CN102160967A - Lining-reinforced hollow fiber membrane tube as well as preparation device and preparation method thereof - Google Patents
Lining-reinforced hollow fiber membrane tube as well as preparation device and preparation method thereof Download PDFInfo
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- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention relates to a lining-reinforced hollow fiber membrane tube as well as a preparation device and preparation method thereof, belonging to the field of preparation of polymer hollow fiber microporous membranes. In the membrane tube, a film forming chimney is designed reasonably, a coating layer on a braided tube led from a coating machine is subjected to controllable steam diffusion-induced phase inversion firstly, and then enters a coagulating bath, so that an open-pore surface skin layer with high porosity is formed on a film separation layer, and the radial direction of the membrane layer is in an integral asymmetric and interpenetrating cell-shaped structure; a composite material is selected to prepare a transition layer, so that the transition layer has excellent adhesive force and hardness, excellent compatibility with a surface separation layer and tiny cubical contraction in a phase conversion process at the same time; optimized braided tube size and braiding density are selected to ensure that the braided tube has lower flexibility; and a method capable of maintaining reasonable roundness and the like in the production process ensures that the lining polyvinylidene fluoride (PVDF) hollow ultrafiltration membrane tube has the advantages of integral asymmetric structure with high integrity, high-porosity surface separation layer, higher back pressure enduring capability and the like.
Description
Technical field
The invention belongs to polymeric hollow fiber microporous barrier preparation field, relate to a kind of liner enhancement mode hollow fiber film tube and preparation facilities and preparation method.
Background technology
Along with the continuous lifting of industrialization degree and going from bad to worse of all kinds of water sources quality, chemical stability is good, mechanical strength is high, contamination resistance becomes by force the more and more general requirement of separation membrane performance.Simultaneously, owing to the degree of depth of a large amount of water bodys is polluted the water quality type lack of water that causes, make the MBR process become the wastewater processing technology that market prospects are arranged most.Since building up from the exemplary engineering of first MBR of nineteen ninety, the special-purpose membrane component of MBR process is from flat hollow form or the multichannel external form of expanding to.Current hollow form membrane component has occupied than clear superiority in the MBR in whole world engineering is used, especially liner enhancement mode hollow membrane element, though the shortcoming that exists the film separating layer to peel off from enhancement layer the fracture of wire situation can occur hardly, thereby market application foreground is good.The liner type hollow membrane element of developing at the desired high mechanical properties of MBR process mainly is made up of the surface isolation layer of coating and braided tube or other type backing material, undertakes respectively and separates and two functions of high strength.
The film forming principle of surface isolation layer is consistent with immersion phase inversion masking technique, selectable membrane material is basically identical also, comprises that therefore membrane material commonly used such as polyacrylonitrile (PAN), polyether sulfone (PES) or Kynoar (PVDF) all is used to prepare liner enhancement mode membrane component.United States Patent (USP) 4,061,821 disclose a kind of method for preparing the PAN hollow-fibre membrane of liner braided tube, U.S. KOCH company
The MBR membrane component is surface isolation layer material (Judd S.2006, The MBR BOOK) with PES, United States Patent (USP) 5,472, and 607 disclose a kind of PVDF solution coating tubular braid to form the method for the hollow-fibre membrane of being strengthened by braid.Thereafter, patent US7,306,105, CN 1829597A, CN 1864828A, CN1281299C, disclosed enhancement mode hollow fibre membrane components such as CN 101239281A, CN 101254420A all be the polymer raw material of surface isolation layer with PVDF.Though PAN, PES and PVDF have comparatively ideal chemical stability, and aspect anti-oxidant and antioxidant, PAN and polysulfones series material all are weaker than PVDF.The PVDF resin has the characteristic of fluororesin and resins for universal use concurrently, has good high temperature resistant and resistance to chemical corrosion; The pH scope that can bear reaches 1～12 even wideer, is the most outstanding membrane material of oxidation resistance, can stand harsh oxidant cleaning condition, anti-biodegradation and x radiation x.In engineering of water treatment, clorox is generally used for membrane component as the free chlorine source and cleans and former water sterilization.Therefore the membrane component of PVDF material becomes the first-selected core parts of these engineering of water treatment.
The material of surface isolation layer has determined the chemical stability of enhancement mode membrane component, and flux and separation factor then depend on the microstructure of separating layer.United States Patent (USP) 5,472, thus the surperficial percent opening of 607 disclosed liner enhancement mode PVDF hollow fiber ultrafiltration membrane is low and the overlay section has macrovoid and causes filtration flux on the low side.In its follow-up patent, US5 with the casting solution of the method formation blend of poly-(the acetate hexenyl ester) that add partial hydrolysis and alpha-alumina particle, compares with the milipore filter that does not contain alpha-alumina particle in 914,039, shows higher water permeability.Yet this class casting solution often physico-chemical property is unstable and be difficult to make, thereby causes relatively poor repeatability.US5, the hydrophilic component poly-(acetate hexenyl ester) that the casting solution in 472,607, US5,914,039 and US6,354,444 uses generates through partial hydrolysis.Use the concentrated sulfuric acid to make catalyst, reaction is at high temperature carried out for a long time, and degree of hydrolysis is wayward.And alpha-alumina particle easily from casting solution partly precipitated come out, the precipitation degree changes in time, thereby causes the inhomogeneous and relatively poor film reproducibility of overlay.
Said method all is in order to improve the PVDF hydrophobicity by add hydrophilic composition in casting solution, thereby improves the membrane filtration flux.Because, in application field of water treatment, have a kind of viewpoint to think: the membrane material of good hydrophilic property just is not easy to be blocked up by dirt, also clean easily after dirty stifled and recover, therefore have many academic documents and patent to adopt the hydrophily that strengthens the PVDF resin such as blend, copolymerization, grafting or the method that film surface or body are carried out modification such as crosslinked.There is not specific logical relation in fact between the strainability of the hydrophily of polymer and membrane component.Result of study also shows, comes the antifouling property of evaluated for film that a lot of problems are arranged with hydrophily.Pollutant character in the former water is very complicated on the one hand, and hydrophily practical manifestation to film in certain scope does not have decisive influence; On the other hand, with the structure of concentration polarization, film separating layer and supporting layer the stability influence of membrane filtration characteristic is compared, the influence of the character of membrane material own often can be ignored, and in fact people have exaggerated the adverse effect of hydrophobicity to membrane flux to a certain extent.Face inclined to one side with it and emphasize the initial pure water flux of membrane component not as paying close attention to membrane material surface and supporting layer structure to the mechanical strength of film and the influence of strainability with making or have much ado more.Hollow-fibre membrane with unsymmetric structure characteristics is made up of very thin and fine and close relatively surface isolation layer and relatively more loose supporting layer, under the ideal state, pollutant is blocked in outside the selective separating, can not enter the inside of film, blocks up thereby alleviated irreversible dirt to a certain extent.Factors such as bridge formation in hole of the inhomogeneities of film surface holes in fact, the absorption between the shape of impurity particle, impurity and the membrane material, impurity, winding make the perfect condition of this surface filtration not exist.So flux progressively descends, the necessity of Chemical cleaning etc. all is in esse.Can selectivity prepare surface isolation layer and supporting layer structure towards application by designing suitable filming technology, to be adapted to the types of applications field, in fact, membrane structure control is the technological core of film preparation.
But, development trend from membrane preparation technology, thin and fine and close cortex is not best structure for perforated membrane, because the perforated membrane element is usually used in serious pollution water source, as the MBR engineering, enter in the former water of membrane component and contain a large amount of solid particles, and need bear long-time frequent cleaning and current (or air-flow) washing away on the film surface.Can cause the decline of membrane component separative efficiency after the so thin top layer wearing and tearing.Therefore quality preferably perforated membrane should be whole asymmetry.On the one hand, the surface isolation layer has the characteristics of open-celled structure and high opening rate; On the other hand, surface isolation layer and membrane material main body (supporting layer) are an integral body, and both are not significantly boundary at aspects such as structure, porosity, aperture sizes, just radially become big from the top layer to the supporting layer aperture gradually by little.Chinese patent (CN1099309C) discloses the method that a kind of dried spray-wet spinning prepares whole asymmetry microporous membrane of polyethersulfone, the supporting layer of the doughnut poly (ether sulfone) film of this method preparation has symmetry polygon cell shape structure, the cell size changes to the opposite side top layer gradually and stably from a side top layer, briefly, composition by casting solution, and film-forming process realize controlled hole gradient, reach separating layer percent opening height, supporting layer does not contain the purpose that macrovoid and filtration resistance are ignored.
When dried spray-wet spinning was used to prepare PVDF doughnut perforated membrane, the hydrophobicity that the PVDF resin is stronger made and realizes that whole asymmetry structure faces very big difficulty.Because the equal phase region of PVDF (1)-solvent (2)-water (3) ternary system is very little, after nascent membrane structure enters coagulating bath, gel takes place and forms compacted zone in the top layer in the extremely short time, thereby having hindered non-solvent spreads in the film main body, the slow The apparent phenomenon of PVDF gelation rate occurs, also caused delay phase-splitting and the continuous result who grows up of macropore under the top layer.Therefore be difficult to prepare the hollow-fibre membrane silk of high surperficial percent opening, and more macrovoid unavoidably appears in supporting layer with dried spray-wet spinning.Therefore film silk flux is low, and mechanical strength is relatively poor.
Liner enhancement mode hollow membrane pipe drawback of greatest concern is: the adhesive effect of surface isolation layer and enhancement layer.More existing patents and document propose multiple solution pointedly.Wherein representative scheme can be divided three classes: the structure optimization method of investment, transition zone bonding method and inner lining material.
Investment: in order to increase the bonding force of two class materials, fortifying fibre and casting solution can pass through spinning head together, through making hollow-fibre membrane (for example CN1695777A) behind the coagulating bath gel, fortifying fibre vertically is embedded in the wall of hollow-fibre membrane in this film then.Perhaps, earlier spin out hollow-fibre membrane with casting solution, immerse again in the polymer material film liquid after this film outside is woven into net with synthetic fibers then, strengthen hollow-fibre membrane (CN1864828A) through making reticular fibre behind the coagulating bath gel, netted braid is embedded in the supporting layer of hollow-fibre membrane.Because it is flexible that reinforcing material produces with the swing of film pipe, thereby cause the structural damage of film support, too high retractility can cause non-response damage.
Transition zone bonding method: except that surface isolation layer and enhancement mode, increase a transition zone and be used to improve the adhesive force of surface isolation layer on enhancement layer.U.S. Pat 7,306,105 make enhancing braid and casting solution together by spinning head, and the hollow-fibre membrane of making behind the gel and the casting solution of another composition are spun into the liner hollow-fibre membrane by spinning head for the second time.Perhaps, hollow braid, adhesive and casting solution are made the liner hollow-fibre membrane by the coating head together, as patent US 7,165,682, wherein adhesive is coated on the hollow braid, casting solution covers on the adhesive, and the effect of adhesive is the bond strength that increases between film and braid.Yet all there is the consistency problem between layer and the layer in above-mentioned two kinds of methods, and transition zone has formed smooth interface on its surface after passing through gel, the surface isolation layer can not with very firm bonding of its formation.And adhesive contacted water as epoxy resin, polyurethane before not solidifying, and more can lose bonding performance.
Transition zone can improve the bonding force of surface isolation layer and enhancement layer, but need the film preparation process remain the layer with layer between compatibility, transition zone can be undertaken two other important function in fact, has on the one hand the braiding lines on the little floating braiding enhancement layer of the feature surface of stronger bonding force and volume contraction with it; On the other hand, transition zone should have fabulous compatibility with the surface isolation layer, becomes an overall structure on chemical feature, and on this basis, transition zone should possess more outstanding hardness and bear the ability of back pressure to improve film pipe integral body.
The structure optimization method of inner lining material: United States Patent (USP) 6,354,444 disclose a kind of physical method that rete is peeled off problem that solves, and just use dissimilar inner lining materials as surface isolation layer supporter, it has different patterns for knitting, for example regular pattern composite, god of unusual strength's type and diamond pattern.It is found that weavy grain has better rete cohesive than rule and the tighter diamond pattern braid of god of unusual strength's braid.Yet rete is peeled off problem and is still existed.In fact, think that with it weavy grain influences the cohesive of film separating layer and enhancement layer, not as thinking: the tightness degree of weavy grain is bigger to fusible influence.
Summary of the invention
At the problem that prior art exists, technical purpose of the present invention provides a kind of preparation facilities of liner enhancement mode hollow fiber film tube; Another technical purpose of the present invention provides the method for utilizing this equipment to prepare liner enhancement mode hollow fiber film tube; Another technical purpose of the present invention provides the liner type hollow fiber film tube product that utilizes the said equipment and method to prepare; By realizing technical purpose of the present invention, the liner enhancement mode hollow fiber film tube that obtains has distinct surface isolation layer, transition zone and braided tube enhancement layer three-decker.
In order to realize technical purpose of the present invention, technical scheme of the present invention is as follows.
One, a kind of liner enhancement mode hollow fiber film tube preparation facilities mainly is made up of casting film flow container (1), deaeration jar (2), the former liquid storage tank of blend (3), manifold (4), transition zone precoating jar (7), coating head (8), film forming path (9), coagulating bath (10), potcher (11), godet (12) and reel (13); Wherein, described manifold (4) inside is respectively arranged with blend liquid pump (5) and casting film liquid pump (6); Applying head (8) is arranged in the film forming path (9);
On the one hand, the liquid outlet of the former liquid storage tank of blend (3) connects the inlet of blend liquid pump (5) by valve, the top lateral opening of the feed liquid distribution grid (202) of the tank body (205) of the outlet connection transition zone precoating jar (7) of blend liquid pump (5), go out (202) of transition zone precoating jar (7) connect the inlet that applies head (8), and apply the outlet of head (8) and the consistent UNICOM of outlet in its residing film forming path (9); The outlet in film forming path (9) connects the inlet of coagulating bath (10), and the outlet of coagulating bath (10) connects the inlet of potcher (11), and the outlet of potcher (11) connects reel (13) after connecting godet (12) again;
On the other hand, the outlet of deaeration jar (2) is by the inlet of valve connection casting film flow container (1), and the outlet of casting film flow container (1) connects the inlet of casting film liquid pump (6), and the outlet of casting film liquid pump (6) connects on the coating head (8).
Further, the outer temperature and humidity control system (15) that also is connected in described film forming path (9).
Further, described transition zone precoating jar (7) is made up of feed liquid distribution grid (202), tank body (205), connector (203) and scraping blade (204); Wherein feed liquid distribution grid (202) is arranged on the top of tank body (205), and in the tank body lateral location opening of feed liquid distribution grid (202) top and the outlet UNICOM of blend liquid pump (5); Connector (203) in the tank body (205) is connected scraping blade (204) the interior feed liquid distribution grid of tank body (205) (202) below, goes out (206) top; The emptying of tank body (205) bottom sides opening.
Further, described film forming path (9) is made up of airflow-distribution board (302), inner chamber (304), coating head (8), permeable wall (306) and delivery pump (303); Wherein, airflow-distribution board (302) is arranged on the top of inner chamber (304), and the below of airflow-distribution board (302) is provided with coating head (8), and the bottom that permeable wall (306) is arranged at coating head (8) is the bottom of inner chamber (304); Inner chamber (304) is positioned at the lateral opening of airflow-distribution board (302) top, and the lateral opening of permeable wall (306), and this two places opening is by delivery pump (303) UNICOM; The lateral opening in the exit of inner chamber (304) connects nitrogen inlet.
Further, film forming path (9) length is adjustable in 5～100 centimetres, and as preferably, path length is 5～30 centimetres.
Two, utilize the described liner enhancement mode of claim 1 hollow fiber film tube preparation facilities to prepare the method for liner enhancement mode hollow-fibre membrane, it is characterized in that may further comprise the steps.
The liner braided tube is formed by the braiding of chemical fibre multifilament, has excellent chemical stability and mechanical strength.Material is one or both shufflings in Fypro, polyester fiber and the polyurethane fibre.The size and the performance of factor affecting internal lining pipes such as count, chemical-fibres filaments dawn number, braiding number of spindles.Count of the present invention is 20～60 orders, and the internal lining pipe deformation of high count is little, but yields poorly; And the problem during low-density is the percentage elongation height, and is yielding, and then influences film pipe overall performance, and as preferably, count is 25～40 orders.The braiding number of spindles is 16～32 ingots.When the filament denier of selecting for use is high, can adopt the braiding of 16 ingots; And adopt 24 or 32 ingots when braiding, can be made into the internal lining pipe that has than large diameter.In addition, higher number of spindles can cause external diameter to increase, and produces the problem that easily is crushed.
Wherein, described casting solution mainly is made up of PVDF resin, solvent, non-solvent, hydrophilic macromolecule pore former and thickener; And described PVDF resin quality degree is 15%～20%, described solvent quality degree is 50%～65%, described water soluble polymer pore former mass percentage content is 10～20%, described hydrophily thickener qualities degree is 5%～15%, and described non-solvent mass percentage content is 0.5～1.5%; Hydrophily thickener, macromolecule pore former and non-solvent are dissolved in the solvent,, are pressed into the middle vacuum defoamation of deaeration jar (2) 4～10 hours fully after the dissolving, change casting solution storage tank (1) then after filtering over to again to wherein adding the polyvinylidene fluoride resin raw material.
The composite that inorganic nano-particle and PVDF resin, solvent, additive blend are formed.Hydrophily thickener and water soluble polymer pore former are dissolved in the solvent, again to wherein adding PVDF resin and nano-powder, blend forms viscosity 10,000～30,000 centipoise blend stostes, and the mass percentage content of described PVDF resin is 5%～10%, the mass percentage content of described solvent is 50%～70%, the mass percentage content of described water soluble polymer pore former is 10～20%, described hydrophily thickener qualities degree is 5%～15%, and the mass percentage content of described nano material is 0.5～5%; To change in the former liquid storage tank of blend (3) after the blend stoste process deaeration processing.
Advantage of mixing small amounts of inorganic oxide nano-particles or macromolecular fibre in transition zone of the present invention is: adding inorganic nano-particle can combine heat-resisting, the chemical stability of inorganic material with the pliability and the low cost of polymer, can improve the transition zone rigidity and and the cohesive force of surface isolation layer and enhancement layer; Adding high polymer nanometer fiber can increase and substrate macromolecule material effect entangled to each other, strengthens the intensity and the pliability of transition zone.
The nanoparticle surface active atomic is many, is easy to adsorb fully with polymer, bonding.When being subjected to external force, particle is difficult for breaking away from matrix.And, absorb lot of energy because the interaction of stress field produces a lot of little deformed areas in matrix.This just makes the transition zone composite can transmit the external carbuncle of being born preferably, can cause the matrix surrender again, consumes a large amount of impact energys, thereby reaches effect toughness reinforcing simultaneously and that strengthen.But the nanometer powder particle diameter is little, and surface area is big, is easy to reunite.Therefore when the compound transition zone of polymer of nanometer powder is added in preparation, be difficult to obtain the composite of nanostructured with common blending method.In order to increase the interface binding power of nanometer additive and polymer, improve the even dispersibility of nanoparticle in macromolecular material, need nanometer powder is carried out surface modification.Surface modified powder has reduced the surperficial energy state of particle, eliminates the surface charge of nano particle, improves the affinity of nano particle and organic facies, weakens the surface polarity of nano particle etc.The present invention uses the inorganic nanometer powder of surface modifications such as oleic acid, stearic acid, silane coupler, has strengthened nanoparticle dispersibility in polymer matrix, obtains the compound transition zone of nanostructured.The morphology microstructure that uses can be spherical, sheet, bar-shaped, columnar nanometer particle, or even nano wire, nanotube, nanometer film etc.; What the present invention preferentially used is nano wire and nano bar-shape powder, because of nano wire and the fine physical entanglement effect that generates with chain structure and polymer matrix of the existing particle of nanometer rods, have the chemical bond effect that causes owing to surface-active again, in polymer is filled, show good reinforcing action.Adopt the transition zone composite of modified Nano powder preparation, its hot strength can increase, and fracture elongation improves, and young modulus of material increases.Though the porosity of membrane material descends to some extent, pure water flux and hydrophily increase.The present invention with solution or the direct blend of emulsion form, prepares the compound buffer layer material of nano-powder/PVDF with nano unit, macromolecule resin and other additive of modification.
Further, described nano material is hydrophobic silica, aluminium oxide, zirconia, titanium oxide inorganic nano-particle, or high polymer nanometer fiber.
Described transition zone blend stoste has lower viscosity (10,000～30,000 centipoise).Braided tube at first applies blend stoste, the rough woven pattern of floating braided tube.Reach the surface smoothness that improves the surface isolation layer on the one hand, on the other hand, the not contractility of nano material causes the integral hardness of film to improve.
The temperature of control manifold (4) is at 25～95 ℃, enters in the tank body (205) blend stoste is pressed into the feed liquid distribution grid (202) of precoating jar (7) from the former liquid storage tank of blend (3) by blend liquid pump (5) after; Simultaneously, liner braided tube (201) penetrates from tank body (205) top, scrape floating whole weavy grain slit through the scraping blade (204) that is fixed in jar interior both sides by connector (203) in tank body (205), obtain drawing from tank body (205) outlet at bottom (206) again with the liner braided tube that blend stoste is scraped after smearing.Tank body (205) bottom sides is provided with evacuation port, helps on the one hand discharging air to the slack tank material feeding time, makes things convenient for the cleaning operation of precoating jar on the other hand, when equipment normally moves, is normally off.
Manifold (4) is the square box of steel plate welding, in establish the circulating hot water passage.Manifold is provided with the spin manifold temperature demonstration and casting solution pressure shows.The Controllable Temperature scope of manifold is 25～95 ℃, and as preferably, the temperature of manifold is set between 50～80 ℃.Casting film liquid pump (6) all is placed in the manifold with blend liquid pump (5), makes the temperature of casting solution and blended liquid keep stable before being coated on braided tube.
At first by precoating jar (7), the essential structure of precoating jar as shown in Figure 4 for braided tube (201).The blended liquid that is mixed with inorganic particulate is pressed into by blend liquid pump (5), through entering jar interior (205) behind the feed liquid distribution grid (202), braided tube penetrates from the tank body top, tank base outlet (206) is drawn, two scraping blades (204) are fixed in jar interior both sides by connector (203) in the tank body, are used for the weavy grain slit of floating braided tube.
The liner braided tube (201) of passing precoating jar (7) enters film forming path (9), at first passes through airflow-distribution board (302), continues across coating head (8) in again in inner chamber (304); By casting film liquid pump (6) casting solution is pressed into by casting solution storage tank (1) on the one hand and applies head (8), by applying head (8), obtain nascent film pipe (305) simultaneously being coated with the liner braided tube outside coating casting solution of blend stoste; Delivery pump (303) will be carried mixed vapour from bottom to up in inner chamber (304), make nascent film pipe (305) process vapor phase conversion process in film forming path (9), promptly begin to take shape the film surface isolation layer (101) of porous in nascent film pipe (305) outside; Permeable wall (306) is made as porous ceramics or sintered stainless steel by the anti-solvent material of porous, is used for strengthening the uniformity that air-flow distributes in the path.The nitrogen input quantity of control nitrogen inlet can be regulated the humidity in the path complementaryly.
The braided tube (201) of passing precoating jar (7) enters film forming path (9), and the structure in film forming path as shown in Figure 5.Mainly constitute by airflow-distribution board (302), inner chamber (304), permeable wall (306).And the outer coating of coating head (8), coating head (8) places the top in film forming path.The bottom, path is near coagulating bath.Braided tube (201) continues across the coating head in the film forming path, the nascent film pipe (305) of outside coating blend stoste and casting solution is process vapor phase conversion process in the path, the film pipe outside begins to take shape the surface isolation layer of porous, path length is adjustable in 5～100 centimetres, as preferably, path length is 5～30 centimetres, when coating speed is slow, select less length, the double diffusive process of the solvent on film silk surface and non-solvent make the time of staying of film pipe in the path keep stable, because can be finished in the extremely short time.And the long time only can cause the excessive volatilization of film tube outer surface solvent.The path lower ending opening also stretches into coagulating bath, so the solvent in the coagulating bath and non-solvent also can spread in the path, thereby influences the content of temperature, solvent and non-solvent in the path.
Temperature in the film forming path, moisture and solvent obtain strict control.In a so in check atmosphere, the separating layer partial solvent of film tube outer surface volatilization also absorbs the moisture in the surrounding environment and tentatively solidifies.The volatile quantity of the temperature effect solvent in the path and the feature that balances each other of casting solution, and moisture in the path and solvent mainly influence the convection current diffusion rate of solvent-nonsolvent.
Further, described film forming path is that humidity is 50～90% in 40～80 ℃ the scope by temperature and humidity control system (15) control temperature.
By in the coating membrane equipment, adding these parts of path, vapor phase is transformed with immersion inversion of phases process combine.Nascent film separating layer is experience vapor phase conversion process in the path at first, be not separated even do not produce, the casting solution on top layer is formed also can be owing to solvent evaporates, moisture penetration change, this variation will help the uniformity of casting solution phase separation speed in the coagulating bath, thereby produce the surface of high opening rate.After the internal lining pipe of surface applied casting solution enters coagulating bath, the surface with high opening rate more help non-solvent by the coagulating bath main body to the overlay diffused inside, make film separating layer and transition zone after the moulding be whole asymmetrical cell shape structure.
Step 6, the immersion inversion of phases takes place and the gel typing in nascent film pipe (305) in the coagulating agent of coagulating bath (10), and described coagulating agent is the mixture of solvent and water, and wherein the mass percentage content of solvent is 30%～60%, and the temperature of coagulating agent is 30 ℃～90 ℃; Inner lining film pipe silk journey of process in described coagulating bath is 10～30 meters;
The inner lining film pipe of finishing the vapor phase conversion process in the film forming path enters the coagulating basin below the path, and immersion inversion of phases process takes place.The coagulating agent of coagulating basin is the mixture of solvent and non-solvent.
In coagulating bath, the typing of skin covering of the surface separating layer and transition zone generation immersion inversion of phases and gel.Therefore the distance of film pipe process in coagulating bath (silk journey) is decided according to gelation rate and coating speed, and gelation rate is subjected to the composition and the Temperature Influence of coagulating bath.Further, the distance of inner lining film pipe process in described coagulating bath (silk journey) is 10～30 meters.According to result of the test, the silk journey of preferred coagulating bath is 5～10 meters.After separating layer and transition zone were separated, it was rich stingy with polymer to form polymer, and richness develops into the main body of this double-layer structure mutually, stingyly was made up of solvent, non-solvent and most additive, can dissolve each other with water.
The processing of preserving moisture of step 9, glycerine.Soak being placed in the glycerine water solution again behind the dried free moisture content of film management and control, the hole of film tube-surface separating layer can further farthest kept in the dry run, also reduce the shrinkage factor of film separating layer and transition zone simultaneously.Described film pipe soak time in glycerine water solution is 12～24 hours, and wherein the quality of glycerine is 10%～50% than concentration.As preferably, the quality of glycerine is 20%～30% than concentration.
In the method for the invention, the weight average molecular weight of described PVDF resin is between 20～800,000 dalton, and alternative PVDF resin brand has: Kynar 461, Kynar 740, Kynar 760, and Kynar 761, and HSV 900, FR 904, Solef 1010, and Solef 1015, and Solef 6010, Solef 6020, and Solef 6030 and other weight average molecular weight are greater than 200,000 resin.Have as preferred brand: Kynar 760, and Kynar 761, and HSV 900, and FR 904, and Solef 1010, and Solef 1015, and Solef 6020, and Solef 6030.
Further, described solvent is a kind of in N-methyl pyrrolidone (NMP), dimethyl formamide (DMF), dimethylacetylamide (DMAC), the dimethyl sulfoxide (DMSO) (DMSO).These four kinds of fine solvents that reagent all is the PVDF resin be to be simplified the composition of prescription, only select wherein a kind of for use.Because similar to the solvability of PVDF, so consumption is basic identical.As preferably, solvent is selected dimethylacetylamide (DMAC) and N-methyl pyrrolidone (NMP) for use.
Further, described non-solvent is that one or more of water, ethanol, isopropyl alcohol, glycerine, n-butanol, ethylene glycol, diglycol mix.Non-solvent is the material that causes that casting solution is separated, and causes the overlay gel solidification.In casting solution, add non-solvent, can accelerate the inner phase separation of overlay.The amount that adds non-solvent is then very crucial.Non-solvent is strong more, and consumption is few more.In addition, strong, the weak non-solvent use of can arranging in pairs or groups.As preferably, described non-solvent is water or glycerine.When selecting strong non-solvent water, consumption is less than 1.0%.
Further, described hydrophily thickener is 1, one or more mixtures in 4-butyrolactone, phosphorus benzene bis-acid potassium dibutyl ester, low molecular polyethylene glycol (MW:200～600), the polyvinyl alcohol (MW:200～600).Add an amount of hydrophily thickener in casting solution after, can regulate and control the viscosity of casting solution, increase equal phase region scope, also can promote the diffusion of non-solvent ecto-entad simultaneously, overall effect is that the finger-like pore that suppresses in the supporting layer occurs.
Further, described water soluble polymer pore former is high molecular weight polyethylene glycol (MW:2,000～10,000), PEO (MW:10,000～50,000), polyvinyl alcohol (MW:10,000～50,000), one or more mixtures in the polyvinylpyrrolidone (MW:10,000～400,000).Water-soluble pore former constantly comes out with solvent elution owing in the rinse cycle after gelation except that the effect that possesses described thickener, and increases the porosity of supporting layer.As preferably, the macromolecule pore former is that PEG is or/and PVP.The range of choice of the molecular weight of described PVP is between 10000～100000, and the molecular weight of described PEG is between 1000～10000.
Three, the liner enhancement mode hollow fiber film tube for preparing according to method of the present invention.
Liner type enhancement mode hollow fiber film tube of the present invention is by film surface isolation layer (101), transition zone (103) and (104) three layers of formation of braided tube enhancement layer, as shown in Figure 1.Film surface isolation layer (101) is the function body of hollow membrane pipe, by the preparation of diffusion phase inversion, is whole asymmetry structure, and material is the polyvinylidene fluoride resin that pliability is good, oxidation resistance is strong.Transition zone (103) is used to improve the rigidity of film pipe, and the bonding force of overlay and enhancement layer, and thickness is 0.05～0.15mm, and material is the composite of polyvinylidene fluoride resin and inorganic nano-particle, nanometer rods or nano-fibre blend.Braided tube enhancement layer (104) is formed by the braiding of chemical fibre multifilament, has excellent chemical stability and mechanical strength.Thickness is 0.3～0.7mm.
Beneficial effect of the present invention is:
At first, the liner enhancement mode hollow membrane control that proposes by the present invention be equipped with that technology produces the film pipe, overlay has the good whole asymmetry, the cell shape structure that is IPN, do not form the macrovoid that influences the membrane material separative efficiency, so the film pipe has improved the ratio in active hole under the prerequisite that does not increase porosity.By the transition zone hardness height that composite is made, in the film liquid-phase conversion process, the transition zone cubical contraction is little, so the ability that the film pipe bears back pressure has reduced the probability that the film separating layer is peeled off from enhancement layer above 0.35MPa.Enhancement layer count height, axial percentage elongation is minimum, so the film pipe also can not damage the overlay of film pipe under fluid impact.
Secondly, the present invention passes through: the film forming path that (1) is reasonable in design, after at first causing inversion of phases through controlled diffusion of vapor, overlay on the coating head braided tube of drawing enters coagulating bath, make the film separating layer form the open surface cortex of high porosity, thereby cause the cell shape structure of whole asymmetric and IPN of radially being of rete; (2) select the Composite Preparation transition zone, make transition zone have good bonding force and hardness simultaneously, possess minimum cubical contraction in the compatibility good, the inversion of phases process with the surface isolation layer; (3) the braided tube size and the count of selection optimization, make braided tube have very low retractility, can safeguard methods such as rational roundness in process of production, make liner type PVDF hollow fiber ultrafiltration film pipe be equipped with the good whole asymmetry structure of integrality, high opening rate surface isolation layer and higher advantages such as back pressure ability to bear.
At last, the present invention designs suitable film forming path, diffusion of vapor is caused the diffusion of inversion of phases and solvent to be caused the inversion of phases process and combines, make overlay at first form the top layer of high opening rate, with the solvent after the quickening overlay immersion coagulating bath and the reverse diffusion process of non-solvent, it is advantageous that: film separating layer structure is tending towards whole asymmetry, as shown in Figure 1.Among the figure (101), (103) are respectively film separating layer and transition zone.From the cross-section of face, even structure does not have the described macrovoid of Fig. 4 (102), and transition zone is then more loose, and desirable film separating layer has the high surface of percent opening (105).In contrast, a lot of diffusions cause the polymeric membrane cross section of inversion of phases method preparation and usually find macrovoid, this structure influences the mechanical performance of membrane material on the one hand, on the other hand can be in dry run owing to shrinkage stress cause defective, its comprehensive result makes the membrane module can't be by integrity test.For liner type film Guan Eryan, though do not influence the overall mechanical properties of membrane material, the disappearance of integrality aspect still merits attention.Have macroporous inner lining film pipe and have feature shown in Figure 2.
Description of drawings
Fig. 1 is a liner enhancement mode film pipe schematic diagram (24 ingot);
Wherein, 101-film surface isolation layer; The 103-transition zone; 104-braided tube enhancement layer; The 105-surface.
Fig. 2 is a liner enhancement mode film pipe schematic diagram (16 ingot);
Wherein, 101-film surface isolation layer; The 103-transition zone; 104-braided tube enhancement layer; The 105-surface.
Fig. 3 is a liner enhancement mode film pipe schematic diagram (32 ingot);
Wherein, 101-film surface isolation layer; The 103-transition zone; 104-braided tube enhancement layer; The 105-surface.
Fig. 4 is the liner enhancement mode hollow membrane pipe schematic diagram that contains macroporous structure;
Wherein, 101-film surface isolation layer; The 102-macrovoid; The 103-transition zone; 104-braided tube enhancement layer; The 105-surface.
Fig. 5 is a liner enhancement mode hollow fiber film tube preparation facilities schematic diagram of the present invention;
Wherein, 1-casting film flow container; 2-deaeration jar; The former liquid storage tank of 3-blend; The 4-manifold; 5-blend liquid pump; 6-casting film liquid pump; 7-transition zone precoating jar; 8-applies head; 9-film forming path; The 10-coagulating bath; The 11-potcher; The 12-godet; The 13-reel.
Fig. 6 is a precoating jar schematic diagram;
Wherein, 201-liner braided tube; 202-feed liquid distribution grid; The 203-connector; The 204-scraping blade; The 205-tank body; The 206-outlet; 5-blend liquid pump.
Fig. 7 is film forming path and appurtenances schematic diagram;
Wherein, 201-liner braided tube; The 302-airflow-distribution board; The 303-delivery pump; The 304-inner chamber; The 305-film pipe of coming into being; The 306-permeable wall; 8-applies head.
Fig. 8 is the Nano bars of alumina electromicroscopic photograph.
Fig. 9 is a liner enhancement mode hollow membrane pipe (example 1).
Figure 10 is a liner enhancement mode hollow membrane pipe (comparative example 1).
The specific embodiment
Present embodiment illustrates the structure and the structure of liner enhancement mode doughnut membrane preparation device of the present invention.
Liner enhancement mode doughnut membrane preparation device of the present invention mainly is made up of casting film flow container 1, deaeration jar 2, the former liquid storage tank 3 of blend, manifold 4, transition zone precoating jar 7, coating head 8, film forming path 9, coagulating bath 10, potcher 11, godet 12 and reel 13; Wherein, described manifold 4 inside are respectively arranged with blend liquid pump 5 and casting film liquid pump 6; Applying head 8 is arranged in the film forming path 9;
On the one hand, the liquid outlet of the former liquid storage tank 3 of blend connects the inlet of blend liquid pump 5 by valve, the top lateral opening of the feed liquid distribution grid 202 on the tank body 205 of the outlet connection transition zone precoating jar 7 of blend liquid pump 5, the outlet 202 of transition zone precoating jar 7 connects the inlet that applies head 8, and applies the outlet of head 8 and the consistent UNICOM of outlet in its residing film forming path 9; The outlet in film forming path 9 connects the inlet of coagulating bath 10, and the outlet of coagulating bath 10 connects the inlet of potcher 11, and the outlet of potcher 11 connects reel 13 after connecting godet 12 again;
On the other hand, the outlet of deaeration jar 2 is by the inlet of valve connection casting film flow container 1, and the outlet of casting film flow container 1 connects the inlet of casting film liquid pump 6, and the outlet of casting film liquid pump 6 connects on the coating head 8.
Further, the described film forming path 9 outer temperature and humidity control systems 15 that also are connected to.
Further, described transition zone precoating jar 7 is made up of feed liquid distribution grid 202, tank body 205, connector 203 and scraping blade 204; Wherein feed liquid distribution grid 202 is arranged on the top of tank body 205, and the outlet UNICOM of tank body lateral location opening above feed liquid distribution grid 202 and blend liquid pump 5; Connector 203 in the tank body 205 is connected feed liquid distribution grid 202 belows in the tank body 205, outlet 206 tops with scraping blade 204; Tank body 205 bottom sides opening emptyings.
Further, described film forming path 9 by airflow-distribution board 302, inner chamber 304, apply head 8, permeable wall 306 and delivery pump 303 and form; Wherein, airflow-distribution board 302 is arranged on the top of inner chamber 304, and the below of airflow-distribution board 302 is provided with coating head 8, and the bottom that permeable wall 306 is arranged at coating head 8 is the bottom of inner chamber 304; Inner chamber 304 is positioned at the lateral opening of airflow-distribution board 302 tops, and the lateral opening of permeable wall 306, and this two places opening is by delivery pump 303 UNICOMs; The lateral opening in the exit of inner chamber 304 connects nitrogen inlet.
Further, film forming path 9 length are adjustable in 5～100 centimetres, and as preferably, path length is 5～30 centimetres.
The present embodiment explanation utilizes embodiment 1 described liner enhancement mode hollow fiber film tube preparation facilities to prepare the method for liner enhancement mode hollow fiber film tube.
The liner braided tube is formed by the braiding of chemical fibre multifilament, has excellent chemical stability and mechanical strength.Material is one or both shufflings in Fypro, polyester fiber and the polyurethane fibre.The size and the performance of factor affecting internal lining pipes such as count, chemical-fibres filaments dawn number, braiding number of spindles.Count of the present invention is 20～60 orders, and the internal lining pipe deformation of high count is little, but yields poorly; And the problem during low-density is the percentage elongation height, and is yielding, and then influences film pipe overall performance, and as preferably, count is 25～40 orders.The braiding number of spindles is 16～32 ingots.When the filament denier of selecting for use is high, can adopt the braiding of 16 ingots; And adopt 24 or 32 ingots when braiding, can be made into the internal lining pipe that has than large diameter.In addition, higher number of spindles can cause external diameter to increase, and produces the problem that easily is crushed.
Wherein, described casting solution mainly is made up of PVDF resin, solvent, non-solvent, hydrophilic macromolecule pore former and thickener; And described PVDF resin quality degree is 15%～20%, described solvent quality degree is 50%～65%, described water soluble polymer pore former mass percentage content is 10～20%, described hydrophily thickener qualities degree is 5%～15%, and described non-solvent mass percentage content is 0.5～1.5%; Hydrophily thickener, macromolecule pore former and non-solvent are dissolved in the solvent,, are pressed into the middle vacuum defoamation of deaeration jar (2) 4～10 hours fully after the dissolving, change casting solution storage tank (1) then after filtering over to again to wherein adding the polyvinylidene fluoride resin raw material.
The composite that inorganic nano-particle and PVDF resin, solvent, additive blend are formed.Hydrophily thickener and water soluble polymer pore former are dissolved in the solvent, again to wherein adding PVDF resin and nano-powder, blend forms viscosity 10,000～30,000 centipoise blend stostes, and the mass percentage content of described PVDF resin is 5%～10%, the mass percentage content of described solvent is 50%～70%, the mass percentage content of described water soluble polymer pore former is 10～20%, described hydrophily thickener qualities degree is 5%～15%, and the mass percentage content of described nano material is 0.5～5%; To change in the former liquid storage tank of blend (3) after the blend stoste process deaeration processing.
Advantage of mixing small amounts of inorganic oxide nano-particles or macromolecular fibre in transition zone of the present invention is: adding inorganic nano-particle can combine heat-resisting, the chemical stability of inorganic material with the pliability and the low cost of polymer, can improve the transition zone rigidity and and the cohesive force of surface isolation layer and enhancement layer; Adding high polymer nanometer fiber can increase and substrate macromolecule material effect entangled to each other, strengthens the intensity and the pliability of transition zone.
The nanoparticle surface active atomic is many, is easy to adsorb fully with polymer, bonding.When being subjected to external force, particle is difficult for breaking away from matrix.And, absorb lot of energy because the interaction of stress field produces a lot of little deformed areas in matrix.This just makes the transition zone composite can transmit the external carbuncle of being born preferably, can cause the matrix surrender again, consumes a large amount of impact energys, thereby reaches effect toughness reinforcing simultaneously and that strengthen.But the nanometer powder particle diameter is little, and surface area is big, is easy to reunite.Therefore when the compound transition zone of polymer of nanometer powder is added in preparation, be difficult to obtain the composite of nanostructured with common blending method.In order to increase the interface binding power of nanometer additive and polymer, improve the even dispersibility of nanoparticle in macromolecular material, need nanometer powder is carried out surface modification.Surface modified powder has reduced the surperficial energy state of particle, eliminates the surface charge of nano particle, improves the affinity of nano particle and organic facies, weakens the surface polarity of nano particle etc.The present invention uses the inorganic nanometer powder of surface modifications such as oleic acid, stearic acid, silane coupler, has strengthened nanoparticle dispersibility in polymer matrix, obtains the compound transition zone of nanostructured.The morphology microstructure that uses can be spherical, sheet, bar-shaped, columnar nanometer particle, or even nano wire, nanotube, nanometer film etc.; What the present invention preferentially used is nano wire and nano bar-shape powder, because of nano wire and the fine physical entanglement effect that generates with chain structure and polymer matrix of the existing particle of nanometer rods, have the chemical bond effect that causes owing to surface-active again, in polymer is filled, show good reinforcing action.Adopt the transition zone composite of modified Nano powder preparation, its hot strength can increase, and fracture elongation improves, and young modulus of material increases.Though the porosity of membrane material descends to some extent, pure water flux and hydrophily increase.The present invention with solution or the direct blend of emulsion form, prepares the compound buffer layer material of nano-powder/PVDF with nano unit, macromolecule resin and other additive of modification.
Further, described nano material is hydrophobic silica, aluminium oxide, zirconia, titanium oxide inorganic nano-particle, or high polymer nanometer fiber.
Described transition zone blend stoste has lower viscosity (10,000～30,000 centipoise).Braided tube at first applies blend stoste, the rough woven pattern of floating braided tube.Reach the surface smoothness that improves the surface isolation layer on the one hand, on the other hand, the not contractility of nano material causes the integral hardness of film to improve.
The temperature of control manifold (4) is at 25～95 ℃, enters in the tank body (205) blend stoste is pressed into the feed liquid distribution grid (202) of precoating jar (7) from the former liquid storage tank of blend (3) by blend liquid pump (5) after; Simultaneously, liner braided tube (201) penetrates from tank body (205) top, scrape floating whole weavy grain slit through the scraping blade (204) that is fixed in jar interior both sides by connector (203) in tank body (205), obtain drawing from tank body (205) outlet at bottom (206) again with the liner braided tube that blend stoste is scraped after smearing.Tank body (205) bottom sides is provided with evacuation port, helps on the one hand discharging air to the slack tank material feeding time, makes things convenient for the cleaning operation of precoating jar on the other hand, when equipment normally moves, is normally off.
Manifold (4) is the square box of steel plate welding, in establish the circulating hot water passage.Manifold is provided with the spin manifold temperature demonstration and casting solution pressure shows.The Controllable Temperature scope of manifold is 25～95 ℃, and as preferably, the temperature of manifold is set between 50～80 ℃.Casting film liquid pump (6) all is placed in the manifold with blend liquid pump (5), makes the temperature of casting solution and blended liquid keep stable before being coated on braided tube.
At first by precoating jar (7), the essential structure of precoating jar as shown in Figure 4 for braided tube (201).The blended liquid that is mixed with inorganic particulate is pressed into by blend liquid pump (5), through entering jar interior (205) behind the feed liquid distribution grid (202), braided tube penetrates from the tank body top, tank base outlet (206) is drawn, two scraping blades (204) are fixed in jar interior both sides by connector (203) in the tank body, are used for the weavy grain slit of floating braided tube.
The liner braided tube (201) of passing precoating jar (7) enters film forming path (9), at first passes through airflow-distribution board (302), continues across coating head (8) in again in inner chamber (304); By casting film liquid pump (6) casting solution is pressed into by casting solution storage tank (1) on the one hand and applies head (8), by applying head (8), obtain nascent film pipe (305) simultaneously being coated with the liner braided tube outside coating casting solution of blend stoste; Delivery pump (303) will be carried mixed vapour from bottom to up in inner chamber (304), make nascent film pipe (305) process vapor phase conversion process in film forming path (9), promptly begin to take shape the film surface isolation layer (101) of porous in nascent film pipe (305) outside; Permeable wall (306) is made as porous ceramics or sintered stainless steel by the anti-solvent material of porous, is used for strengthening the uniformity that air-flow distributes in the path.The nitrogen input quantity of control nitrogen inlet can be regulated the humidity in the path complementaryly.
The braided tube (201) of passing precoating jar (7) enters film forming path (9), and the structure in film forming path as shown in Figure 5.Mainly constitute by airflow-distribution board (302), inner chamber (304), permeable wall (306).And the outer coating of coating head (8), coating head (8) places the top in film forming path.The bottom, path is near coagulating bath.Braided tube (201) continues across the coating head in the film forming path, the nascent film pipe (305) of outside coating blend stoste and casting solution is process vapor phase conversion process in the path, the film pipe outside begins to take shape the surface isolation layer of porous, path length is adjustable in 5～100 centimetres, as preferably, path length is 5～30 centimetres, when coating speed is slow, select less length, the double diffusive process of the solvent on film silk surface and non-solvent make the time of staying of film pipe in the path keep stable, because can be finished in the extremely short time.And the long time only can cause the excessive volatilization of film tube outer surface solvent.The path lower ending opening also stretches into coagulating bath, so the solvent in the coagulating bath and non-solvent also can spread in the path, thereby influences the content of temperature, solvent and non-solvent in the path.
Temperature in the film forming path, moisture and solvent obtain strict control.In a so in check atmosphere, the separating layer partial solvent of film tube outer surface volatilization also absorbs the moisture in the surrounding environment and tentatively solidifies.The volatile quantity of the temperature effect solvent in the path and the feature that balances each other of casting solution, and moisture in the path and solvent mainly influence the convection current diffusion rate of solvent-nonsolvent.
Further, described film forming path is that humidity is 50～90% in 40～80 ℃ the scope by temperature and humidity control system (15) control temperature.
By in the coating membrane equipment, adding these parts of path, vapor phase is transformed with immersion inversion of phases process combine.Nascent film separating layer is experience vapor phase conversion process in the path at first, be not separated even do not produce, the casting solution on top layer is formed also can be owing to solvent evaporates, moisture penetration change, this variation will help the uniformity of casting solution phase separation speed in the coagulating bath, thereby produce the surface of high opening rate.After the internal lining pipe of surface applied casting solution enters coagulating bath, the surface with high opening rate more help non-solvent by the coagulating bath main body to the overlay diffused inside, make film separating layer and transition zone after the moulding be whole asymmetrical cell shape structure.
Step 6, the immersion inversion of phases takes place and the gel typing in nascent film pipe (305) in the coagulating agent of coagulating bath (10), and described coagulating agent is the mixture of solvent and water, and wherein the mass percentage content of solvent is 30%～60%, and the temperature of coagulating agent is 30 ℃～90 ℃; Inner lining film pipe silk journey of process in described coagulating bath is 10～30 meters;
The inner lining film pipe of finishing the vapor phase conversion process in the film forming path enters the coagulating basin below the path, and immersion inversion of phases process takes place.The coagulating agent of coagulating basin is the mixture of solvent and non-solvent.
In coagulating bath, the typing of skin covering of the surface separating layer and transition zone generation immersion inversion of phases and gel.Therefore the distance of film pipe process in coagulating bath (silk journey) is decided according to gelation rate and coating speed, and gelation rate is subjected to the composition and the Temperature Influence of coagulating bath.Further, the distance of inner lining film pipe process in described coagulating bath (silk journey) is 10～30 meters.According to result of the test, the silk journey of preferred coagulating bath is 5～10 meters.After separating layer and transition zone were separated, it was rich stingy with polymer to form polymer, and richness develops into the main body of this double-layer structure mutually, stingyly was made up of solvent, non-solvent and most additive, can dissolve each other with water.
The processing of preserving moisture of step 9, glycerine.Soak being placed in the glycerine water solution again behind the dried free moisture content of film management and control, the hole of film tube-surface separating layer can further farthest kept in the dry run, also reduce the shrinkage factor of film separating layer and transition zone simultaneously.Described film pipe soak time in glycerine water solution is 12～24 hours, and wherein the quality of glycerine is 10%～50% than concentration.As preferably, the quality of glycerine is 20%～30% than concentration.
In the method for the invention, the weight average molecular weight of described PVDF resin is between 20～800,000 dalton, and alternative PVDF resin brand has: Kynar 461, Kynar 740, Kynar 760, and Kynar 761, and HSV 900, FR 904, Solef 1010, and Solef 1015, and Solef 6010, Solef 6020, and Solef 6030 and other weight average molecular weight are greater than 200,000 resin.Have as preferred brand: Kynar 760, and Kynar 761, and HSV 900, and FR 904, and Solef 1010, and Solef 1015, and Solef 6020, and Solef 6030.
Further, described solvent is a kind of in N-methyl pyrrolidone (NMP), dimethyl formamide (DMF), dimethylacetylamide (DMAC), the dimethyl sulfoxide (DMSO) (DMSO).These four kinds of fine solvents that reagent all is the PVDF resin be to be simplified the composition of prescription, only select wherein a kind of for use.Because similar to the solvability of PVDF, so consumption is basic identical.As preferably, solvent is selected dimethylacetylamide (DMAC) and N-methyl pyrrolidone (NMP) for use.
Further, described non-solvent is that one or more of water, ethanol, isopropyl alcohol, glycerine, n-butanol, ethylene glycol, diglycol mix.Non-solvent is the material that causes that casting solution is separated, and causes the overlay gel solidification.In casting solution, add non-solvent, can accelerate the inner phase separation of overlay.The amount that adds non-solvent is then very crucial.Non-solvent is strong more, and consumption is few more.In addition, strong, the weak non-solvent use of can arranging in pairs or groups.As preferably, described non-solvent is water or glycerine.When selecting strong non-solvent water, consumption is less than 1.0%.
Further, described hydrophily thickener is 1, one or more mixtures in 4-butyrolactone, phosphorus benzene bis-acid potassium dibutyl ester, low molecular polyethylene glycol (MW:200～600), the polyvinyl alcohol (MW:200～600).Add an amount of hydrophily thickener in casting solution after, can regulate and control the viscosity of casting solution, increase equal phase region scope, also can promote the diffusion of non-solvent ecto-entad simultaneously, overall effect is that the finger-like pore that suppresses in the supporting layer occurs.
Further, described water soluble polymer pore former is high molecular weight polyethylene glycol (MW:2,000～10,000), PEO (MW:10,000～50,000), polyvinyl alcohol (MW:10,000～50,000), one or more mixtures in the polyvinylpyrrolidone (MW:10,000～400,000).Water-soluble pore former constantly comes out with solvent elution owing in the rinse cycle after gelation except that the effect that possesses described thickener, and increases the porosity of supporting layer.As preferably, the macromolecule pore former is that PEG is or/and PVP.The range of choice of the molecular weight of described PVP is between 10000～100000, and the molecular weight of described PEG is between 1000～10000.
Present embodiment prepares hollow fiber film tube according to the method for embodiment 2, and wherein the condition of Xuan Zeing is as follows with the film pipe character for preparing:
Select for use the chemical-fibres filaments polyester fiber to prepare braided tube, braided tube density is 45 orders, and the braiding number of spindles is 24 ingots, gained braided tube external diameter 1.65mm, internal diameter 0.85mm.Select for use the polyvinylidene fluoride resin blend of 900 two kinds of different weight average molecular weight of Solef 1010 and HSV to be modulated into casting solution, solvent is selected dimethylacetylamide (DMAC) for use, and content is 56%.Macromolecular water-soluble pore former, hydrophily thickener and non-solvent are selected polyvinylpyrrolidone (PVP) K17, PEG400 and glycerine respectively for use, and the content of each composition is listed in table 1.Above raw material is by solid behind the first liquid, and the order of macromolecule drops in the reactor behind the first small-molecular weight, stirs down at 75～80 ℃ and makes uniform buff casting solution, and casting solution viscosity is 58000 centipoises (80 ℃).Changed in the deaeration jar of uniform temp deaeration after the dissolving fully over to 8 hours, it is stand-by that the casting solution after the deaeration is pressed into fluid reservoir with clean air.Gear wheel metering pump is clamp-oned coating head with casting solution from fluid reservoir with constant speed.
Be used to prepare the blend stoste employing raw material similar to casting solution of transition zone, the main content that is not both the PVDF resin is low, and has added the Al of oleic acid modification
2O
3Nanometer rods, as shown in Figure 6, the about 30nm of particle diameter.Each component content in the blended liquid is listed in table 1.The concocting method and the casting solution of blended liquid are similar, and each component drops in the reactor successively, stir down at 75～80 ℃, to change the blended liquid storage tank over to through deaeration, after leaving standstill stand-by.Gear wheel metering pump is clamp-oned precoating jar with blended liquid from fluid reservoir with constant speed.
Table 1, casting solution and blended liquid are formed
Braided tube by precoating jar and coating head, enters the film forming path successively under the traction of reel.The elongated degree in river in Zhejiang Province is 15 centimetres, contains 50% solvent in the coagulating bath, and the temperature of coagulating bath is controlled at 80 ℃, and the film silk is 40 seconds in the time of staying of coagulating bath.The medium of potcher is a water, and temperature is controlled at 80 ℃, and the film silk is 60 seconds in the time of staying of potcher.Coating speed is 12 meter per seconds.Film Guan Jing solidifies, rinsing and reel after, put into the water rinsing, and the film pipe carried out glycerine preserve moisture, vanning is stand-by after the drying process.Fig. 9 is the electromicroscopic photograph of the film liner enhancement mode film tube section of this examples preparation.Can find that from the SEM photo inner liner braiding lines is tight, overlay (surface isolation layer and transition zone) average thickness is 0.1mm, does not have macrovoid.The back pressure test result of finished film pipe shows overlay and inner liner anti-peel off pressure, and film envelope point pressure all above 0.3MPa, the pure water stabilized flux of film pipe can reach 450LMH/bar.
Comparative example:
Adopt liner braided tube weaving method and the coated technique identical, but the braiding number of spindles of internal lining pipe is 32, change formula of casting and blended liquid prescription such as table 2 with embodiment 3.Therefore, dried film pipe has the external diameter bigger than example 3, external diameter 2.0mm, internal diameter 1.4mm on macroscopic view.Cause the cross section to present macroporous structure because the content of polymeric additive is low simultaneously.When carrying out the integrity test of film pipe, bubble point pressure is lower than 0.02MPa.
Table 2, casting solution and blended liquid are formed (comparative example)
Present embodiment prepares hollow fiber film tube according to the method for embodiment 2, and wherein the condition of Xuan Zeing is as follows with the film pipe character for preparing:
The preparation method of braided tube is consistent with embodiment 3.Select the main component of Kynar 761 resins as casting solution for use, because the weight average molecular weight of Kynar 761 resins is lower than HSV900, so the total amount of resin is 20% of a casting solution gross weight.Solvent is dimethylacetylamide (DMAC), and the composition and the proportioning of casting solution and blended liquid are listed in table 3.Above material is by solid behind the first liquid, and the order of macromolecule drops in the agitator tank behind the first small-molecular weight, stirs down at 75～80 ℃ and makes uniform buff casting solution, and casting solution viscosity is 53000 centipoises (80 ℃).Coating process such as example 3.The back pressure test result of finished film pipe shows overlay and inner liner anti-peel off pressure, and film envelope point pressure all above 0.3MPa, the pure water stabilized flux of film pipe can reach 500LMH/bar.
Table 3, casting solution and blended liquid are formed
| Composition | Casting solution | Blended liquid |
| ?PVDF，Kynar?761 | 20％ | 10.0％ |
| ?DMAC | 55.0％ | 64.0％ |
| PVP，K30 | 14.0％ | 14.0％ |
| PEG?400 | 10.0％ | 10.0％ |
| GLY | 1.0％ | 0.0％ |
| Al 2O 3 | 0.0％ | 2.0％ |
Present embodiment prepares hollow fiber film tube according to the method for embodiment 2, and wherein the condition of Xuan Zeing is as follows with the film pipe character for preparing:
Select for use the chemical-fibres filaments polyurethane fibre to prepare braided tube, braided tube density is 20 orders, and the braiding number of spindles is 16 ingots, gained braided tube external diameter 1.50mm, internal diameter 0.50mm.Select the polyvinylidene fluoride resin blend of FR904 and 1,015 two kinds of different weight average molecular weight of Solef for use, the total amount of resin is that 19%, two kind of resin of casting solution gross weight is mixed with 8: 2 ratio.Solvent is N-methyl pyrrolidone (NMP), and the composition and the proportioning of casting solution and blended liquid are listed in table 4.Above material is by solid behind the first liquid, and the order of macromolecule drops in the agitator tank behind the first small-molecular weight, stirs down at 75～80 ℃ and makes uniform buff casting solution, and the viscosity of casting solution is similar to example 4, is 55000 centipoises (80 ℃).Coating process such as example 1, the back pressure test result of finished film pipe show overlay and inner liner anti-peel off pressure, and film envelope point pressure all above 0.3MPa, the pure water stabilized flux of film pipe can reach 500L/ (m
2Hrbar).
Table 4, casting solution and blended liquid are formed
| Composition | Casting solution | Blended liquid |
| PVDF，FR904 | 15.2％ | 10.0％ |
| PVDF，Solef?1015 | 3.8％ | 0.0％ |
| NMP | 56.0％ | 64.0％ |
| PVP，K17 | 14.0％ | 14.0％ |
| PEG?400 | 10.0％ | 10.0％ |
| GLY | 1.0％ | 0.0％ |
| Al 2O 3 | 0.0％ | 2.0％ |
Embodiment 6～11
Adopt the equipment and technology of embodiment 2 to prepare liner enhancement mode pvdf membrane pipe, used material, technological parameter and film pipe performance are listed in table 5.
Claims (19)
1. a liner enhancement mode hollow fiber film tube preparation facilities mainly is made up of casting film flow container (1), deaeration jar (2), the former liquid storage tank of blend (3), manifold (4), transition zone precoating jar (7), coating head (8), film forming path (9), coagulating bath (10), potcher (11), godet (12) and reel (13); Wherein, described manifold (4) inside is respectively arranged with blend liquid pump (5) and casting film liquid pump (6); Applying head (8) is arranged in the film forming path (9);
On the one hand, the liquid outlet of the former liquid storage tank of blend (3) connects the inlet of blend liquid pump (5) by valve, the top lateral opening of the feed liquid distribution grid (202) on the tank body (205) of the outlet connection transition zone precoating jar (7) of blend liquid pump (5), the outlet (202) of transition zone precoating jar (7) connects the inlet that applies head (8), and applies the outlet of head (8) and the consistent UNICOM of outlet in its residing film forming path (9); The outlet in film forming path (9) connects the inlet of coagulating bath (10), and the outlet of coagulating bath (10) connects the inlet of potcher (11), and the outlet of potcher (11) connects reel (13) after connecting godet (12) again;
On the other hand, the outlet of deaeration jar (2) is by the inlet of valve connection casting film flow container (1), and the outlet of casting film flow container (1) connects the inlet of casting film liquid pump (6), and the outlet of casting film liquid pump (6) connects coating head (8).
2. liner enhancement mode hollow fiber film tube preparation facilities according to claim 1 is characterized in that the external temperature and humidity control system in described film forming path (9) (15).
3. liner enhancement mode hollow fiber film tube preparation facilities according to claim 1 is characterized in that described transition zone precoating jar (7) is made up of feed liquid distribution grid (202), tank body (205), connector (203) and scraping blade (204); Wherein feed liquid distribution grid (202) is arranged on the top of tank body (205), and in the tank body lateral location opening of feed liquid distribution grid (202) top and the outlet UNICOM of blend liquid pump (5); Connector (203) in the tank body (205) is connected the interior feed liquid distribution grid of tank body (205) (202) below, outlet (206) top with scraping blade (204); The emptying of tank body (205) bottom sides opening.
4. liner enhancement mode hollow fiber film tube preparation facilities according to claim 1, it is characterized in that described film forming path (9) by airflow-distribution board (302), inner chamber (304), apply head (8), permeable wall (306) and delivery pump (303) and form; Wherein, airflow-distribution board (302) is arranged on the top of inner chamber (304), and the below of airflow-distribution board (302) is provided with coating head (8), and the bottom that permeable wall (306) is arranged at coating head (8) is the bottom of inner chamber (304); Inner chamber (304) is positioned at the lateral opening of airflow-distribution board (302) top, and the lateral opening of permeable wall (306), and this two places opening is by delivery pump (303) UNICOM; The lateral opening in the exit of inner chamber (304) connects nitrogen inlet.
5. liner enhancement mode hollow fiber film tube preparation facilities according to claim 4 is characterized in that described film forming path (9) length is 5～100 centimetres.
6. utilize the described liner enhancement mode of claim 1 hollow fiber film tube preparation facilities to prepare the method for liner enhancement mode hollow-fibre membrane, it is characterized in that may further comprise the steps:
Step 1, prepare the liner braided tube: selecting count for use is 20～60 orders, the braiding number of spindles is the chemical fibre multifilament of 16～32 ingots; Wherein, the material of chemical fibre multifilament is one or both in Fypro, polyester fiber and the polyurethane fibre;
Step 2, the allotment casting solution: wherein, described casting solution mainly is made up of PVDF resin, solvent, non-solvent, hydrophilic macromolecule pore former and hydrophily thickener; And described PVDF resin quality degree is 15%～20%, described solvent quality degree is 50%～65%, described water soluble polymer pore former mass percentage content is 10～20%, described hydrophily thickener qualities degree is 5%～15%, and described non-solvent mass percentage content is 0.5～1.5%; Thickener, macromolecule pore former and non-solvent are dissolved in the solvent,, are pressed into the middle vacuum defoamation of deaeration jar (2) 4～10 hours fully after the dissolving, change casting solution storage tank (1) then after filtering over to again to wherein adding the PVDF resin;
Step 3, the blend stoste of preparation transition zone: with the hydrophily thickener, the hydrophilic macromolecule pore former is dissolved in the solvent, again to wherein adding PVDF resin and nano-powder, blend forms viscosity 10,000～30,000 centipoise blend stostes, and the mass percentage content of described PVDF resin is 5%～10%, the mass percentage content of described solvent is 50%～70%, the mass percentage content of described water soluble polymer pore former is 10～20%, described hydrophily thickener qualities degree is 5%～15%, and the mass percentage content of described nano material is 0.5～5%; To change in the former liquid storage tank of blend (3) after the blend stoste process deaeration processing;
Step 4, blend stoste is coated on liner braided tube surface: the temperature of control manifold (4) is at 25～95 ℃, enters in the tank body (205) blend stoste is pressed into the feed liquid distribution grid (202) of precoating jar (7) from the former liquid storage tank of blend (3) by blend liquid pump (5) after; Simultaneously, liner braided tube (201) penetrates from tank body (205) top, scrape floating whole weavy grain slit through the scraping blade (204) that is fixed in jar interior both sides by connector (203) in tank body (205), obtain drawing from tank body (205) outlet at bottom (206) again with the liner braided tube that blend stoste is scraped after smearing;
Step 5, the liner braided tube surface that is coated with blend stoste applies casting solution again: the liner braided tube (201) of passing precoating jar (7) enters film forming path (9), at first pass through airflow-distribution board (302), in inner chamber (304), continue across coating head (8) again; By casting film liquid pump (6) casting solution is pressed into by casting solution storage tank (1) on the one hand and applies head (8), by applying head (8), obtain nascent film pipe (305) simultaneously being coated with the liner braided tube outside coating casting solution of blend stoste; Delivery pump (303) will be carried mixed vapour from bottom to up in inner chamber (304), make nascent film pipe (305) process vapor phase conversion process in film forming path (9), promptly begin to take shape the film surface isolation layer (101) of porous in nascent film pipe (305) outside; Described film forming path is 40～80 ℃ by temperature and humidity control system (15) control temperature, and humidity is 50～90%;
Step 6, the immersion inversion of phases takes place and the gel typing in nascent film pipe (305) in the coagulating agent of coagulating bath (10), and described coagulating agent is the mixture of solvent and water, and wherein the mass percentage content of solvent is 30%～60%, and the temperature of coagulating agent is 30 ℃～90 ℃; Inner lining film pipe silk journey of process in described coagulating bath is 10～30 meters;
Step 7, the nascent film pipe that does not solidify fully enters potcher (11), further finishes process of setting, replaces solvent residual in the membrane pipe and additive simultaneously; Described film pipe silk journey of process in potcher is 30～60 meters; Potcher medium be pure water, its temperature is 25 ℃～95 ℃;
Step 8, the film pipe is collected bunchy through godet (12) by reel (13), puts into tank and soaks 24 hours, thoroughly displaces solvent and additive;
Step 9, the glycerine processing of preserving moisture: the film management and control done to be placed in the glycerine water solution behind the free moisture content again soak, the hole of film tube-surface separating layer can further farthest kept in the dry run, also reduce the shrinkage factor of film separating layer and transition zone simultaneously; Described film pipe soak time in glycerine water solution is 12～24 hours, and wherein the mass percent concentration of glycerine is 10%～50%;
Step 10 is carried out drying with the film pipe and is handled, and promptly obtains liner enhancement mode hollow membrane pipe.
7. method according to claim 6 is characterized in that the establishment density of selecting for use in the described step 1 is 25～40 orders.
8. method according to claim 6 is characterized in that the nano-powder described in the described step 3 is hydrophobic silica, aluminium oxide, zirconia, titanium oxide inorganic nano-particle, or high polymer nanometer fiber.
9. method according to claim 6, the temperature that it is characterized in that manifold in the described step 4 is 50～80 ℃.
10. method according to claim 6, the silk journey that it is characterized in that coagulating bath in the described step 6 is 5～10 meters.
11. method according to claim 6 is characterized in that weight average molecular weight 20～800,000 dalton of the PVDF resin described in described step 2, step 3 or the step 6; And be Kynar 461, Kynar 740, and Kynar 760, and Kynar 761, and HSV 900, and FR 904, and Solef 1010, and Solef 1015, and Solef 6010, and Solef 6020, and perhaps Solef 6030.
12. method according to claim 11 is characterized in that described PVDF resin is Kynar 760, Kynar 761, and HSV 900, and FR 904, and Solef 1010, and Solef 1015, and Solef 6020, and perhaps Solef 6030.
13. method according to claim 6 is characterized in that the solvent described in described step 2, step 3 or the step 6 is N-methyl pyrrolidone, dimethyl formamide, dimethylacetylamide or dimethyl sulfoxide (DMSO); Preferred dimethylacetylamide or N-methyl pyrrolidone.
14. method according to claim 6 is characterized in that the non-solvent described in described step 2, step 3 or the step 6 is water, ethanol, isopropyl alcohol, glycerine, n-butanol, ethylene glycol, diglycol or its combination.
15. method according to claim 14 is characterized in that described non-solvent is a water.
16. method according to claim 6, it is characterized in that the hydrophily thickener described in described step 2, step 3 or the step 6 is 1,4-butyrolactone, phosphorus benzene bis-acid potassium dibutyl ester, molecular weight are that 200～600 polyethylene glycol, molecular weight are 200～600 polyvinyl alcohol or its combination.
17. method according to claim 6, it is characterized in that the hydrophilic macromolecule pore former described in described step 2, step 3 or the step 6 is that molecular weight is 2,000～10,000 polyethylene glycol, molecular weight are 10,000～50,000 PEO, molecular weight are 10,000～50,000 polyvinyl alcohol, molecular weight are 10,000～400,000 polyvinylpyrrolidone, perhaps its combination.
18. method according to claim 17, it is characterized in that described hydrophilic macromolecule pore former is that polyethylene glycol is or/and polyvinylpyrrolidone, and the range of choice of the molecular weight of described polyethylene glycol is 10000～100000, and the molecular weight of described polyvinylpyrrolidone is 1000～10000.
19. the liner enhancement mode hollow membrane pipe that method according to claim 6 prepares.
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Effective date of registration: 20151103 Address after: 211800 Nanjing District, Jiangsu, Pukou garden ideas No. 1 Patentee after: NANJING JIUYING MEMBRANE TECHNOLOGIES CO.,LTD. Address before: 210009, A, Nanjing science and Technology Square, 5 new exemplary Road, Nanjing, Jiangsu Patentee before: Nanjing Tech University |