CN101642683A - Double-layer composite hollow fiber nano-filtration membrane and preparation method and special tool thereof - Google Patents
Double-layer composite hollow fiber nano-filtration membrane and preparation method and special tool thereof Download PDFInfo
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Abstract
The invention discloses a double-layer composite hollow fiber nano-filtration membrane and preparation method and special tool thereof, wherein the nano-filtration membrane comprises a selective separating outer sheath layer and a mechanical inner supporting layer; the selective separating outer sheath layer with the thickness of 10-10000 nm is provided with the membrane holes with the hole diameter of 0.5-2 nm, wherein the thickness of the mechanical inner supporting layer is 1-3mm; the selective separating outer sheath layer and the mechanical inner supporting layer of the double-layer composite hollow fiber nano-filtration membrane are respectively dissolved into the solvent through the high polymer of the selective separating outer sheath layer and the high polymer of the mechanical inner supporting layer. The invention can control the thickness of the selective separating outer sheath layer to be 10-100 nm, thereby greatly reducing the materials of the selective separating outer sheath layer and greatly lowering the cost. The invention effectively controls the internal/external diameter of the membrane, the effective hole diameter of the membrane, the hole rate and the hole diameter distribution by controlling the components of the liquid materials, the spinning condition, the condensing bath and the post processes so as to obtain the high effective separating membrane provided with the good hydrophilic performance, pollution proof and large water flux.
Description
Technical field
The invention belongs to the membrane separation technique field, relate to a kind of two-layer compound hollow fiber nanofiltration membrane and preparation method thereof and specific purpose tool.
Background technology
Nanofiltration (NF) film comes across 70 generation ends of 20th century the earliest. and be the pressure drive membrane between ultrafiltration (UF) film and counter-infiltration (RO) film, once be called as low pressure reverse osmosis film, loose reverse osmosis membrane etc.NF membrane is to develop new membrane isolation technics faster in recent years in the world, has two distinguishing features in application: (1) physics holds back or screening effect-can hold back relative molecular mass 100-2000, and molecular size is about the dissolved constituent of 1nm; (2) charge-inorganic salts are had certain rejection, wherein the rejection to monovalention lower (10%-40%) is then higher to the rejection of divalence and multivalent ion.The special performance of NF membrane technology makes it have the irreplaceable status of other membrane technology in a lot of fields, film separation process that its appearance is not only perfect, and substituting some traditional separation method gradually.
The application of NF membrane maximum is that small organic molecule etc. is separated to soften drinking water and remove organic matter with water, inorganic salts, in addition industrial downstream product desalination and concentrated aspect, it is replacing technologies such as traditional centrifugation, vacuum distillation, heating evaporation, its also be used to give up (dirt) water treatment regeneration.The application of nanofiltration also relates to numerous industries such as pharmacy, dyestuff, petrochemical industry, papermaking, weaving.Nanofiltration not only can provide medicinal water in medicine production, carries out efficient concentration operation, and runs off for economizing on resources and cleaner production provides possible.Nanofiltration also provides new production technology for the dyestuff desalination with concentrating.Aspects such as nanofiltration concentrates at amino acid in addition, organic acid is purified, active substance of plant extracts and concentrate have also obtained extensive use.The sale of domestic 8 inches thick nanofiltration membrane components breaks through more than 10,000 in recent years, more than one hundred million yuans of market scales.
Though the market of NF membrane is so big, and annual demand is along with very surprising of the Application and Development amplification in more voluminous industry, but the main production and supply of NF membrane is still monopolized by offshore company, as Japan day eastern electrician (NittoDenko) group, east beautiful (Toray) company, Hydranautics (the Hydranautics of the U.S., became the wholly-owned subsidiary of Japan eastern worker of day group in 1987), Filmtec (becoming the wholly-owned subsidiary of U.S.'s Dow Chemcal (DOW Chemical) company in 1985), Fluid system (now being the subsidiary of U.S. KOCH company), Desel (now being the subsidiary of U.S. Osmonics company), companies such as Trisep.China since the later stage eighties 20th century research of NF membrane, research unit mainly contains the Dalian Chemistry and Physics Institute of the Chinese Academy of Sciences, National Bureau of Oceanography's Hangzhou water treatment centers, ecological cyclisation center, Beijing, Shanghai atomic nucleus institute, Tianjin University of Technology, Zhejiang University, Fudan University, Beijing University of Chemical Technology etc., but great majority also are in laboratory stage.
The traditional preparation process technology of NF membrane and the preparation of reverse osmosis membrane are similar, mainly contain phase inversion and composite algorithm etc.Phase inversion is the comparatively simple method of preparation NF membrane, but need carry out modification to membrane material, and adopt this legal system to be equipped with difficulty of composite nanometer filter membrane process, the film of phase inversion preparation does not simultaneously have superior high permeating flux, therefore difficult its filming technology that improves: it is that raw material adopts phase inversion to produce the method for NF membrane with the sulfonated polyether sulfone that Chinese patent 00125306.9 discloses a kind of, this film is under 0.3-0.7MPa, and water flux only is 13-150L/ (m
2H).
It is that (it is basement membrane that Chinese patent 200510014733.1 discloses with polysulfones or polyvinylidene fluoride (PVDF) ultrafiltration membrane as basement membrane employing interface coating process with milipore filter that composite algorithm prepares NF membrane, the surface dip-coating polyacrylate and amino esters polymer aqueous solution is then by the crosslinked method for preparing composite nanometer filtering film of β x ray irradiation x), (Chinese patent 200710172172.7 discloses the method for preparing crosslinked hyperbranched polyalcohol composite nano filter membrance on the porous support membrane by polyalcohol and polynary acyl chlorides interfacial polymerization aromatic polyester function cortex of utilizing to interfacial polymerization; Chinese patent 200410098783.8 discloses a kind of technology that is prepared NF membrane by the big molecule of polyamide and polyacid, multicomponent isocyanate and the interfacial polymerization on porous supporting body of first acyl chlorides), (Chinese patent 200510111540.8 discloses a kind of technology of milipore filter being made NF membrane by the irradiation copolymerized grafting to chemic modified method; Chinese patent 200410053257.X discloses a kind of employing surface grafting, mainly be the method for preparing NF membrane by methods such as low temperature plasma irradiation, ultraviolet irradiation and high-energy ray irradiations) etc., composite algorithm be most widely used at present, also be the most effective method for preparing NF membrane, its advantage is can choose different materials respectively to produce basement membrane and composite bed, makes its performance (as selectivity, permeability, chemistry and heat endurance) reach optimization.But the technological difficulties of composite membrane manufacturing are will be in the product film of wide 1.0-1.6 rice, long hundreds of rice be produced, and forming surperficial uniform thickness is 10-100 nanometer, the flat composite membrane that does not allow needle pore defect.Thick coating can reduce membrane flux, and the thin local defect that can form of coating influences separating property.
Hollow-fibre membrane, as the thin hollow pipe-type film that a kind of oneself supports, when making membrane module, the bulk density of film is big, the effective film area ratio height (10000-30000m in the unit volume
2/ m
3), make that assembly is easy, cost is low, the reasonable distribution by fluid can effectively reduce effects of Concentration Polarization.
Summary of the invention
The performance of NF membrane is closely related with the material of film and preparation technology, obtain structure and performance and satisfy the NF membrane that particular separation requires, and the selection of membrane material and technology of preparing is crucial.When containing better rigidity chemical group such as phenyl ring, heterocycle in the functional layer material of composite membrane (as aromatic polyamides, poly-piperazine amide, fragrant fat mixed polyamide, polyphenyl imipramine, SPSF, the sulfonated polyether sulfone etc.) main chain, close property of the resistance to compression of film and hear resistance are better; Tolerant mechanical strength in the intensity decision composite nanometer filtering film use of basement membrane is so high strength basement membrane (as polysulfones, polyether sulfone, polyacrylonitrile, polyvinyl chloride etc.) will be first-selected.The structure of the ultra-thin function cortex of composite nanometer filtering film directly influences the separating property of film, as adopt certain method to control the crosslinking degree of functional layer network, improve the film surface charge density, can improve the selectivity of NF membrane, improve its chemical stability and stain resistance etc.In addition, the effective aperture of composite nanometer filtering film ultrathin functional layer and pore-size distribution also are the key parameters of decision membrane separating property.The interior external diameter of film forming, effective aperture, porosity and the pore-size distribution of film be can effectively control by regulating feed liquid composition, the control of spinning condition, the setting and the postprocessing working procedures of solidification liquid, good hydrophilic property, antipollution, high-efficient diffusion barrier that water flux is big obtained.
First purpose of the present invention provides the two-layer compound hollow fiber nanofiltration membrane of a kind of separation, resistance to compression, antipollution, chemistry and Heat stability is good.
The technical scheme that realizes first purpose is: a kind of two-layer compound hollow fiber nanofiltration membrane comprises Selective Separation exodermis and mechanical support internal layer; On the Selective Separation exodermis fenestra is arranged, the fenestra aperture is 0.5～2 nanometer; Selective Separation exodermis thickness is 10～10000 nanometers; Layer thickness is 1～3 millimeter in the mechanical support; The Selective Separation exodermis of two-layer compound hollow fiber nanofiltration membrane and mechanical support internal layer are dissolved in the solvent by Selective Separation exodermis high polymer and mechanical support internal layer high polymer respectively.
Solvent described in this programme is N, N '-dimethyl formamide (DMF), N, a kind of in N '-dimethylacetylamide (DMAc), dimethyl pyrrolidone (NMP), dimethyl sulfoxide (DMSO) (DMSO), the oxolane (THF).
Described Selective Separation exodermis high polymer is a kind of in polybenzimidazoles (PBI), sulfonated polyether sulfone (SPES), the SPSF (SPSF), is dissolved in the solvent of claim 2; The two mass percent is 15～25%:75～85%.
High polymer, the mass percent that described mechanical support internal layer high polymer is a mass percent 10～20% is that 2～10% amphipathic nature polyalcohol and mass percent are that the mixture of 2～10% aperture adjustment agent is dissolved in the solvent that mass percent is 60～86% claim 2; Wherein high polymer is a kind of in polysulfones (PSF), polyether sulfone (PES), polyacrylonitrile (PAN), the polyvinyl chloride (PVC); Amphipathic nature polyalcohol is a kind of in styrene-ethylene alcohol copolymer (PSE), styrene-propene acid copolymer (PSA), the styrene-ethylene pyrrolidones copolymer (PSP); The aperture adjustment agent is a kind of in polyethylene glycol (PEG), polyvinylpyrrolidone http://www.tx21.com.cn/test/suliao/200809/81158.html (PVP), the diethylene glycol (DEG) (DG).
Second purpose of the present invention provides a kind of instrument of preparation two-layer compound hollow fiber nanofiltration membrane of special use.
The technical scheme that realizes second purpose is that a kind of specific purpose tool for preparing the two-layer compound hollow fiber nanofiltration membrane comprises special-purpose spray silk instrument, core liquid chamber, internal layer casting film liquid chamber and outer casting film liquid chamber; A described special-purpose spray silk instrument is the triple channel spinning head, comprises the core liquid passage, the internal layer casting solution passage that surrounds core liquid passage that are positioned at the innermost layer, is positioned at outermost outer casting solution passage and is positioned at the spinning nozzle of lower end; The upper end of described core liquid passage, internal layer casting solution passage and outer casting solution passage communicates with core liquid chamber, internal layer casting film liquid chamber and outer casting film liquid chamber respectively, and the lower end communicates with spinning nozzle.
The internal diameter of the core liquid passage lower end of the spinning head of triple channel described in this programme is 0.3～0.85 millimeter; The internal diameter of internal layer casting solution passage lower end is 0.8～1.65 millimeter; The internal diameter of the lower end of outer casting solution passage is 1.2～2 millimeters.
As preferably, comprise that also first of spinning head one side that is positioned at the triple channel spinning head solidifies bathing pool and second and solidify bathing pool; First solidifies bathing pool and second solidifies and is provided with many godets in the bathing pool.
The 3rd purpose of the present invention provides a kind of technology two-layer compound hollow fiber nanofiltration membrane preparation method simple, with low cost.
The scheme that realizes the 3rd purpose is: a kind of method for preparing the two-layer compound hollow fiber nanofiltration membrane may further comprise the steps:
1. the configuration of casting solution: outer casting solution is evenly made 20～60 ℃ of following stirring and dissolving by the Selective Separation exodermis high polymer of claim 3 and the solvent of claim 2; The internal layer casting solution is evenly made 20～60 ℃ of following stirring and dissolving by the solvent of mechanical support internal layer high polymer, amphipathic nature polyalcohol and the aperture adjustment agent and the claim 2 of claim 4;
2. the moulding of two-layer compound hollow fiber nanofiltration membrane: the core liquid passage, internal layer casting solution passage and the outer casting solution passage that core liquid, outer casting solution and internal layer casting solution are injected described triple channel spinning head respectively, be emitted into the tubulose liquid film through spinning nozzle, this liquid film enters first after through 0～20 centimetre the air gap successively and solidifies bathing pool and second and solidify bathing pool, and be wrapped on the wire wrapping wheel, phase transformation is frozen into double-deck hollow-fibre membrane then;
3. cleaning-drying: with solid-state double-deck hollow-fibre membrane after 20～30 ℃ of water loggings bubbles clean 24～72 hours, put into 50 again: the glycerine of 50wt% and aqueous mixtures soaked 24～72 hours, dried to obtain described two-layer compound hollow fiber nanofiltration membrane in air.
Described the 2. the core liquid in the step be the mixture of solvent in 20～60 ℃ water or water and the claim 2 or the mixture of water and non-solvent; Described non-solvent is a kind of in methyl alcohol, ethanol, isopropyl alcohol, the acetone.
Described the 3. in the step, and first to solidify the coagulating bath I that bathing pool (5) plants be the mixture of solvent in water or water and the claim 2 or the mixture of water and non-solvent; Described non-solvent is a kind of in methyl alcohol, ethanol, isopropyl alcohol, the acetone;
The second coagulating bath II that solidifies in the bathing pool (6) is a water.
Compared with prior art, the present invention has following beneficial effect:
(1) polybenzimidazoles (PBI), sulfonated polyether sulfone (SPES), SPSF (SPSF) etc. all are outstanding NF membrane materials, but the price of their costlinesses or difficult synthetic their application in general NF membrane production technology that limited to a great extent.Two-layer compound hollow fiber nanofiltration membrane of the present invention has internal layer to do main mechanical support, and the thickness of selecting row to separate exodermis can be accomplished thin as far as possible, and can not weaken the mechanical strength of film integral body.So, make very thin outer selection cortex by adopting expensive high performance membrane material, and select more cheap high molecular polymer to do the mechanical support inner layer material, can reduce the manufacturing cost of film greatly.The structure of double-layered compound film can improve the material selection space of inside and outside two membranes greatly in addition.
(2) Selective Separation exodermis high polymer of the present invention is selected separation, resistance to compression, antipollution, chemistry and the Heat stability is good of polybenzimidazoles (PBI), sulfonated polyether sulfone (SPES), SPSF (SPSF), can be widely used in the water treatment under some bad working environments.
(3) mechanical support internal layer high polymer of the present invention is by the blend of high polymer, amphipathic nature polyalcohol and aperture adjustment agent, hydrophilic ethylene alcohol, acrylic acid or vinylpyrrolidone unit can improve the hydrophily of internal layer blend film, and hydrophobic styrene units helps the stability of amphipathic copolymer in internal layer blend film body; The aperture adjustment agent can improve the aperture and the porosity of internal layer blend film body, thereby improves the water flux in the processing procedure.
(4) two-layer compound hollow fiber nanofiltration membrane of the present invention has good nanofiltration characteristic: this film to monovalence and divalence inorganic ion rejection be respectively～40% and～90%, can hold back high price and organic molecule, be～85% and～95% as the rejection to methyl green and sunset yellow dyestuff.
(5) Selective Separation cortex of the present invention places the skin of hollow fiber nanofiltration membrane, helps the degree of depth modification to the selectivity cladding material, and chemical stability, resistance tocrocking that improves film etc. is applied to some specific operating mode.
(6) the present invention is owing to have on the interface of double membrane structure and intermolecularly interpenetrate and act on, by selective membrane material rightly with optimize spinning condition, to produce synergy, thereby improve the performances such as separation, resistance to compression, antipollution, chemistry and heat endurance of film greatly.
(7) the present invention extrudes once moulding method simultaneously by the triple channel spinning head and produces the doughnut composite nanometer filtering film, combines the two-fold advantage of phase inversion and composite algorithm, and the making of hollow-fibre membrane is once finished.By controlled Selective Separation exodermis thickness, can significantly reduce the application of these high-performance, expensive material, reduce by 90% membrane material cost.Form and spinning condition by regulating feed liquid, the effective aperture of composite nanometer filtering film and pore-size distribution can be precisely controlled.The humidity in temperature that can be by the control temperature of casting solution and composition, core liquid and the temperature of composition, air gap height, coagulating bath I and II and composition, spinning room, the interior external diameter that doughnut collection rate parameters such as (drawing speeds) is regulated film easily with film thickness, membrane aperture is with pore-size distribution, porosity and separate cutoff performance etc.
Description of drawings
Content of the present invention is easier to be expressly understood in order to make, and according to specific embodiment also in conjunction with the accompanying drawings, the present invention is further detailed explanation below, wherein:
Fig. 1 is the schematic diagram of triple channel spinning head of the present invention.
Fig. 2 is the A place enlarged drawing of Fig. 1.
Fig. 3 is a device structure schematic diagram of the present invention.
Fig. 4 is the electromicroscopic photograph of two-layer compound hollow fiber nanofiltration membrane of the present invention.
Label is in the accompanying drawing:
Triple channel spinning head 1, core liquid passage 1-1, internal layer casting solution passage 1-2, outer casting solution passage 1-3, spinning nozzle 1-4, core liquid chamber 2, internal layer casting film liquid chamber 3, outer casting film liquid chamber 4, the first solidifies bathing pool 5, second solidifies bathing pool 6, gear pump 7, heating muff 8, wire wrapping wheel 9.
The specific embodiment
(embodiment 1)
See Fig. 4, the centre of figure is the two-layer compound hollow fiber nanofiltration membrane of present embodiment, comprises Selective Separation exodermis and mechanical support internal layer; Wherein, upper left is the outer surface of Selective Separation exodermis, and upper right is the inner surface of Selective Separation exodermis, the outer surface of position, lower-left mechanical support internal layer, the inner surface of position, bottom right mechanical support internal layer.On the Selective Separation exodermis fenestra is arranged, the fenestra aperture is 0.5～2 nanometer; Selective Separation exodermis thickness is 10～10000 nanometers; Layer thickness is 1～3 millimeter in the mechanical support; The Selective Separation exodermis of two-layer compound hollow fiber nanofiltration membrane and mechanical support internal layer are dissolved in the solvent by Selective Separation exodermis high polymer and mechanical support internal layer high polymer respectively.
See Fig. 1 and Fig. 2, the preparation specific purpose tool of present embodiment comprises: comprise triple channel spinning head 1, core liquid chamber 2, internal layer casting film liquid chamber 3, outer casting film liquid chamber 4, solidify bathing pool 5, second and solidify bathing pool 6, gear pump 7, heating muff 8 and wire wrapping wheel 9.
Triple channel spinning head 1 comprises the core liquid passage 1-1 that is positioned at the innermost layer, surround the internal layer casting solution passage 1-2 of core liquid passage 1-1, be positioned at outermost outer casting solution passage 1-3 and be positioned at the spinning nozzle 1-4 of lower end; The upper end of core liquid passage 1-1, internal layer casting solution passage 1-2 and outer casting solution passage 1-3 communicates with core liquid chamber 2, internal layer casting film liquid chamber 3 and outer casting film liquid chamber 4 respectively, and the lower end communicates with spinning nozzle 1-4.The internal diameter of the core liquid passage 1-1 lower end of triple channel spinning head 1 is 0.3～0.85 millimeter; The internal diameter of internal layer casting solution passage 1-2 lower end is 0.8～1.65 millimeter; The internal diameter of the lower end of outer casting solution passage 1-3 is 1.2～2 millimeters.Core liquid chamber 2, internal layer casting film liquid chamber 3 store core liquid, internal layer casting solution and outer casting solution respectively, are pressed into triple channel spinning head 1 by gear pump 7, and spray from spinning nozzle 1-4.First solidifies bathing pool 5, second solidifies spinning head 1-4 one side that bathing pool 6 and wire wrapping wheel 9 are positioned at triple channel spinning head 1; First solidifies bathing pool 5 and second solidifies and is provided with many godets 10 in the bathing pool 6., enter first successively and solidify bathing pool 5, second and solidify bathing pool 6 through behind the heating muff 8 from the silk of spinning nozzle 1-4 ejection, through the transmission of godet 10 on wire wrapping wheel 9.
Concrete preparation process is:
1. the configuration of casting solution: outer casting solution by PBI and LiCl and DMAc according to mass percent: 20～60 ℃ following stirring and dissolving evenly make at 22: 2: 76, be stored in the outer casting film liquid chamber 3; The internal layer casting solution by high polymer PES, aperture adjustment agent PVP, amphipathic nature polyalcohol PSA, solvent DMAc according to mass percent: 16: 5: 5: 74 evenly made 20～60 ℃ of following stirring and dissolving, are stored in the internal layer casting solution 4;
2. the moulding of two-layer compound hollow fiber nanofiltration membrane: make core liquid with 20～60 ℃ water and solvent DMA at 90: 10 according to mass percent, be stored in the core liquid chamber 2;
The first coagulating bath I that solidifies in the bathing pool 5 is that water mixes according to mass percent with isopropyl alcohol at 50: 50, and temperature is 25 ℃;
The second coagulating bath II that solidifies bathing pool 6 is that temperature is 25 ℃ a water.
Core liquid, outer casting solution and internal layer casting solution are injected core liquid passage 1-1, internal layer casting solution passage 1-2 and the outer casting solution passage 1-3 of triple channel spinning head 1 respectively by gear pump 7, be emitted into the tubulose liquid film through spinning nozzle 1-4, this liquid film enters first after through 0～20 centimetre the air gap successively and solidifies bathing pool 5, second and solidify bathing pool 6 and be wrapped on the wire wrapping wheel 9, phase transformation is frozen into double-deck hollow-fibre membrane, and the thickness of double-deck hollow-fibre membrane is controlled to be 10 meters of per minutes by the rotating speed of wire wrapping wheel 9;
3. cleaning-drying: with solid-state double-deck hollow-fibre membrane after 20～30 ℃ of water loggings bubbles clean 24～72 hours, put into 50 again: the glycerine of 50wt% and aqueous mixtures soaked 24～72 hours, dried to obtain described two-layer compound hollow fiber nanofiltration membrane in air.
Concrete proportioning and process conditions see Table one, the preparation of PBI-PES two-layer compound hollow fiber nanofiltration membrane.
The preparation of table one PBI-PES two-layer compound hollow fiber nanofiltration membrane
| Selective Separation exodermis casting solution (wt%) | ??PBI(22)/LiCl(2)/DMAc(76) |
| Exodermis casting solution flow velocity (ml/min) | ??0.5 |
| Support internal layer casting solution (wt%) | ??PES(16)/PVP(5)/PSA(5)/DMAc(74) |
| Internal layer casting solution flow velocity (ml/min) | ??5 |
| Core liquid is formed (wt%) | DMAc/ water (90/10) |
| Core flow velocity (ml/min) | ??2 |
| Air gap (cm) | ??20 |
| Coagulating bath I forms (wt%), temperature (℃) | Water/isopropyl alcohol (50/50wt%); 25 |
| Coagulating bath II, temperature (℃) | Water; 25 |
| Casting solution and core liquid temp (℃) | ??25 |
| Spinning room humidity (%) | ??70 |
| Drawing speed (m/min) | ??10 |
| Drying condition | Water logging bubble 72 hours; Glycerine soaked 24 hours; Dry in the air |
Those hollow fiber nanofiltration membrane assemblies of making sodium chloride rejection to 1mM under 1 kilogram of operating pressure, external-compression type operator scheme is 40%; Magnesium chloride rejection to 1mM is 87%; Rejection to methyl green and sunset yellow dyestuff is 87% and 98%; Pure water flux is 2L/ (m
2Hratm).
(embodiment 2)
The present embodiment used tool is identical with embodiment 1, and selected proportioning and process conditions see Table two, the preparation of SPSF-PVC two-layer compound hollow fiber nanofiltration membrane.
The preparation of table two SPSF-PVC two-layer compound hollow fiber nanofiltration membrane
| Selective Separation exodermis casting solution (wt%) | ??SPSF(16)/DMF(84) |
| Exodermis casting solution flow velocity (ml/min) | ??2 |
| Support internal layer casting solution (wt%) | ??PVC(20)/PEG(5)/PSE(5)/DMF(70) |
| Internal layer casting solution flow velocity (ml/min) | ??0.6 |
| Core liquid is formed (wt%) | DMF/ water (85/15) |
| Core flow velocity (ml/min) | ??1 |
| Air gap (cm) | ??10 |
| Coagulating bath I forms (wt%), temperature (℃) | Water/acetone (70/30); 40 |
| Coagulating bath II, temperature (℃) | Water; 40 |
| Casting solution and core liquid temp (℃) | ??25 |
| Spinning room humidity (%) | ??80 |
| Drawing speed (m/min) | ??20 |
| Drying condition | Water logging bubble 72 hours; Glycerine soaked 48 hours; Dry in the air |
Those hollow fiber nanofiltration membrane assemblies of making sodium chloride rejection to 1mM/L under 1 kilogram of operating pressure, external-compression type operator scheme is 15%; Magnesium chloride rejection to 1mM/L is 80%; Rejection to methyl green and sunset yellow dyestuff is 85% and 95%; Pure water flux is 0.8L/ (m
2Hratm).
(embodiment 3)
The present embodiment used tool is identical with embodiment 1, and selected proportioning and process conditions see Table three, the preparation of SPES-PAN two-layer compound hollow fiber nanofiltration membrane.
The preparation of table Three S's PES-PAN two-layer compound hollow fiber nanofiltration membrane
| Selective Separation exodermis casting solution (wt%) | ??SPES(25)/NMP(75) |
| Exodermis casting solution flow velocity (ml/min) | ??1 |
| Support internal layer casting solution (wt%) | ??PAN(20)/DG(5)/PSA(2)/NMP(73) |
| Internal layer casting solution flow velocity (ml/min) | ??10 |
| Core liquid is formed (wt%) | ??NMP/water(90/10) |
| Core flow velocity (ml/min) | ??2 |
| Air gap (cm) | ??0 |
| Coagulating bath I forms (wt%), temperature (℃) | Water/ethanol (50/50); 25 |
| Coagulating bath II, temperature (℃) | Water; 25 |
| Casting solution and core liquid temp (℃) | ??25 |
| Spinning room humidity (%) | ??70 |
| Drawing speed (m/min) | ??30 |
| Drying condition | Water logging bubble 72 hours; Glycerine soaked 24 hours; Dry in the air |
Those hollow fiber nanofiltration membrane assemblies of making sodium chloride rejection to 1mM/L under 1 kilogram of operating pressure, external-compression type operator scheme is 10%; Magnesium chloride rejection to 1mM/L is 82%; Rejection to methyl green and sunset yellow dyestuff is 89% and 95%; Pure water flux 1.8L/ (m
2Hratm).
(embodiment 4)
The present embodiment used tool is identical with embodiment 1, and selected proportioning and process conditions see Table four, the preparation of PBI-PAN two-layer compound hollow fiber nanofiltration membrane.
The preparation of table four PBI-PAN two-layer compound hollow fiber nanofiltration membrane
| Selective Separation exodermis casting solution (wt%) | ??PBI(22)/LiCl(2)/DMAc(86) |
| Exodermis casting solution flow velocity (ml/min) | ??1 |
| Support internal layer casting solution (wt%) | ??PAN(20)/PEG(5)/PSP(5)/DMSO(70) |
| Internal layer casting solution flow velocity (ml/min) | ??10 |
| Core liquid is formed (wt%) | ??DMSO/water(95/5) |
| Core flow velocity (ml/min) | ??5 |
| Air gap (cm) | ??15 |
| Coagulating bath I forms (wt%), temperature (℃) | Water/methyl alcohol (50/50); 60 |
| Coagulating bath II, temperature (℃) | Water; 60 |
| Casting solution and core liquid temp (℃) | ??25 |
| Spinning room humidity (%) | ??70 |
| Drawing speed (m/min) | ??50 |
| Drying condition | Water logging bubble 72 hours; Glycerine soaked 24 hours; Dry in the air |
Those hollow fiber nanofiltration membrane assemblies of making sodium chloride rejection to 1mM/L under 1 kilogram of operating pressure, external-compression type operator scheme is 25%; Magnesium chloride rejection to 1mM/L is 85%; Rejection to methyl green and sunset yellow dyestuff is 92% and 98%; Pure water flux 5L/ (m
2Hratm).
(embodiment 5)
The present embodiment used tool is identical with embodiment 1, and selected proportioning and process conditions see Table five, the preparation of SPSF-PAN two-layer compound hollow fiber nanofiltration membrane.
The preparation of table five SPSF-PSF two-layer compound hollow fiber nanofiltration membrane
| Selective Separation exodermis casting solution (wt%) | ??SPSF(25)/THF(85) |
| Exodermis casting solution flow velocity (ml/min) | ??1 |
| Support internal layer casting solution (wt%) | ??PSF(20)/PEG(5)/PSP(5)/THF(70) |
| Internal layer casting solution flow velocity (ml/min) | ??10 |
| Core liquid is formed (wt%) | ??THF/water(95/5) |
| Core flow velocity (ml/min) | ??5 |
| Air gap (cm) | ??20 |
| Coagulating bath I forms (wt%), temperature (℃) | Water/isopropyl alcohol (40/60); 50 |
| Coagulating bath II, temperature (℃) | Water; 50 |
| Casting solution and core liquid temp (℃) | ??25 |
| Spinning room humidity (%) | ??70 |
| Drawing speed (m/min) | ??50 |
| Drying condition | Water logging bubble 72 hours; Glycerine soaked 24 hours; Dry in the air |
Those hollow fiber nanofiltration membrane assemblies of making sodium chloride rejection to 1mM/L under 1 kilogram of operating pressure, external-compression type operator scheme is 35%; Magnesium chloride rejection to 1mM/L is 90%; Rejection to methyl green and sunset yellow dyestuff is 95% and 98%; Pure water flux 4L/ (m
2Hratm).
Above-described specific embodiment; purpose of the present invention, technical scheme and beneficial effect are further described; institute is understood that; the above only is specific embodiments of the invention; be not limited to the present invention; within the spirit and principles in the present invention all, any modification of being made, be equal to replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1, a kind of two-layer compound hollow fiber nanofiltration membrane is characterized in that: comprise Selective Separation exodermis and mechanical support internal layer; On the Selective Separation exodermis fenestra is arranged, the fenestra aperture is 0.5～2 nanometer; Selective Separation exodermis thickness is 10～10000 nanometers; Layer thickness is 1～3 millimeter in the mechanical support; The Selective Separation exodermis of two-layer compound hollow fiber nanofiltration membrane and mechanical support internal layer are dissolved in the solvent by Selective Separation exodermis high polymer and mechanical support internal layer high polymer respectively.
2. the two-layer compound hollow fiber nanofiltration membrane of claim 1, it is characterized in that: described solvent is N, N '-dimethyl formamide (DMF), N, a kind of in N '-dimethylacetylamide (DMAc), dimethyl pyrrolidone (NMP), dimethyl sulfoxide (DMSO) (DMSO), the oxolane (THF).
3. the two-layer compound hollow fiber nanofiltration membrane of claim 1, it is characterized in that: described Selective Separation exodermis high polymer is a kind of in polybenzimidazoles (PBI) and its stabilizing agent lithium chloride (LiCl), sulfonated polyether sulfone (SPES), the SPSF (SPSF), is dissolved in the solvent of claim 2; The two mass percent is 15～25%: 75～85%.
4. the two-layer compound hollow fiber nanofiltration membrane of claim 1 is characterized in that: high polymer, the mass percent that described mechanical support internal layer high polymer is a mass percent 10～20% is that 2～10% amphipathic nature polyalcohol and mass percent are that the mixture of 2～10% aperture adjustment agent is dissolved in the solvent that mass percent is 60～86% claim 2; Wherein high polymer is a kind of in polysulfones (PSF), polyether sulfone (PES), polyacrylonitrile (PAN), the polyvinyl chloride (PVC); Amphipathic nature polyalcohol is a kind of in styrene-ethylene alcohol copolymer (PSE), styrene-propene acid copolymer (PSA), the styrene-ethylene pyrrolidones copolymer (PSP); The aperture adjustment agent is a kind of in polyethylene glycol (PEG), polyvinylpyrrolidone http://www.tx21.com.cn/test/suliao/200809/81158.html (PVP), the diethylene glycol (DEG) (DG).
5. a specific purpose tool for preparing the two-layer compound hollow fiber nanofiltration membrane of claim 1 is characterized in that: comprise special-purpose spray silk instrument, core liquid chamber (2), internal layer casting film liquid chamber (3) and outer casting film liquid chamber (4); A described special-purpose spray silk instrument is triple channel spinning head (1), comprises the core liquid passage (1-1), the internal layer casting solution passage (1-2) that surrounds core liquid passage (1-1) that are positioned at the innermost layer, is positioned at outermost outer casting solution passage (1-3) and is positioned at the spinning nozzle (1-4) of lower end; The upper end of described core liquid passage (1-1), internal layer casting solution passage (1-2) and outer casting solution passage (1-3) communicates with core liquid chamber (2), internal layer casting film liquid chamber (3) and outer casting film liquid chamber (4) respectively, and the lower end communicates with spinning nozzle (1-4).
6. the specific purpose tool of preparation two-layer compound hollow fiber nanofiltration membrane according to claim 5 is characterized in that: the internal diameter of core liquid passage (1-1) lower end of described triple channel spinning head (1) is 0.3～0.85 millimeter; The internal diameter of internal layer casting solution passage (1-2) lower end is 0.8～1.65 millimeter; The internal diameter of the lower end of outer casting solution passage (1-3) is 1.2～2 millimeters.
7. the specific purpose tool of preparation two-layer compound hollow fiber nanofiltration membrane according to claim 5 is characterized in that: comprise that also first of spinning head (1-4) side that is positioned at triple channel spinning head (1) solidifies bathing pool (5), second and solidify bathing pool (6) and wire wrapping wheel (9); First solidifies bathing pool (5) and second solidifies and is provided with many godets (10) in the bathing pool (6).
8. method for preparing the two-layer compound hollow fiber nanofiltration membrane of claim 1 is characterized in that may further comprise the steps:
1. the configuration of casting solution: outer casting solution is evenly made 20～60 ℃ of following stirring and dissolving by the Selective Separation exodermis high polymer of claim 3 and the solvent of claim 2; The internal layer casting solution is evenly made 20～60 ℃ of following stirring and dissolving by the solvent of mechanical support internal layer high polymer, amphipathic nature polyalcohol and the aperture adjustment agent and the claim 2 of claim 4;
2. the moulding of two-layer compound hollow fiber nanofiltration membrane: the core liquid passage (1-1), internal layer casting solution passage (1-2) and the outer casting solution passage (1-3) that core liquid, outer casting solution and internal layer casting solution are injected described triple channel spinning head (1) respectively, (1-4) is emitted into the tubulose liquid film through spinning nozzle, this liquid film enters first after through 0～20 centimetre the air gap successively and solidifies bathing pool (5), second and solidify bathing pool (6) and be wrapped on the wire wrapping wheel (9), phase transformation is frozen into double-deck hollow-fibre membrane, and the thickness of double-deck hollow-fibre membrane is by the rotating speed control of wire wrapping wheel (9);
3. cleaning-drying: with solid-state double-deck hollow-fibre membrane after 20～30 ℃ of water loggings bubbles clean 24～72 hours, put into 50 again: the glycerine of 50wt% and aqueous mixtures soaked 24～72 hours, dried to obtain described two-layer compound hollow fiber nanofiltration membrane in air.
9. the method for preparing the two-layer compound hollow fiber nanofiltration membrane according to claim 8 is characterized in that: described the 2. the core liquid in the step be the mixture of solvent in 20～60 ℃ water or water and the claim 2 or the mixture of water and non-solvent; Described non-solvent is a kind of in methyl alcohol, ethanol, isopropyl alcohol, the acetone.
10. the method for preparing the two-layer compound hollow fiber nanofiltration membrane according to claim 8, it is characterized in that: described the 3. in the step, and first to solidify the coagulating bath I that bathing pool (5) plants be the mixture of solvent in water or water and the claim 2 or the mixture of water and non-solvent; Described non-solvent is a kind of in methyl alcohol, ethanol, isopropyl alcohol, the acetone; The second coagulating bath II that solidifies in the bathing pool (6) is a water.
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