow fiber nanofiltration membrane permeates within the unit interval, measure water flux according to formula (1), calculate respectively feeding liquid concentration and diffusate concentration by measuring the electrical conductivity of feeding liquid and the electrical conductivity of diffusate, calculate the rejection of magnesium sulfate, sodium chloride according to formula (2).
In formula (1), J
wfor water flux, the volume that V is infiltration water, A is the effective area (being the external surface area of film) of film in membrane module, Δ t is the infiltration time used;
In formula (2), R is rejection, C
ffor feeding liquid concentration, C
pfor diffusate concentration.
Measure 25 ℃, the rejection of the sodium-chloride water solution of the pure water flux of film and the magnesium sulfate solution of 1g/L and 1g/L under 0.6MPa pressure, test under outside casing part (being that water or feeding liquid are oozed out by inner chamber under pressure after doughnut film outer surface separates): water flux is 15Lm-
2h
-1, the rejection of magnesium sulfate is 93%, the rejection of sodium chloride is 56%.
Comparative example 1
Select conventional thermic to be at present separated polyacrylonitrile film surface coating cross-linking method as a comparison, the polyacrylonitrile that is 10: 90 by mass ratio and dimethyl sulfone add in stirred tank and mix, and are heated to 160 ℃, are stirred well to mixture and are tied to form after homogeneous phase solution, standing and defoaming, obtains casting solution; Selecting glycerine is core liquid; Casting solution and core liquid, under 160 ℃, 0.2MPa pressure, are extruded by the outer hole of ring-type spinneret with the speed of 3 ms/min, is immersed in the air bath of 30 ℃, generate the hollow film of coming into being; After extracting dimethyl sulfone again in the water-bath of 40 ℃, make polyacrylonitrile hollow membrane; The polyethyleneimine: amine aqueous solution dip-coating of 5g/L, in polyacrylonitrile hollow fiber membrane surface, then is soaked 8 hours in the hexane solution of 2g/L benzyl dichloride, take out, obtain polyacrylonitrile hollow fiber nanofiltration membrane.
Above-mentioned hollow fiber nanofiltration membrane is made to the rejection of test water flux and magnesium sulfate after membrane module, sodium chloride, test is with embodiment 1, measure 25 ℃, the rejection of the sodium-chloride water solution of the pure water flux of film and the magnesium sulfate solution of 1g/L and 1g/L under 0.6MPa pressure, under outside casing part, test, water flux is 44Lm
-2h
-1(0.1MPa)
-1, magnesium sulfate rejection rate is 60%, the rejection of sodium chloride is 30%.Water flux is large, little to magnesium sulfate sodium chloride rejection be due to the problem such as have defect in compound separating layer and peel off.
Embodiment 2
To select mass ratio be polyacrylonitrile, the propene carbonate of 20: 80: 1 and benzyl dichloride is added in stirred tank and mixed, and is heated to 160 ℃, is stirred well to mixture and is tied to form after homogeneous phase solution, and standing and defoaming, obtains casting solution; Selecting glycerine is core liquid; By casting solution and core liquid under 160 ℃, 0.2MPa pressure, with the speed of 3 ms/min by ring-type spinneret outside hole extrude, then immerse in the air bath of 30 ℃, obtain the nascent film of hollow.Nascent hollow film is soaked 8 hours in the polymethylacrylic acid dimethylaminoethyl ethanolic solution that 40 ℃, polymethylacrylic acid dimethylaminoethyl concentration are 5g/L, take out, obtain polyacrylonitrile hollow fiber nanofiltration membrane.
Above-mentioned hollow fiber nanofiltration membrane is made to the rejection of test water flux and magnesium sulfate after membrane module, sodium chloride, test is with embodiment 1, measure 25 ℃, the rejection of the sodium-chloride water solution of the pure water flux of film and the magnesium sulfate solution of 1g/L and 1g/L under 0.6MPa pressure, under outside casing part, test, water flux is 31Lm
-2h
-1, the rejection of magnesium sulfate is 87%, the rejection of sodium chloride is 51%.
To select mass ratio be Kynoar, the cyclohexanone of 30: 70: 3 and benzyl dichloride is added in stirred tank and mixed, and is heated to 140 ℃, is stirred well to mixture and is tied to form after homogeneous phase solution, and standing and defoaming, obtains casting solution; Selecting number-average molecular weight is that 200 polyethylene glycol is core liquid; By casting solution and core liquid under 140 ℃, 0.2MPa pressure, with the speed of 5 ms/min by ring-type spinneret outside hole extrude, then immerse in the air bath of 20 ℃, obtain the nascent film of hollow.Nascent hollow film is soaked 12 hours in the polymine ethanolic solution that 60 ℃, polymine concentration are 15g/L, take out, obtain polyvinylidene fluoride hollow fiber NF membrane.
Above-mentioned hollow fiber nanofiltration membrane is made to the rejection of test water flux and magnesium sulfate after membrane module, sodium chloride, test is with embodiment 1, measure 25 ℃, the rejection of the sodium-chloride water solution of the pure water flux of film and the magnesium sulfate solution of 1g/L and 1g/L under 0.6MPa pressure, under outside casing part, test, water flux is 25Lm
-2h
-1, the rejection of magnesium sulfate is 90%, the rejection of sodium chloride is 47%.
Embodiment 4
To select mass ratio be Kynoar, the gamma-butyrolacton of 30: 70: 3 and benzyl dichloride is added in stirred tank and mixed, and is heated to 140 ℃, is stirred well to mixture and is tied to form after homogeneous phase solution, and standing and defoaming, obtains casting solution; Selecting number-average molecular weight is that 200 polyethylene glycol is core liquid; By casting solution and core liquid under 140 ℃, 0.2MPa pressure, with the speed of 5 ms/min by ring-type spinneret outside hole extrude, then immerse in the air bath of 20 ℃, obtain the nascent film of hollow.Nascent hollow film is soaked 12 hours in the polymethylacrylic acid dimethylaminoethyl aqueous solution that 60 ℃, polymethylacrylic acid dimethylaminoethyl concentration are 15g/L, take out, obtain polyvinylidene fluoride hollow fiber NF membrane.
Above-mentioned hollow fiber nanofiltration membrane is made to the rejection of test water flux and magnesium sulfate after membrane module, sodium chloride, test is with embodiment 1, measure 25 ℃, the rejection of the sodium-chloride water solution of the pure water flux of film and the magnesium sulfate solution of 1g/L and 1g/L under 0.6MPa pressure, under outside casing part, test, water flux is 29Lm
-2h
-1, the rejection of magnesium sulfate is 89%, the rejection of sodium chloride is 49%.
Selecting mass ratio is that Kynoar, propene carbonate and the glutaraldehyde of 40: 60: 3 adds in stirred tank and mix, and is heated to 140 ℃, is stirred well to mixture and is tied to form after homogeneous phase solution, and standing and defoaming, obtains casting solution; Selecting glycerine is core liquid; By casting solution and core liquid under 140 ℃, 0.2MPa pressure, with the speed of 5 ms/min by ring-type spinneret outside hole extrude, then immerse in the air bath of 20 ℃, obtain the nascent film of hollow.Nascent hollow film is soaked 12 hours in the chitosan sulfate aqueous solution of ester that 60 ℃, chitosan sulfate ester concentration are 15g/L, take out, obtain polyvinylidene fluoride hollow fiber NF membrane.
Above-mentioned hollow fiber nanofiltration membrane is made to the rejection of test water flux and magnesium sulfate after membrane module, sodium chloride, test is with embodiment 1, measure 25 ℃, the rejection of the sodium-chloride water solution of the pure water flux of film and the magnesium sulfate solution of 1g/L and 1g/L under 0.6MPa pressure, under outside casing part, test, water flux is 19Lm
-2h
-1, the rejection of magnesium sulfate is 92%, the rejection of sodium chloride is 48%.
To select mass ratio be Kynoar, the repefral of 20: 80: 3 and benzyl dichloride is added in stirred tank and mixed, and is heated to 140 ℃, is stirred well to mixture and is tied to form after homogeneous phase solution, and standing and defoaming, obtains casting solution; By casting solution and nitrogen under 140 ℃, 0.2MPa pressure, with the speed of 5 ms/min by ring-type spinneret outside hole extrude, then immerse in the air bath of 20 ℃, obtain the nascent film of hollow.Nascent hollow film is soaked 12 hours in the polymine ethanolic solution that 60 ℃, polymine concentration are 5g/L, take out, obtain polyvinylidene fluoride hollow fiber NF membrane.
Above-mentioned hollow fiber nanofiltration membrane is made to the rejection of test water flux and magnesium sulfate after membrane module, sodium chloride, test is with embodiment 1, measure 25 ℃, the rejection of the sodium-chloride water solution of the pure water flux of film and the magnesium sulfate solution of 1g/L and 1g/L under 0.6MPa pressure, under outside casing part, test, water flux is 21Lm
-2h
-1, the rejection of magnesium sulfate is 90%, the rejection of sodium chloride is 50%.
Selecting mass ratio is that Kynoar, dibutyl phthalate and the hexamethylene diisocyanate of 20: 80: 3 adds in stirred tank and mix, and is heated to 140 ℃, is stirred well to mixture and is tied to form after homogeneous phase solution, and standing and defoaming, obtains casting solution; Selecting glycerine is core liquid; By casting solution and core liquid under 140 ℃, 0.2MPa pressure, with the speed of 5 ms/min by ring-type spinneret outside hole extrude, then immerse in the air bath of 20 ℃, obtain the nascent film of hollow.Nascent hollow film is soaked 12 hours in the polymine ethanolic solution that 60 ℃, polymine concentration are 5g/L, take out, obtain polyvinylidene fluoride hollow fiber NF membrane.
Above-mentioned hollow fiber nanofiltration membrane is made to the rejection of test water flux and magnesium sulfate after membrane module, sodium chloride, test is with embodiment 1, measure 25 ℃, the rejection of the sodium-chloride water solution of the pure water flux of film and the magnesium sulfate solution of 1g/L and 1g/L under 0.6MPa pressure, under outside casing part, test, water flux is 25Lm
-2h
-1, the rejection of magnesium sulfate is 88%, the rejection of sodium chloride is 48%.
To select mass ratio be Kynoar, the dimethyl sulfone of 10: 90: 3 and benzyl dichloride is added in stirred tank and mixed, and is heated to 120 ℃, is stirred well to mixture and is tied to form after homogeneous phase solution, and standing and defoaming, obtains casting solution; Selecting ethylene glycol is core liquid; By casting solution and core liquid under 120 ℃, 0.3MPa pressure, with the speed of 10 ms/min by ring-type spinneret outside hole extrude, then immerse in the air bath of 30 ℃, obtain the nascent film of hollow.In the ethanol/water mixed solution (in ethanol/water, the volume fraction of ethanol is 50%) of the polymine that is 5g/L at 30 ℃, polymine concentration by nascent hollow film, soak 6 hours, take out, obtain polyvinylidene fluoride hollow fiber NF membrane.
Above-mentioned hollow fiber nanofiltration membrane is made to the rejection of test water flux and magnesium sulfate after membrane module, sodium chloride, test is with embodiment 1, measure 25 ℃, the rejection of the sodium-chloride water solution of the pure water flux of film and the magnesium sulfate solution of 1g/L and 1g/L under 0.6MPa pressure, under outside casing part, test, water flux is 20Lm
-2h
-1, the rejection of magnesium sulfate is 92%, sodium chloride rejection is 49%.
To select mass ratio be Kynoar, the dimethyl sulfone of 20: 80: 2 and benzyl dichloride is added in stirred tank and mixed, and is heated to 120 ℃, is stirred well to mixture and is tied to form after homogeneous phase solution, and standing and defoaming, obtains casting solution; Selecting BDO is core liquid; By casting solution and core liquid under 120 ℃, 0.3MPa pressure, with the speed of 10 ms/min by ring-type spinneret outside hole extrude, then immerse in the air bath of 30 ℃, obtain the nascent film of hollow.In the ethanol/water mixed solution (in ethanol/water, the volume fraction of ethanol is 50%) of the polymine that is 5g/L at 30 ℃, polymine concentration by nascent hollow film, soak 6 hours, take out, obtain polyvinylidene fluoride hollow fiber NF membrane.
Above-mentioned hollow fiber nanofiltration membrane is made to the rejection of test water flux and magnesium sulfate after membrane module, sodium chloride, test is with embodiment 1, measure 25 ℃, the rejection of the sodium-chloride water solution of the pure water flux of film and the magnesium sulfate solution of 1g/L and 1g/L under 0.6MPa pressure, under outside casing part, test, water flux is 16Lm
-2h
-1, the rejection of magnesium sulfate is 93%, the rejection of sodium chloride is 53%.
Embodiment 10
To select mass ratio be Kynoar, the dimethyl sulfone of 30: 70: 2 and benzyl dichloride is added in stirred tank and mixed, and is heated to 120 ℃, is stirred well to mixture and is tied to form after homogeneous phase solution, and standing and defoaming, obtains casting solution; Selecting BDO is core liquid; By casting solution and core liquid under 120 ℃, 0.3MPa pressure, with the speed of 20 ms/min by ring-type spinneret outside hole extrude, then immerse in the air bath of 30 ℃, obtain the nascent film of hollow.In the ethanol/water mixed solution (in ethanol/water, the volume fraction of ethanol is 50%) of the polymine that is 1g/L at 30 ℃, polymine concentration by nascent hollow film, soak 2 hours, take out, obtain polyvinylidene fluoride hollow fiber NF membrane.
Above-mentioned hollow fiber nanofiltration membrane is made to the rejection of test water flux and magnesium sulfate after membrane module, sodium chloride, test is with embodiment 1, measure 25 ℃, the rejection of the sodium-chloride water solution of the pure water flux of film and the magnesium sulfate solution of 1g/L and 1g/L under 0.6MPa pressure, under outside casing part, test, water flux is 13Lm
-2h
-1, the rejection of magnesium sulfate is 94%, the rejection of sodium chloride is 58%.
Embodiment 11
To select mass ratio be Kynoar, the dimethyl sulfone of 40: 60: 2 and benzyl dichloride is added in stirred tank and mixed, and is heated to 120 ℃, is stirred well to mixture and is tied to form after homogeneous phase solution, and standing and defoaming, obtains casting solution; Selecting BDO is core liquid; By casting solution and core liquid under 120 ℃, 0.3MPa pressure, with the speed of 20 ms/min by ring-type spinneret outside hole extrude, then immerse in the air bath of 30 ℃, obtain the nascent film of hollow.In the ethanol/water mixed solution (in ethanol/water, the volume fraction of ethanol is 50%) of the polymine that is 1g/L at 30 ℃, polymine concentration by nascent hollow film, soak 2 hours, take out, obtain polyvinylidene fluoride hollow fiber NF membrane.
Above-mentioned hollow fiber nanofiltration membrane is made to the rejection of test water flux and magnesium sulfate after membrane module, sodium chloride, test is with embodiment 1, measure 25 ℃, the rejection of the sodium-chloride water solution of the pure water flux of film and the magnesium sulfate solution of 1g/L and 1g/L under 0.6MPa pressure, under outside casing part, test, water flux is 11Lm
-2h
-1, the rejection of magnesium sulfate is 95%, the rejection of sodium chloride is 61%.
Embodiment 12
Selecting mass ratio is that cellulose acetate, dimethyl sulfone and the hexamethylene diisocyanate of 20: 80: 1 adds in stirred tank and mix, and is heated to 140 ℃, is stirred well to mixture and is tied to form after homogeneous phase solution, and standing and defoaming, obtains casting solution; Selecting dibutyl phthalate is core liquid; By casting solution and core liquid under 140 ℃, 0.1MPa pressure, with the speed of 0.5 m/min by ring-type spinneret outside hole extrude, then immerse in the air bath of 40 ℃, obtain the nascent film of hollow.Nascent hollow film is soaked 12 hours in the sodium cellulose glycolate aqueous solution that 30 ℃, sodium cellulose glycolate concentration are 5g/L, take out, obtain acetyl cellulose hollow fiber nano filter membrane.
Above-mentioned hollow fiber nanofiltration membrane is made to the rejection of test water flux and magnesium sulfate after membrane module, sodium chloride, test is with embodiment 1, measure 25 ℃, the rejection of the sodium-chloride water solution of the pure water flux of film and the magnesium sulfate solution of 1g/L and 1g/L under 0.6MPa pressure, under outside casing part, test, water flux is 14Lm
-2h
-1, the rejection of magnesium sulfate is 92%, the rejection of sodium chloride is 51%.
Embodiment 13
Selecting mass ratio is that cellulose acetate, dimethyl sulfone and the hexamethylene diisocyanate of 30: 70: 1 adds in stirred tank and mix, and is heated to 140 ℃, is stirred well to mixture and is tied to form after homogeneous phase solution, and standing and defoaming, obtains casting solution; Selecting dibutyl phthalate is core liquid; By casting solution and core liquid under 140 ℃, 0.1MPa pressure, with the speed of 0.5 m/min by ring-type spinneret outside hole extrude, then immerse in the air bath of 40 ℃, obtain the nascent film of hollow.Nascent hollow film is soaked 12 hours in the sodium cellulose glycolate aqueous solution that 30 ℃, sodium cellulose glycolate concentration are 5g/L, take out, obtain acetyl cellulose hollow fiber nano filter membrane.
Above-mentioned hollow fiber nanofiltration membrane is made to the rejection of test water flux and magnesium sulfate after membrane module, sodium chloride, test is with embodiment 1, measure 25 ℃, the rejection of the sodium-chloride water solution of the pure water flux of film and the magnesium sulfate solution of 1g/L and 1g/L under 0.6MPa pressure, under outside casing part, test, water flux is 9Lm
-2h
-1, the rejection of magnesium sulfate is 96%, the rejection of sodium chloride is 54%.
Embodiment 14
To select mass ratio be polyether sulfone, dimethyl sulfone/1-METHYLPYRROLIDONE mixture (wherein the mass percent of 1-METHYLPYRROLIDONE is 20%) of 20: 80: 3 and benzyl dichloride is added in stirred tank and mixed, be heated to 160 ℃, being stirred well to mixture is tied to form after homogeneous phase solution, standing and defoaming, obtains casting solution; Selecting glycerine is core liquid; By casting solution and core liquid under 160 ℃, 0.2MPa pressure, with the speed of 10 ms/min by ring-type spinneret outside hole extrude, then immerse in the air bath of 50 ℃, obtain the nascent film of hollow.Nascent hollow film is soaked 12 hours in the polymine ethanolic solution that 40 ℃, polymine concentration are 15g/L, take out, obtain Polyethersulfone Hollow Fiber Plasma NF membrane.
Above-mentioned hollow fiber nanofiltration membrane is made to the rejection of test water flux and magnesium sulfate after membrane module, sodium chloride, test is with embodiment 1, measure 25 ℃, the rejection of the sodium-chloride water solution of the pure water flux of film and the magnesium sulfate solution of 1g/L and 1g/L under 0.6MPa pressure, under outside casing part, test, water flux is 19Lm
-2h
-1, the rejection of magnesium sulfate is 91%, the rejection of sodium chloride is 47%.
Embodiment 15
Selecting mass ratio is that polyether sulfone, dimethyl sulfone/1-METHYLPYRROLIDONE mixture (wherein the mass percent of 1-METHYLPYRROLIDONE is 30%) and the hexamethylene diisocyanate of 30: 70: 3 adds in stirred tank and mix, be heated to 160 ℃, being stirred well to mixture is tied to form after homogeneous phase solution, standing and defoaming, obtains casting solution; Selecting number-average molecular weight is that 200 polyethylene glycol is core liquid; By casting solution and core liquid under 160 ℃, 0.3MPa pressure, with the speed of 20 ms/min by ring-type spinneret outside hole extrude, then immerse in the air bath of 50 ℃, obtain the nascent film of hollow.Nascent hollow film is soaked 12 hours in the chitosan sulfate aqueous solution of ester that 40 ℃, chitosan sulfate ester concentration are 15g/L, take out, obtain Polyethersulfone Hollow Fiber Plasma NF membrane.
Above-mentioned hollow fiber nanofiltration membrane is made to the rejection of test water flux and magnesium sulfate after membrane module, sodium chloride, test is with embodiment 1, measure 25 ℃, the rejection of the sodium-chloride water solution of the pure water flux of film and the magnesium sulfate solution of 1g/L and 1g/L under 0.6MPa pressure, under outside casing part, test, water flux is 12Lm
-2h
-1, the rejection of magnesium sulfate is 93%, the rejection of sodium chloride is 53%.
Embodiment 16
To select mass ratio be polysulfones, dimethyl sulfone/1-METHYLPYRROLIDONE mixture (wherein the mass percent of 1-METHYLPYRROLIDONE is 50%) of 20: 80: 3 and benzyl dichloride is added in stirred tank and mixed, be heated to 160 ℃, being stirred well to mixture is tied to form after homogeneous phase solution, standing and defoaming, obtains casting solution; Selecting glycerine is core liquid; By casting solution and core liquid under 160 ℃, 0.3MPa pressure, with the speed of 20 ms/min by ring-type spinneret outside hole extrude, then immerse in the air bath of 50 ℃, obtain the nascent film of hollow.Nascent hollow film is soaked 8 hours in the polymethylacrylic acid dimethylaminoethyl ethanolic solution that 50 ℃, polymethylacrylic acid dimethylaminoethyl concentration are 10g/L, take out, obtain polysulfone hollow fibre NF membrane.
Above-mentioned hollow fiber nanofiltration membrane is made to the rejection of test water flux and magnesium sulfate after membrane module, sodium chloride, test is with embodiment 1, measure 25 ℃, the rejection of the sodium-chloride water solution of the pure water flux of film and the magnesium sulfate solution of 1g/L and 1g/L under 0.6MPa pressure, under outside casing part, test, water flux is 21Lm
-2h
-1, the rejection of magnesium sulfate is 90%, the rejection of sodium chloride is 49%.
Embodiment 17
Selecting mass ratio is that polyimides, dimethyl sulfone/1-METHYLPYRROLIDONE mixture (wherein the mass percent of 1-METHYLPYRROLIDONE is 50%) and the epoxychloropropane of 20: 80: 3 adds in stirred tank and mix, be heated to 120 ℃, being stirred well to mixture is tied to form after homogeneous phase solution, standing and defoaming, obtains casting solution; Selecting glycerine is core liquid; By casting solution and core liquid under 120 ℃, 0.3MPa pressure, with the speed of 20 ms/min by ring-type spinneret outside hole extrude, then immerse in the air bath of 30 ℃, obtain the nascent film of hollow.Nascent hollow film is soaked 12 hours in the chitosan sulfate aqueous solution of ester that 50 ℃, chitosan sulfate ester concentration are 15g/L, take out, obtain polyimide hollow fiber NF membrane.
Above-mentioned hollow fiber nanofiltration membrane is made to the rejection of test water flux and magnesium sulfate after membrane module, sodium chloride, test is with embodiment 1, measure 25 ℃, the rejection of the sodium-chloride water solution of the pure water flux of film and the magnesium sulfate solution of 1g/L and 1g/L under 0.6MPa pressure, under outside casing part, test, water flux is 14Lm
-2h
-1, the rejection of magnesium sulfate is 91%, the rejection of sodium chloride is 45%.
Embodiment 18
Selecting mass ratio is that PEI, dimethyl sulfone/1-METHYLPYRROLIDONE mixture (wherein the mass percent of 1-METHYLPYRROLIDONE is 50%) and the epoxychloropropane of 20: 80: 3 adds in stirred tank and mix, be heated to 120 ℃, being stirred well to mixture is tied to form after homogeneous phase solution, standing and defoaming, obtains casting solution; Selecting glycerine is core liquid; By casting solution and core liquid under 120 ℃, 0.3MPa pressure, with the speed of 20 ms/min by ring-type spinneret outside hole extrude, then immerse in the air bath of 30 ℃, obtain the nascent film of hollow.Nascent hollow film is soaked 8 hours in the sodium cellulose glycolate aqueous solution that 50 ℃, sodium cellulose glycolate concentration are 10g/L, take out, obtain PEI hollow fiber nanofiltration membrane.
Above-mentioned hollow fiber nanofiltration membrane is made to the rejection of test water flux and magnesium sulfate after membrane module, sodium chloride, test is with embodiment 1, measure 25 ℃, the rejection of the sodium-chloride water solution of the pure water flux of film and the magnesium sulfate solution of 1g/L and 1g/L under 0.6MPa pressure, under outside casing part, test, water flux is 12Lm
-2h
-1, the rejection of magnesium sulfate is 92%, the rejection of sodium chloride is 55%.
Claims (6)
1. be separated/interface-cross-linked synchronous legal system of thermic, for a method for hollow fiber nanofiltration membrane, is characterized in that, comprises the following steps:
(1) polymer, diluent and crosslinking agent are mixed, be mixed into homogeneous phase solution at 120 ℃～160 ℃, standing and defoaming, obtains casting solution; Wherein the mass ratio of polymer, diluent and crosslinking agent is 10～40:60～90:1～3;
Described polymer comprises Kynoar, polyacrylonitrile, polysulfones, polyether sulfone, cellulose acetate, polyimides or PEI;
(2) by the casting solution in the casting solution in step (1) and core liquid or step (1) and nitrogen under 120 ℃～160 ℃, 0.1MPa～0.3MPa pressure, speed with 0.5 m/min～20 ms/min is extruded by ring-type spinneret, immerse in the cooling bath of 20 ℃～50 ℃, obtain the nascent film of hollow;
(3) crosslinked prepolymer is mixed with to the extract of 1g/L～15g/L, nascent the hollow in step (2) film is soaked 2 hours～12 hours in the extract of 30 ℃～60 ℃, obtain hollow fiber nanofiltration membrane;
Described crosslinked prepolymer is polymine, polymethylacrylic acid dimethylaminoethyl, sulfated chitosan or sodium cellulose glycolate.
2. be separated/interface-cross-linked synchronous legal system of thermic according to claim 1 is for the method for hollow fiber nanofiltration membrane, it is characterized in that, described diluent is a kind of or dimethyl sulfone in cyclohexanone, gamma-butyrolacton, propene carbonate, repefral, dibutyl phthalate, dimethyl sulfone and the mixture of 1-METHYLPYRROLIDONE.
3. be separated/interface-cross-linked synchronous legal system of thermic according to claim 2 is for the method for hollow fiber nanofiltration membrane, it is characterized in that, in described dimethyl sulfone and the mixture of 1-METHYLPYRROLIDONE, the mass percent of 1-METHYLPYRROLIDONE is greater than 0 and be less than or equal to 50%.
4. be separated/interface-cross-linked synchronous legal system of thermic according to claim 1, for the method for hollow fiber nanofiltration membrane, is characterized in that, described crosslinking agent is to benzyl dichloride, glutaraldehyde, epoxychloropropane or hexamethylene diisocyanate.
5. be separated/interface-cross-linked synchronous legal system of thermic according to claim 1, for the method for hollow fiber nanofiltration membrane, is characterized in that, described cooling bath adopts air.
6. be separated/interface-cross-linked synchronous legal system of thermic according to claim 1, for the method for hollow fiber nanofiltration membrane, is characterized in that, the solvent of described extract is the mixture of water, ethanol or water and ethanol.
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| CN103952784A (en) * | 2014-05-09 | 2014-07-30 | 浙江省纺织测试研究院 | Method for preparing polypropylene nanofiber on large scale |
| CN109853087B (en) * | 2018-11-08 | 2021-09-03 | 大连工业大学 | Lignin/cellulose acetate based epoxy modified carbon fiber and preparation method and application thereof |
| CN111013413B (en) * | 2019-12-26 | 2022-03-04 | 贵州省材料产业技术研究院 | Method for preparing loose nanofiltration composite membrane through one-step crosslinking |
| CN112657343A (en) * | 2020-12-02 | 2021-04-16 | 清华大学 | Polyamide hollow fiber composite separation membrane and preparation method thereof |
| CN112657342B (en) * | 2020-12-02 | 2022-12-06 | 清华大学 | Polyamide hollow fiber composite separation membrane and preparation method thereof |
| CN114011248B (en) * | 2021-09-29 | 2023-10-20 | 广州先进技术研究所 | Thermally induced phase separation film-making method capable of changing core liquid type |
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