WO2011069441A1 - Procédé de préparation d'une membrane fibre creuse poreuse multicouche composite et dispositif et produit associés - Google Patents

Procédé de préparation d'une membrane fibre creuse poreuse multicouche composite et dispositif et produit associés Download PDF

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Publication number
WO2011069441A1
WO2011069441A1 PCT/CN2010/079531 CN2010079531W WO2011069441A1 WO 2011069441 A1 WO2011069441 A1 WO 2011069441A1 CN 2010079531 W CN2010079531 W CN 2010079531W WO 2011069441 A1 WO2011069441 A1 WO 2011069441A1
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Prior art keywords
hollow fiber
coating
membrane
composite multilayer
phase separation
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PCT/CN2010/079531
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English (en)
Chinese (zh)
Inventor
杨新浩
葛海霖
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广州美能材料科技有限公司
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Priority to US13/377,825 priority Critical patent/US8967391B2/en
Publication of WO2011069441A1 publication Critical patent/WO2011069441A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/08—Hollow fibre membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/08—Hollow fibre membranes
    • B01D69/087—Details relating to the spinning process
    • B01D69/0871—Fibre guidance after spinning through the manufacturing apparatus

Definitions

  • the present invention relates to a method of preparing a filtration membrane, a device and a product thereof, and more particularly to a method, apparatus and product for preparing a composite multilayer porous hollow fiber filtration membrane. More particularly, the present invention relates to a process for making a composite multilayer porous hollow fiber filtration membrane for water treatment, and apparatus and apparatus therefor. Background technique
  • ultrafiltration (U) and microfiltration (MF) separation membranes have been widely used in the food industry, medical field, domestic and municipal water, industrial and municipal wastewater treatment, etc.
  • U ultrafiltration
  • MF microfiltration
  • This method requires the porous hollow fiber membrane to be used to have a high void ratio and a narrow pore size distribution to improve separation efficiency and separation accuracy; moreover, the membrane is required to have a pore diameter most suitable for separating the object, for bacteria, suspension
  • the granule and turbidity components have high blocking properties; at the same time, the membrane filament of the membrane must have high mechanical strength and high water flux, so that it can be used for long-term operation under the conditions of cleaning with chemical reagents for contaminated membrane filaments and high operating pressure. use.
  • PVDF polyvinylidene fluoride
  • NIPS non-solvent phase separation method
  • a braid or a tubular braid made of a polymer having excellent high mechanical strength is used as the separation membrane.
  • a film such a film has a greater thickness, which increases the resistance to fluid flow, thereby significantly reducing water permeability.
  • the acrylonitrile support material will shrink to cause peeling, polyethylene (PE), polyethylene terephthalate (PET) or nylon braid Unlike polyvinylidene fluoride (PVDF) materials, peeling is more likely to occur after long-term use and at pH greater than 10.
  • the non-solvent phase separation method (NIPS) process has a large number of film forming factors, which affects the film structure or film properties. Therefore, it is difficult to control the film forming operation process and lacks reproducibility.
  • TIPS thermal induced phase separation
  • AU653528 discloses an early thermally induced phase separation (TIPS) method for preparing a hollow fiber membrane by mixing a polyvinylidene fluoride resin with an organic pore former, forming a molten material at 220 Torr and a partial vacuum, and then passing The hollow molding nozzle extrudes hollow fibers at 215 ° C, and the hollow fiber membrane thus formed has a low porosity.
  • TIPS thermally induced phase separation
  • the prepared membrane has an inner diameter of 1.10 mm, a wall thickness of 0.45 mm, an average pore diameter of 0.05-5 mm, and a breaking strength of 7-20. mPa.
  • a disadvantage of this method is that as the membrane wall becomes thinner as the inner diameter of the membrane becomes thinner, the pressure resistance of the membrane, the water flux decreases.
  • JP-A No. 3-215535 discloses a manufacturing process of a polyvinylidene fluoride resin (PVDF) hollow fiber porous film having a large mechanical strength and a high pressure resistance.
  • PVDF polyvinylidene fluoride resin
  • the polyvinylidene fluoride resin is mixed with an organic pore former such as n-octyl phthalate (DOP) and an inorganic nano powder of hydrophobic silica as an inorganic pore former, which is melt-extruded at a temperature of up to 250 Torr.
  • organic and inorganic pore formers are extracted, so that a symmetric membrane having a uniform pore diameter on the inner and outer surfaces without a skin layer is obtained, and the filtration precision of such a type membrane is greatly reduced, and the void ratio is also low.
  • the outer surface layer of the film produced by the thermally induced phase separation (TIPS) process is rougher than the outer surface of the film produced by the non-solvent phase separation (NIPS) process, thereby easily reducing the contamination resistance of the film.
  • one of the objects of the present invention is to provide a method for preparing a composite multilayer porous hollow fiber filter membrane to improve mechanical strength, water flux, filtration precision and pollution resistance of the membrane, and to avoid multiple layers. The possibility of peeling between.
  • the present invention further develops a new stable production technology by combining a thermally induced phase separation (TIPS) process and a non-solvent phase separation (NIPS) process to prepare a high strength, high filtration precision. , high binding strength, high anti-pollution, high water flux, composite multilayer porous hollow fiber membrane.
  • TIPS thermally induced phase separation
  • NIPS non-solvent phase separation
  • a method for preparing a composite multilayer porous hollow fiber membrane of the present invention comprises the following steps -
  • thermoplastic polymer resin organic pore former, inorganic pore former and auxiliary agent in a ratio of 30-50: 20-40: 10-30: 0-5 by weight, by extrusion Extrusion and extrusion, to obtain uncured hollow fiber;
  • thermoplastic polymer resin, the hydrophilic polymer pore former, the surfactant, the good solvent and the poor solvent are in a ratio by weight to 5-30: 1-20: 1-20: 40 -90:
  • the ratio of 1-10 is mixed in the coating raw liquid tank as a coating layer stock solution;
  • step (2) After the uncured hollow fiber obtained in the step (1) is passed through 0-5 cm into the non-solvent phase separation process coating device in the step (2), the step (2) The coating layer stock solution is coated on the outer surface layer of the uncured hollow fiber obtained in the step (1) while being solidified to obtain a hollow fiber having an ultra-thin outer skin layer;
  • thermoplastic polymer of step (1) and step (2) in the method of the invention is referred to as thermal induced phase transfer (TIPS)
  • TIPS thermal induced phase transfer
  • Thermoplastic high molecular polymer resins suitable for use in non-solvent phase transfer (NIPS) processes including polyvinylidene fluoride homopolymers or copolymers, such as: poly(vinylidene fluoride-hexafluoropropane), poly(poly) Fluoroethylene-chlorotrifluoroethylene), poly(vinylidene fluoride-ethylene), etc., polysulfone, polyethersulfone, ethylene-vinyl alcohol copolymer, and the like. It is preferable to use a polyvinylidene fluoride homopolymer excellent in chemical resistance or a copolymer thereof, and most preferably a polyvinylidene fluoride homopolymer.
  • the support inner layer of the composite multilayer porous hollow fiber membrane prepared by the thermally induced phase separation method (TIPS) of the present invention is prepared in the following parts by weight:
  • auxiliary agents such as an antioxidant, a lubricant, an anti-blocking agent, a heat stabilizer and an ultraviolet absorber may be added as needed, and the total weight is 0-5. %.
  • the organic pore former of the step (1) is dimethyl phthalate (DMP), diethyl phthalate (DEP), dibutyl phthalate (DBP), phthalic acid Phthalate esters such as octyl ester (DOP), ⁇ -butyrolactone, benzoic acid esters, sebacic acid esters, adipates, trimellitates or phosphates, etc.
  • DMP dimethyl phthalate
  • DEP diethyl phthalate
  • DBP dibutyl phthalate
  • phthalic acid Phthalate esters such as octyl ester (DOP), ⁇ -butyrolactone, benzoic acid esters, sebacic acid esters, adipates, trimellitates or phosphates, etc.
  • the amount of porogen can be one or a mixture thereof.
  • the inorganic pore former (specific surface area: 30-150 m 2 /g, average particle diameter ⁇ 100 nm) of the step (1) is at least one of an active nano oxide and an active organic clay, including active nano zinc oxide, Active nano-CaCO3, active nano-oxide or other active nano-oxide or active organoclay, active nano-diatomite, active nano-kaolin ("active” means organic hydrophobic treatment of the surface of the substance, making the material very Well dispersed in organic systems), either natural or synthetic, can be used alone or in combination.
  • active means organic hydrophobic treatment of the surface of the substance, making the material very Well dispersed in organic systems
  • the present invention further prefers active nano zinc oxide and active nano calcium carbonate having good dispersibility and easy post treatment.
  • the amount of polyvinylidene fluoride (PVDF) is mainly to have sufficient mechanical strength, and the total amount of organic pore former should be as much as possible.
  • the amount of ethylene (PVDF) is constant, the more the amount of organic pore former, the more the inner layer of large pore size can be formed to increase the porosity of the membrane, and at the same time, the resistance during filtration can be reduced, saving Energy consumption.
  • the inorganic pore former has a three-dimensional void structure when the pore diameter in the membrane is newly formed, and the inorganic pore former is used in an amount as much as possible, but too much due to the viscosity of the material of the membrane. Large, difficult to film.
  • the preferred weight fraction ratio is - polyvinylidene fluoride 30-50
  • the ultra/micro filter coating having a precision filtration effect on the surface prepared by the non-solvent phase transfer method (NIPS) process of the present invention is made up of the following parts by weight:
  • thermoplastic polymer resin is preferably a polyvinylidene fluoride resin.
  • the polymer pore forming agent is a hydrophilic soluble polymer which can be dissolved in the coagulating liquid or the post-treatment liquid.
  • the hydrophilic polymer pore former may be polyvinylpyrrolidone (PVP), polyethylene glycol (PEG), methyl cellulose, carboxymethyl cellulose, polyvinyl alcohol, polyacrylic acid and esters thereof. Etc., they can be used alone or in combination.
  • the surfactant may be an anionic surfactant, a cationic surfactant, an amphoteric surfactant or a nonionic surfactant, specifically, Tween-80, sodium dodecylsulfonate. , sodium dodecylbenzenesulfonate, dodecylbenzylammonium chloride, cetyltrimethylammonium bromide, etc., which may be used singly or in combination.
  • the good solvent may be dimethylformamide (DMF), dimethylacetamide (DMAc), N-methylpyrrolidone (NMP), dimethyl sulfoxide (DMSO), methyl ethyl ketone, acetone, ⁇ - As the butyrolactone or the like, one or a mixture of two kinds of such good solvents can be used.
  • the poor solvent or non-solvent may be a low molecular polyol such as glycerin, ethylene glycol, butanediol or propylene glycol or an alcohol such as methanol, ethanol, n-butanol or isopropanol or one or two of water. mixing.
  • a low molecular polyol such as glycerin, ethylene glycol, butanediol or propylene glycol or an alcohol such as methanol, ethanol, n-butanol or isopropanol or one or two of water. mixing.
  • a coating layer having a precision ultrafiltration (micro), hydrophilic, and anti-pollution filtration function is coated in a manner capable of covering the surface of the hollow fiber membrane to support the internal support layer.
  • the material of the inner support layer is polyvinylidene fluoride (PVDF) and the polyvinylidene fluoride (PVDF) in the coating layer is the same kind of high molecular polymer resin material. And before the new inner support layer is uncured, the coating is applied, so the two are completely fused together.
  • the thickness of the coating layer can be controlled to 0.01-0.5 mm, the pore size of the filter layer on the outer surface can be controlled to 0.01-0.5 ⁇ m, and the amount of polyvinylidene fluoride (PVDF) acts to cover the surface of the inner support layer of the entire hollow fiber membrane.
  • PVDF polyvinylidene fluoride
  • the amount of vinylidene fluoride (PVDF) is too large, the viscosity of the coating solution is large, the thickness is increased, the porosity is lowered, and the water resistance is increased.
  • the amount of polyvinylidene fluoride (PVDF) is too small, the coating liquid of the coating layer is too thin to be uniformly coated, and it does not function as a fine filtration layer.
  • the amount of the hydrophilic polymer porogen added depends on the stability of the film-forming stock solution, neither emulsification nor phase separation, and the uniformly dispersed coating layer has a high void ratio. .
  • the surfactant compensates for the deficiency of the high molecular pore former in the process of forming the liquid, and the stability of the film preparation liquid is improved by its penetration and emulsifying property.
  • the poor solvent can promote the microphase separation of the membrane preparation liquid, which is beneficial to obtain the large pore size filtration coating, but the excess will lead to the deterioration of the stability of the membrane preparation liquid, and the amount of the good solvent is to coordinate the viscosity and stability of the entire membrane preparation liquid.
  • the preferred parts by weight ratio is - thermoplastic polymer resin 5-15
  • thermoplastic polymer resin is preferably a polyvinylidene fluoride resin.
  • the uncured hollow fiber material produced by the thermally induced phase transfer (TIPS) process enters the non-solvent phase transfer method (NIPS) process coating device and the walking distance can be 0-5 cm, due to the need for uncured hollow fiber
  • the coating is applied outside and formed into a firm one, so the shorter the distance between the two is, the better the distance is 0-0.5cm. If the distance is more than 2cm, the boundary between the two phases can be observed under scanning electron microscopy. Peel strength Therefore it may be weakened.
  • the thickness of the coating layer is controlled by the speed of travel of the uncured hollow fiber material produced by the thermally induced phase transfer (TIPS) process into the non-solvent phase transfer (IPS) process coating apparatus.
  • the thickness of the coating layer is 0.01-0.5 mm, and the preferred thickness is 0.015-0.2 mm.
  • the coating layer on the outer surface is solidified.
  • the coagulating liquid may be a non-solvent of polyvinylidene fluoride resin (PDVF) such as an alcohol such as methanol or ethanol, a low molecular polyol such as glycerin or ethylene glycol, and one or two kinds of water, or may be added in a non-solvent.
  • PDVF polyvinylidene fluoride resin
  • a good amount of good solvent dimethyl Formamide (DMF), dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO), methyl ethyl ketone, acetone, and ⁇ -butyrolactone, etc., tetrahydrofuran, etc. are structures for controlling the formation of the outer layer, such as finger pore layers.
  • the sponge layer structure when the water in the water solvent is used as the coagulating liquid, a good solvent of polyvinylidene fluoride (PVDF) dimethylacetamide CDMA C ) can be added 10-80%, so that the outer film is not crushed. There is no excessive filtering resistance.
  • PVDF polyvinylidene fluoride
  • the preferred weight percentage of dimethylacetamide (DMAc) in water as a coagulating solution is 20-60% by considering reducing the ratio of the finger layer or without the pore layer structure.
  • the organic pore former and the solvent in the formed composite multilayer hollow fiber membrane can be extracted by a polar solvent at an extraction temperature of 20-80 ° C, mainly without dissolving the thermoplastic polymer resin used. And denaturation, and the liquid is volatile, so that it can be easily removed from the hollow fiber membrane after extraction.
  • the low-boiling polar solvent is an alcohol such as methanol, ethanol or isopropanol, dichloromethane and dichloroethane. Isochlorinated hydrocarbons, preferred polar solvents are environmentally friendly alcohols.
  • the inorganic pore-forming agent in the composite multilayer hollow fiber membrane can be selected according to different properties thereof, such as an alkaline solution with an acidic solution such as hydrochloric acid, sulfuric acid, phosphoric acid, etc.
  • An alkaline solution for the oxide such as sodium hydroxide, potassium hydroxide or calcium hydroxide.
  • an acidic solution having a pH of > 1 is preferably used.
  • the composite multilayer hollow fiber membrane filament can be stretched before or after extraction and extraction as necessary to increase the mechanical strength and water flux of the membrane, and the elongation ratio can be between 10 and 100%, preferably The stretch ratio used is 20-50%.
  • the composite multilayer porous hollow fiber membrane yarn after extraction and extraction is washed with pure water, immersed in a 50% glycerin solution, and finally dried in a hot environment of 20-80 °C.
  • a second object of the present invention is to provide a composite multilayer porous hollow fiber filter membrane obtained by the above preparation process, which membrane is composed of an inner support layer and an outer surface layer, and the inner support layer is a large pore structure, and the inner surface is The pore size is 0.1-10 ⁇ , the outer surface layer is ultra-fine pore structure, the outer diameter of the membrane is 0.01-1 ⁇ , the porosity is 50-90%, and the pure water flux is 500-5000 L/m2 hr@0.1 mPa, 25 ° C, tensile breaking strength 8-25 mPa, tensile elongation at break 100-250%, film tensile strength 0.8-2.0 mPa.
  • the outer diameter is 0.5-3 mm and the wall thickness is 0.1-1 mm.
  • the radial cross-sectional structure of the composite multilayer porous hollow fiber membrane has no obvious layered interface, and the density of the sponge-like structure increases mainly from the inside to the outer surface. Therefore, no filament layer is found in the whole tensile fracture test. Peeling phenomenon with the layer, but directly breaking.
  • the composite multilayer hollow fiber membrane is immersed in a sodium hydroxide (NaOH) 2% solution at room temperature for one month without peeling during stretching, and the elongation is maintained at 95% or more.
  • NaOH sodium hydroxide
  • a third object of the present invention is to provide an apparatus for preparing a composite multilayer porous hollow fiber filtration membrane by the above method, which comprises an extruder, a melt pump, a spinning mold, an adjustable fixing member, a coating raw material coating device, a coating raw liquid filling, a coating polymer raw liquid conveying pump, a coagulation bath, a winding wheel, the extruder, the melt pump, and the spinning mold are sequentially connected, and the spraying
  • the wire mold and the coating raw material coating device are connected by the adjustable fixing member, and the coating raw liquid is poured through the coating polymer raw liquid transfer pump and the coating raw material coating device, the coating raw liquid
  • the coating device sequentially connects the coagulation bath and the winding wheel.
  • the present invention has the following beneficial effects:
  • the thermally induced phase separation method (TIPS) process of the present invention uses an active nano-zinc oxide, an active nano-oxidation and the like to prepare an internal support layer, and it is easy to use at room temperature by using a strongly acidic extract. Quickly remove the inorganic pore former in the membrane to avoid discoloration, surface aging and deterioration of the polyvinylidene film material.
  • a composite multilayer porous hollow fiber membrane formed by a one-step method combined with a thermally induced phase separation (TIPS) process and a non-solution phase separation (NIPS) process which not only solves the non-solution phase separation method (NIPS) Peeling problem between the film layer of the polyvinylidene fluoride (PVDF) hollow fiber membrane prepared by the process coating method and the support layer due to poor adhesion of polyvinylidene fluoride (PVDF) to other high molecular polymers And also solved the use of non-solution phase separation (NIPS)
  • the low mechanical strength of ordinary polyvinylidene fluoride (PVDF) hollow fiber membrane filaments without a support layer produced directly by the art method avoids the filament strength caused by a particularly high pH alkaline solution at a pH greater than 10 And the elongation rate is lowered to make the film filaments brittle, so that the application range of the film is not limited by the disadvantage.
  • the surface of the composite multilayer porous hollow fiber membrane is greatly improved due to the hydrophilic surface-active substance. Anti-pollution, especially the ability to resist organic pollution in industrial wastewater treatment.
  • the membrane prepared by the composite multilayer porous hollow fiber membrane preparation process of the invention has the high mechanical strength, high water flux and non-solvent phase separation membrane formation (NIPS) of the thermally induced phase separation membrane (TIPS) membrane.
  • the membrane has a precise filtration effect and a high stain resistance on the surface of the membrane, and there is no boundary between the layers, and no peeling between the layers occurs in use. Since the resistance of the large pore water of the inner support layer is greatly reduced to save energy, and the fine pore diameter of the surface layer does not lose the filtration precision, the composite multilayer porous hollow fiber membrane has an effective high void ratio and can be widely used. Used in a variety of filtration applications. DRAWINGS
  • Figure 1 is a schematic cross-sectional view showing a composite multilayer porous hollow fiber membrane of the present invention
  • Figure 2 is a schematic view of the apparatus used in the preparation method of the present invention.
  • Figure 3 is an electron micrograph of a cross section of a first preferred embodiment of the composite multilayer porous hollow fiber porous filter membrane of the present invention
  • Figure 4 is an electron micrograph of the surface of the outer coating layer of the composite multilayer porous hollow fiber porous filter membrane of Figure 3;
  • Figure 5 is an electron micrograph of the inner surface of the inner support layer of the composite multilayer porous hollow fiber porous filter membrane of Figure 3;
  • Figure 6 is an electron micrograph of a cross section of a second preferred embodiment of the composite multilayer porous hollow fiber porous filter membrane of the present invention;
  • Figure 7 is an electron micrograph of a cross section of a fourth preferred embodiment of the composite multilayer porous hollow fiber porous filter membrane of the present invention.
  • Figure 8 is an electron micrograph of a cross section of a ninth preferred embodiment of the composite multilayer porous hollow fiber porous filter membrane of the present invention.
  • Figure 9 is an electron micrograph of the surface of the outer coating layer of the composite multilayer porous hollow fiber porous filter membrane of Figure 8;
  • Figure 10 is an electron micrograph of the inner surface of the inner support layer of the composite multilayer porous hollow fiber porous filter membrane of Figure 8.
  • FIG. 1 A schematic cross-sectional view of a composite multilayer porous hollow fiber membrane of the present invention is shown in Fig. 1.
  • a composite multilayer porous hollow fiber membrane in which a thermoplastic polymer resin is formed by a thermally induced phase separation (TIPS) process is hollow.
  • the fibrous film is used as the inner surface layer of the film, and the support main body A having a large pore diameter is coated with a solution of the thermoplastic high molecular polymer resin by a non-solvent phase separation method (NIPS) process. Filter function of the coating 8.
  • TIPS thermally induced phase separation
  • FIG. 2 is a view showing the apparatus used in the production method of the present invention, by which the composite multilayer porous hollow fiber membrane of the present invention is combined with a thermally induced phase separation (TIPS) process and a non-solvent phase separation (NIPS) process.
  • TIPS thermally induced phase separation
  • NIPS non-solvent phase separation
  • the apparatus comprises an extruder 1, a melt pump 3, a spinning die 4, an adjustable fixing member 6, a coating raw material coating device 7, a coating raw liquid irrigation 8, a coating polymer raw liquid delivery pump. 9.
  • the coagulation bath 10, the winding drum 12, the extruder 1, the melt pump 3, the spinning mold 4 are sequentially connected, and the spinning mold 4 and the coating raw material coating device 7 are connected by the adjustable fixing member 6,
  • the coating raw liquid irrigation 8 is connected to the coating raw material coating device 7 through the coating polymer raw liquid delivery pump 9, and the coating raw material coating device 7 is sequentially connected to the coagulation bath 10 and the winding roller 12, and the guide wire is disposed in the solid bath 10.
  • Wheel 11 A hopper 2 is provided on the extruder 1.
  • a nitrogen tank 5 is provided on the spinning mold 4.
  • a uniform powdery mixture of a thermoplastic polymer resin premixed by a high-speed mixer and a raw material such as an organic and inorganic pore former passes through the hopper 2 of the twin-screw extruder 1 through a high temperature.
  • the coating layer device 7 After extrusion, it passes through the melt pump 3 and enters the spinning mold 4 with nitrogen (N 2 ) 5 , and extrudes to form a new uncured hollow fiber, and directly enters a coating film with an adjustable distance of 6 Device 7, the coating layer device 7 is provided with a coating raw liquid storage tank 8 and a polymer raw liquid delivery pump 9, and the coating layer raw liquid is continuously supplied to the coating layer device 7, and the coating raw liquid is the thermoplastic high molecular polymer Resin, polymer pore former, surfactant and good solvent, etc., first stirred and mixed in storage tank 8, defoaming for use.
  • the thickness of the coating is controlled by the formulation and speed of the different coating stock solutions; and the nascent uncured hollow fiber In the coating layer stock solution, it is completely cured and coated.
  • the composite multilayer hollow fiber enters the coagulation bath 10, and the coating layer on the outer surface is solidified, after passing through the godet 11 and finally Winding at the wire winding machine 12, the resulting composite multilayer hollow fiber is subjected to stretching treatment, organic extraction and inorganic extraction treatment, alcohol soaking, and finally immersed in pure water for several times, and then 50% glycerin is used. After immersing for two days, it was air-dried at 50 ° C to obtain a final composite multilayer porous hollow fiber membrane filament.
  • the polyvinylidene fluoride homopolymer is used as a thermoplastic polymer resin, which can be used in a thermally induced phase separation (TIPS) process to form a porous multi-porous support layer in the interior of a composite multilayer porous hollow fiber membrane filament.
  • TIPS thermally induced phase separation
  • the solvent phase separation (NIPS) process is applied to form a fine pore fine outer layer having a microfiltration/ultrafiltration function.
  • the melt-kneaded product (a) consists of 25 parts by weight of active nano-zinc oxide (particle size of 30-50 mm) ), 40 parts by weight of polyvinylidene fluoride (PVDF, molecular weight: 250,000-400,000 Daltons), 33.8 parts by weight of dioctyl phthalate, and parts by weight of 1.2 Dibutyl phthalate is stirred and mixed at a high speed in a high-speed mixer at room temperature to uniformly disperse the solid phase in the organic phase, and to mix and disperse the solid (powdered) material in reserve.
  • PVDF polyvinylidene fluoride
  • NIPS Functional surface non-solvent phase separation composition of polymer mixed solution used in the coating process
  • PVDF Polyvinylidene fluoride
  • PVP Polyvinylpyrrolidone
  • PEG-400 polyethylene glycol-400
  • Tween-80 by weight of 2.1
  • the amide (DMAc) was stirred in a dissolution tank under nitrogen at 13 (TC) until dissolved into a homogeneous solution, then at 13 CTC, after one day of static defoaming.
  • the thermally induced phase separation (TIPS) process uses a twin-screw extruder (screw diameter 20, aspect ratio: 40:1).
  • a high-speed mixed homogeneous powdery material
  • the nozzle mold was passed through an annular slit having an outer diameter of 1.9 mm and an inner diameter of 0.9 mm and the nozzle temperature was controlled at 250 °C.
  • the hollow fiber was extruded at a rate of 40 g/min from the center of the nozzle by injecting air into the hollow at a flow rate of 18 ml/min, directly through a non-solvent phase separation (IPS) process coating apparatus, and thermally induced phase separation ( TIPS) Process twin-screw extruder nozzle mold and non-solvent phase separation method (NIPS) process coating device mold directly connected through the insulation layer (pitch 0, that is, in the thermally induced phase separation method (TIPS) process method
  • TIPS thermally induced phase separation
  • TIPS thermally induced phase separation
  • TIPS thermally induced phase separation method
  • the hollow filaments were made without any contact with air prior to entering the non-solvent phase separation (NIPS) process coating apparatus, and the non-solvent phase separation (NIPS) apparatus was maintained at 130 °C.
  • TIPS thermally induced phase separation
  • NIPS non-solvent phase separation
  • the uncured hollow fiber is fully cured in a non-solvent phase separation (NIPS) process coating apparatus while coating a layer
  • NIPS non-solvent phase separation
  • an aqueous solution containing 30% dimethylacetamide (DMAc) at a temperature of 2 cm and a temperature of 50 ° C was introduced as an external coagulation bath, after passing through the 2 m long outer coagulation bath, The functional outer surface coating is solidified and drawn onto a 3.5 m circumference winding wheel with continuous water rinsing.
  • DMAc dimethylacetamide
  • the composite multilayer hollow fiber molded body unloaded from the winding wheel is subjected to 30% stretching in a 50 ° C water bath before being subjected to extraction and extraction treatment, and then, after stretching, immersed in a 95% ethanol solution and mechanically oscillated.
  • the organic pore-forming agent was extracted and maintained at a temperature of 40 ° C for 0.5 hour, repeated 3 times, then washed with pure water, and then transferred to a 2M sulfuric acid (H 2 S0 4 ) solution, and subjected to mechanical shock in the greenhouse.
  • the inorganic pore former was extracted and finally rinsed and soaked in pure water for 3 hours each time in a greenhouse for 3 times, then immersed in a 50% aqueous glycerin solution for 2 days, and then air-dried at 50 °C.
  • the content of residual zinc (Zn) in the composite multilayer porous hollow fiber membrane yarn obtained was less than 0.3%.
  • the composite multilayer porous polyvinylidene fluoride hollow fiber membrane has an outer diameter of 1.24 mm, an inner diameter of 0.65 mm, a void ratio of 77%, and an average thickness of the composite coating layer of the functional outer surface of 0.02 mm, and a functional outer surface of the membrane.
  • the average pore diameter is 0.05 ⁇
  • the inner surface of the inner support layer has an average pore diameter of ⁇
  • the pure water flux is 1,950 L/m2 hr@0.1 mPa
  • the tensile strength at break is 12 mPa, tensile elongation at break.
  • the anti-squashing strength of the film is >0.8 mPa.
  • FIG. 3 is a cross section of a composite polyvinylidene fluoride multilayer porous hollow fiber membrane showing a sponge-like structural pore.
  • the density gradually increases from the inner surface layer to the outer surface layer, and there is no apparent functional two-layer boundary between the outer coating layer and the inner support layer, so there is no peeling between the outer coating layer and the inner support layer. Phenomenon, the two are completely integrated.
  • the surface of the outer coating shows the surface fine pore structure of the typical non-solvent phase separation (NIPS) process.
  • the inner surface of the inner support layer shows a thick macroporous structure on the surface of a typical thermal induced phase (TIPS) process.
  • NIPS non-solvent phase separation
  • the formulation used in this embodiment is as follows:
  • the inner support layer of the composite multilayer porous hollow fiber membrane filament is thermally induced phase separation (TIPS).
  • TIPS thermally induced phase separation
  • the melt-kneaded product (a) used in the process is: 30 parts by weight of poly(vinylidene fluoride) - Hexafluoropropane), 20 parts by weight of diamyl phthalate, and 10 parts by weight of active nano zinc oxide.
  • composition of the polymer mixture solution used in the functional outer layer non-solvent phase separation (IPS) coating process (b) consists of: 5 parts by weight of poly(vinylidene fluoride-hexafluoropropene), 1 part by weight of polyethylene Pyrrolidone (PVP), 1 part by weight of Tween-80, 40 parts by weight of dimethylformamide (DMF), 1 part by weight of glycerol.
  • the preparation method and process conditions were the same as in Example 3 except that the external coagulation bath was pure water at 50 °C.
  • the residual amount of zinc in the composite multilayer porous hollow fiber membrane yarn obtained was less than 0.3%.
  • the composite multilayer porous polyvinylidene fluoride hollow fiber membrane has an outer diameter of 1.24 mm, an inner diameter of 0.66 mm, a void ratio of 79.5%, and an average thickness of the composite coating layer of the functional outer surface of 0.018 mm, and a functional outer surface of the membrane.
  • the average pore diameter is 0.065 ⁇
  • the inner surface of the inner support layer has an average pore diameter of 0.8? ⁇
  • the pure water flux is 2,015 L/m2 hr@0.1 mPa
  • the tensile breaking strength is 12.2 mPa at 25 °C.
  • the anti-shrinking strength of the film is >0.8 mPa.
  • FIG. 6 shows a cross section of a composite polyvinylidene fluoride multilayer porous hollow fiber membrane, showing that the outer layer is very thin.
  • the layer refers to the pore layer, but there is no significant boundary between the functional outer coating layer and the inner support layer.
  • the formulation used in this example is as follows:
  • the inner support layer of the composite multilayer porous hollow fiber membrane filament is thermally induced phase separation (TIPS).
  • TIPS thermally induced phase separation
  • the melt-kneaded product (a) is composed of: 50 parts by weight of poly(vinylidene fluoride). - chlorotrifluoroethylene), 40 parts by weight of methyl benzoate, 30 parts by weight of active nano calcium carbonate and 5 parts by weight of antioxidant.
  • the functional outer layer non-solvent phase separation method (NIPS) coating process used in the polymer mixed solution composition (b) composition 30 parts by weight of poly(vinylidene fluoride-chlorotrifluoroethylene), 20 parts by weight of polyethylene Glycol (PEG), 20 parts by weight of Tween-80, sodium dodecylsulfonate, sodium dodecylbenzenesulfonate, 90 parts by weight of dimethylacetamide (DMAc), 10 parts by weight Ethylene glycol.
  • the preparation method and process were the same as in Example 3 except that the composite multilayer hollow fiber filaments removed from the winding wheel were not subjected to further stretching prior to the extraction and extraction process.
  • the residual amount of zinc in the composite multilayer porous hollow fiber membrane yarn obtained was less than 0.3%.
  • the composite multilayer porous polyvinylidene fluoride hollow fiber membrane has an outer diameter of 1.28 mm, an inner diameter of 0.70 mm, a void ratio of 71.3%, and an average thickness of a composite coating layer of a functional outer surface of 0.023 mm, and a functional outer surface of the membrane.
  • the average pore diameter is 0.01 ⁇
  • the inner surface of the inner support layer has an average pore diameter of 0.4 ⁇
  • the pure water flux is 1,360 L/m2 hr@0.1 mPa
  • the tensile strength at break is 9.3 mPa at 25 °C
  • the tensile elongation at break is 240%
  • the anti-shrinking strength of the film is >0.8 mPa.
  • the formulation used in this embodiment is as follows:
  • the inner support layer of the composite multilayer porous hollow fiber membrane filament is thermally induced phase separation (TIPS).
  • the melt-kneaded product (a) used in the process is: 40 parts by weight of poly(vinylidene fluoride) - ethylene), 30 parts by weight of dimethyl sebacate, 20 parts by weight of active nano-silica and 3 parts by weight of lubricant.
  • the preparation method and process are the same as those in Example 3, except that the uncured polyvinylidene fluoride inner support layer hollow fiber filament extruded from the hot phase separation method (TIPS) process passes through a 1 cm air section and then enters.
  • Non-solvent phase separation method (NIPS) process polyvinylidene fluoride coating stock solution device. The residual amount of zinc in the composite multilayer porous hollow fiber membrane yarn obtained was less than 0.3%.
  • the composite multilayer porous polyvinylidene fluoride hollow fiber membrane has an outer diameter of 1.25 mm, an inner diameter of 0.66 mm, a void ratio of 79.3%, and an average thickness of the composite coating layer of the functional outer surface of 0.025 mm, and a functional outer surface of the membrane.
  • the average pore diameter is 0.06 ⁇
  • the inner surface of the inner support layer has an average pore diameter of 0.85 ⁇
  • the pure water flux is 1,980 L/m 2 hr @ 0.1 mPa
  • the tensile strength at break is 11.8 mPa at 25 ° C
  • the tensile elongation at break is 148%
  • the anti-shrinking strength of the film is >0.8 mPa.
  • Fig. 7 shows the cross section of the composite polyvinylidene fluoride multilayer porous hollow fiber membrane, showing the functional outer coating layer and the inside. There is a blur visible boundary between the support layers. This is because the uncured polyvinylidene fluoride inner support layer hollow fiber filaments are obtained from the hot phase separation method (TIPS) process before entering the non-solvent phase separation (NIPS) process polyvinylidene fluoride coating stock solution. Some of the air in the l cm air section has solidified.
  • TIPS hot phase separation method
  • NIPS non-solvent phase separation
  • the formulation used in this embodiment is as follows:
  • the inner support layer of the composite multilayer porous hollow fiber membrane filament is thermally induced phase separation (TIPS).
  • TIPS thermally induced phase separation
  • the melt-kneaded product (a) used in the process is: 30 parts by weight of polysulfone, 20 parts. Weight of dimethyl adipate, 10 parts by weight of active organoclay.
  • PVDF Polyvinylidene fluoride
  • the residual amount of zinc in the composite multilayer porous hollow fiber membrane yarn obtained was less than 0.3%.
  • the composite multilayer porous polyvinylidene fluoride hollow fiber membrane has an outer diameter of 1.26 mm, an inner diameter of 0.65 mm, a void ratio of 82.3%, and an average thickness of the composite coating layer of the functional outer surface of 0.02 mm, and a functional outer surface of the membrane.
  • the average pore diameter is 0.055 ⁇
  • the inner surface of the inner support layer has an average pore diameter of 1.25 ⁇
  • the pure water flux is 2,460 L/m2 hr@0.1 mPa
  • the tensile strength at break is 10.3 mPa at 25 °C
  • the tensile elongation at break is 162%
  • the anti-shrinking strength of the film is >0.8 mPa.
  • the formulation used in this example is as follows:
  • the inner support layer of the composite multilayer porous hollow fiber membrane filament is thermally induced phase separation (TIPS).
  • the melt-kneaded product (a) used in the process is: 50 parts by weight of polyethersulfone, 40 Parts by weight of trioctyl trimellitate, 30 parts by weight of active diatomaceous earth and 5 parts by weight of anti-blocking agent.
  • the polymer mixed solution used in the coating process consists of (b) composition: 30 parts by weight of polyethersulfone, 20 parts by weight of polyvinyl alcohol, 20 parts by weight of sixteen Alkyltrimethylammonium bromide, 90 parts by weight of methyl ethyl ketone, and 10 parts by weight of methanol.
  • the preparation method and process are the same as those in Example 3, except that the fresh uncured hollow filaments extruded by the thermally induced phase separation (TIPS) process are coated by a non-solvent phase separation (NIPS) process at a rate of 10 m/min.
  • the device, after coating, is introduced into an external coagulation bath sink.
  • the residual amount of zinc in the composite multilayer porous hollow fiber membrane yarn obtained was less than 0.3%.
  • the composite multilayer porous polyvinylidene fluoride hollow fiber membrane has an outer diameter of 1.25 mm, an inner diameter of 0.66 mm, a void ratio of 78.5%, and an average thickness of a composite coating layer of a functional outer surface of 0.05 mm, and a functional outer surface of the membrane.
  • the average pore diameter is 0.062 ⁇
  • the inner surface of the inner support layer has an average pore diameter of 0.85 ⁇
  • the pure water flux is 1,720 L/m 2 hr @ 0.1 mPa
  • the tensile strength at break is 11.5 mPa at 25 ° C
  • the tensile elongation at break is 145%
  • the anti-shrinking strength of the film is >0.8 mPa.
  • the formulation used in this embodiment is as follows:
  • the inner layer of the composite multilayer porous hollow fiber membrane filament is subjected to a thermally induced phase separation (TIPS) process.
  • the melt-kneaded product (a) has a composition of: 40 parts by weight of ethylene-vinyl alcohol copolymerization. 30 parts by weight of tributyl phosphate, 20 parts by weight of activated kaolin and 3 parts by weight of heat stabilizer.
  • the composition of the outer coagulation bath was 20 parts by weight of polyethyl alcohol-400 (PEG-400) and 80 parts by weight of water.
  • the preparation method and process were the same as those in Example 3, and the residual amount of zinc in the composite multilayer porous hollow fiber membrane yarn obtained was less than 0.3%.
  • the composite multilayer porous polyvinylidene fluoride hollow fiber membrane has an outer diameter of 1.26 mm, an inner diameter of 0.67 mm, a void ratio of 74.5%, a functional outer surface average pore diameter of the membrane of 0.043 ⁇ , and an inner surface average pore diameter of the inner support layer. 0.86 ⁇ , pure water flux is 1,320 L/m2 hr@0.1 mPa, 25 °C, tensile rupture strength is 12.2 mPa, tensile elongation at break is 162%, and the tensile strength of the membrane filament is >0.8 mPa.
  • the formulation used in this embodiment is as follows:
  • the inner support layer of the composite multilayer porous hollow fiber membrane filament is thermally induced phase separation (TIPS).
  • the melt-kneaded product (a) used in the process is: 30 parts by weight of poly(vinylidene fluoride) - hexafluoropropane), a mixture of 20 parts by weight of a mixture of trioctyl trimellitate and tributyl phosphate, 10 parts by weight of active nano zinc oxide, active nano calcium carbonate, and active nano silica.
  • the polymer mixture solution used in the coating process consists of: (b) 20 parts by weight of polyvinylidene fluoride (PVDF, molecular weight 400,000-600,000 Daltons), 80 parts Weight of monobutyrolactone.
  • the composition of the outer coagulation bath was 40 parts by weight of dimethyldiamide (DMAc) and 60 parts by weight of ethylene glycol.
  • DMAc dimethyldiamide
  • the preparation method and process were the same as those in Example 3, and the residual amount of zinc in the composite multilayer porous hollow fiber membrane yarn obtained was less than 0.3%.
  • the composite multilayer porous polyvinylidene fluoride hollow fiber membrane has an outer diameter of 1.25 mm, an inner diameter of 0.65 mm and a void ratio of 79.4%.
  • the functional outer surface of the membrane has an average pore diameter of 0.08 ⁇
  • the inner surface of the inner support layer has an average pore diameter of 0.78 ⁇
  • the pure water flux is 2,280 L/m2 hr@0. lmPa, 25 ° C
  • the tensile rupture strength is 14.1 mPa.
  • the tensile elongation at break is 158%, and the crush resistance of the film is >0.8 mPa.
  • Composite multilayer porous polyvinylidene fluoride hollow fiber membrane filament is composed of melt-kneaded material used in internal support layer thermal induced phase separation (TIPS) process (a) 27 parts by weight of active nanometer calcium carbonate (average particle size ⁇ 40 nm ), 37.5 parts by weight of polyvinylidene fluoride (PVDF, molecular weight 250,000-400,000 Daltons), 33.8 parts by weight of dioctyl phthalate, 1.7 parts by weight of dibutyl phthalate, in a high-speed mixer The mixture was stirred at a high speed at room temperature to uniformly disperse the solid phase in the organic phase, and the uniformly dispersed solid (powdered) material was mixed for use.
  • TIPS thermal induced phase separation
  • NIPS Functional outer layer non-solvent phase separation composition of polymer mixed solution used in the coating process
  • PVDF polyvinylidene fluoride
  • PVP Polyvinylpyrrolidone
  • PEG-400 polyethylene glycol-400
  • DMAc dimethylacetamide
  • the thermally induced phase separation (TIPS) process uses a twin-screw extruder (screw diameter 20, aspect ratio: 40:1).
  • the temperature of the cylinder is controlled at 240 °C
  • the high-speed mixed homogeneous powdery material (a) is added for mixing.
  • the hollow fiber was extruded at a rate of 40 g/min from the center of the nozzle by injecting air into the hollow at a flow rate of 17.4 ml/min, directly through a non-solvent phase separation (IPS) process coating apparatus, and thermally induced phase separation ( TIPS) Process twin-screw extruder nozzle mold and non-solvent phase separation method (NIPS) process coating device mold directly connected through the insulation layer (pitch 0, that is, in the thermally induced phase separation method (TIPS) process method
  • TIPS thermally induced phase separation
  • TIPS thermally induced phase separation
  • TIPS thermally induced phase separation method
  • the hollow filaments were made without any contact with air prior to entering the non-solvent phase separation (NIPS) process coating apparatus, and the non-solvent phase separation (NIPS) apparatus was maintained at 130 °C.
  • TIPS thermally induced phase separation
  • NIPS non-solvent phase separation
  • the uncured hollow fiber is fully cured in a non-solvent phase separation (NIPS) process coating apparatus while coating a layer
  • NIPS non-solvent phase separation
  • an aqueous solution containing 30% dimethylacetamide (DMAc) at a temperature of 2 cm and a temperature of 50 ° C was introduced as an external coagulation bath, after passing through the 2 m long outer coagulation bath.
  • DMAc dimethylacetamide
  • the composite multilayer hollow fiber molded body unloaded from the winding wheel is subjected to 30% stretching in a 50 ° C water bath before being subjected to extraction and extraction treatment, and then, after stretching, immersed in a 95% ethanol solution and mechanically oscillated.
  • the organic pore former was extracted and maintained at 40 ° C for 0.5 hour, repeated 3 times, then washed with pure water, transferred into 2M hydrochloric acid (HC1 ) solution, and mechanically shaken for 0.5 hour in the greenhouse.
  • the inorganic pore former was extracted and finally rinsed and soaked in pure water for 3 hours each time in a greenhouse for 3 times, then immersed in a 50% aqueous glycerin solution for 2 days, and then air-dried at 50 °C.
  • the content of residual calcium ( Ca ) in the composite multilayer porous hollow fiber membrane yarn obtained was less than 0.3%.
  • the composite multilayer porous polyvinylidene fluoride hollow fiber membrane has an outer diameter of 1.25 mm, an inner diameter of 0.68 mm, a void ratio of 80.2%, and an average thickness of the composite coating layer of the functional outer surface of 0.03 mm, and a functional outer surface of the membrane.
  • the average pore diameter is 0.06 ⁇
  • the inner surface of the inner support layer has an average pore diameter of 0.75 ⁇
  • the pure water flux is 1,825 L/m 2 hr @ 0.1 mPa
  • the tensile strength at break is 14.7 mPa at 25 ° C
  • the tensile elongation at break is 182%
  • the anti-shrinking strength of the film is >0.8 mPa.
  • the outer coating surface shows the surface fine surface pore structure of a typical non-solvent phase separation (NIPS) process.
  • the inner surface of the inner support layer shows a stout macroporous structure on the surface of a typical thermal induced phase (TIPS) process.
  • TIPS Thermally induced phase separation
  • the polymer mixed solution used in the coating process consists of (b) composition: 30 parts by weight of poly(vinylidene fluoride-hexafluoropropane), 20 parts by weight of polyvinylpyrrole Anthrone (PVP), a mixture of polyethylene glycol (PEG), 20 parts by weight of sodium lauryl sulfonate, 90 parts by weight of a mixture of methyl ethyl ketone, acetone, 10 parts by weight of a mixture of isopropyl alcohol and n-butanol .
  • the preparation method and the process were the same as those in Example 9, and the residual amount of calcium (Ca) in the composite multilayer porous hollow fiber membrane yarn obtained was less than 0.3%.
  • the composite multilayer porous polyvinylidene fluoride hollow fiber membrane has an outer diameter of 1.24 mm, an inner diameter of 0.66 mm, a void ratio of 82.5%, a functional outer surface average pore diameter of the membrane of 0.08 ⁇ , and an inner surface of the inner support layer having an average pore diameter of 0.98 ⁇ , pure water flux is 2,560 L/m2 hr@0.1 mPa, 25°C, tensile breaking strength is 13.3 mPa, tensile elongation at break is 126%, and the anti-shrinking strength of the membrane is >0.8 mPa.
  • the formulation used in this embodiment is as follows:
  • the inner support layer of the composite multilayer porous hollow fiber membrane filament is subjected to a thermally induced phase separation method (TIPS).
  • TIPS thermally induced phase separation method
  • the melt-kneaded product (a) has a composition of: 40 parts by weight of polyvinylidene fluoride, 30 parts by weight of trioctyl trimellitate, 20 parts by weight of a mixture of active diatomaceous earth or activated kaolin and 3 parts by weight of a mixture of an antioxidant, a lubricant, and an antiblocking agent.
  • the preparation method and process were the same as those in Example 9, and the composite hollow fiber porous membrane was obtained to have a residual calcium content of less than 0.3%.
  • the composite multilayer porous polyvinylidene fluoride hollow fiber membrane has an outer diameter of 1.25 mm, an inner diameter of 0.64 mm, a void ratio of 78.6%, a functional outer surface average pore diameter of the membrane of 0.032 ⁇ , and an inner surface of the inner support layer having an average pore diameter of 0.82 ⁇ , pure water flux is 1,360 L/m2 hr@0.1 mPa, 25°C, tensile breaking strength is 14.1mPa, tensile elongation at break is 156%, and the anti-shrinking strength of the membrane filament is >0.8 mPa.

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Abstract

L'invention concerne un procédé de préparation d'une membrane fibre creuse poreuse multicouche composite et le dispositif et le produit associés. Le procédé comprend la préparation de fibres creuses poreuses non durcies ayant des diamètres de pore plus grands en tant que support interne de la membrane à partir de résines polymères macromoléculaires thermoplastiques par un procédé de séparation de phases induit thermiquement, puis la liaison d'une couche de revêtement super-mince à fonction de microfiltration ou de nanofiltration et d'un petit diamètre de pore préparée sur la surface externe des fibres creuses à partir d'une solution des résines polymères macromoléculaires thermoplastiques par un procédé de revêtement en utilisant un procédé de séparation de phases induit par un non-solvant. La membrane fibre creuse poreuse multicouche composite présente une excellente résistance mécanique et un débit d'eau élevé, tout comme les membranes préparées par un procédé de séparation de phases induit thermiquement, un effet de filtration haute précision et une grande résistance à la contamination, tout comme les membranes préparées par un procédé de séparation de phases induit par un non-solvant, et la force d'adhésion élevée de la membrane préparée par le procédé ci-dessus.
PCT/CN2010/079531 2009-12-07 2010-12-07 Procédé de préparation d'une membrane fibre creuse poreuse multicouche composite et dispositif et produit associés WO2011069441A1 (fr)

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