CN210934506U - Enhancement mode hollow fiber membrane, spinning jet and preparation facilities thereof - Google Patents
Enhancement mode hollow fiber membrane, spinning jet and preparation facilities thereof Download PDFInfo
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- CN210934506U CN210934506U CN201920604973.4U CN201920604973U CN210934506U CN 210934506 U CN210934506 U CN 210934506U CN 201920604973 U CN201920604973 U CN 201920604973U CN 210934506 U CN210934506 U CN 210934506U
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Abstract
The utility model provides an enhancement mode hollow fiber membrane, spinning jet and preparation facilities thereof. The reinforced hollow fiber membrane comprises a plurality of hollow fiber membrane filaments, the hollow fiber membrane filaments are arranged into a bundle-shaped membrane filament bundle, a reinforcing rope is arranged in the middle of the membrane filament bundle, and a winding belt is tied outside the membrane filament bundle. The braided rope provides the tensile strength of the integral membrane filaments, which provide the separation properties of the integral membrane bundle. Compared with the membrane filaments with the traditional outer diameter, the preparation method enables the integral membrane bundle to have larger separation specific surface area. Meanwhile, the equipment can prepare the membrane bundle formed in one step and has the advantages of simple operation and high production efficiency.
Description
Technical Field
The utility model relates to an organic hollow fiber membrane preparation field especially relates to an enhancement mode hollow fiber membrane, spinning jet and preparation facilities thereof.
Background
Water resources are a valuable resource for China, and various industries have different requirements on the used water resources. The membrane separation technology is introduced into the field of water resource utilization, so that water resource pretreatment, reclaimed water reuse, standard-reaching discharge of wastewater and the like can be better performed, the water demand of each industry can be met, and the national sustainable development strategy is also met.
The membrane is applied to a membrane bioreactor, ultrapure water preparation and the like to mainly play a role in solid-liquid separation, and is applied to a membrane aeration bioreactor, aquaculture and the like to mainly play a role in gas-liquid contact and increase the dissolved oxygen in a liquid medium. Therefore, the membrane separation technologies such as solid-liquid separation, gas-liquid contact and the like all generate good economic benefits.
The hollow fiber membrane on the market at present has the phenomenon of filament breakage in both column type membrane modules and curtain type membrane modules. The methods currently used on the market are mainly the thermal phase method (TIPS method) and the lining braided tube method. The TIPS method is to dissolve a polymer in a solvent (also called diluent) with a high boiling point and low volatility to form a homogeneous solution, and then cool the solution. During cooling, the system phase separates. The produced film yarn has high tensile strength and aperture ratio, so that the film yarn is not easy to break in the application process, and is mainly represented by Asahi chemical industry and Dongli internationally and represented by Sunnuo domestically. The main disadvantages are that the diluent used in the process of use is more or less toxic and the diluent costs are always high, while the temperatures required in the production process are high and the operation is not convenient. The lining braided tube method is mainly an extension of the NIPS method, and the braided tube is used for replacing core liquid used in the production of the NIPS method. Coating a layer of membrane casting solution on the outer surface of the braided tube uniformly through a special spinning nozzle, and then forming a membrane through liquid-liquid phase separation. The original creation of such a production method was mainly represented by Zenon corporation of Canada (US Patent No.5472607, US2003/0098275A, WO 00/78437A 1), and currently, the production method is represented by Bishui sources and maple family domestically. Meanwhile, the cohesiveness between the braided tube and the membrane separation layer is improved through improving the texture of the braided tube in China. The membrane surface area is much reduced compared to hollow fiber membranes.
In addition, some patents use other special materials to prepare hollow fiber membranes, such as PTFE (CN 102284251A), but the preparation and winding process of flat membrane of PTFE is complicated and difficult to industrialize.
SUMMERY OF THE UTILITY MODEL
In view of the above problems in the prior art, the main object of the present invention is to provide a novel reinforced hollow fiber membrane manufacturing apparatus. A special spinning nozzle and film-making production equipment are designed. The produced membrane filaments are uniformly distributed around the braided rope by taking the braided rope as the center, and then a bundle of hollow fiber membrane filaments is wound into a bundle of whole body by the braiding machine. The prepared hollow fiber membrane yarn is a membrane yarn in appearance, and is actually a bundle of hollow fiber membrane yarns containing braided ropes (hereinafter referred to as a membrane bundle). Wherein, the hollow fiber membrane is prepared by a dry spraying-wet spinning method, has a separation layer and a support layer, and plays a role in separation. The braided rope in the middle of one bundle of membrane filaments mainly plays a role in supporting the hollow fiber membrane filaments so as to prevent the membrane filaments from breaking during the use process, which is similar to the connection between bones and blood vessels. The braided rope can better support the whole membrane bundle than the skeleton, and the blood vessel can better support the membrane filament and can separate and purify the blood vessel. The membrane bundle prepared by the method has the advantages of large effective area, difficult yarn breakage and the like.
The technical scheme is as follows:
the utility model discloses a first aspect provides:
the reinforced hollow fiber membrane comprises a plurality of hollow fiber membrane filaments, wherein the hollow fiber membrane filaments are arranged into a bundle-shaped membrane filament bundle, a reinforcing rope is arranged between the membrane filament bundles, and a winding belt is tied outside the membrane filament bundle.
In one embodiment, the hollow fiber membrane is made of a polymer.
In one embodiment, the hollow fiber membrane filaments have an inner diameter in the range of 0.1 to 3mm and an outer diameter in the range of 0.4 to 5 mm.
The second aspect of the present invention provides:
a preparation method of a reinforced hollow fiber membrane comprises the following steps:
and 2, tightening the film tows obtained in the step 1, and winding a tape on the outer part of the film tows.
In one embodiment, the hollow fiber membrane yarn is obtained by simultaneously ejecting the core solution and the casting solution and then phase-converting the same in a coagulation bath.
The third aspect of the present invention provides:
a hollow fiber membrane spinneret comprising:
a plurality of spinneret orifices are distributed on the spinneret, and weaving rope holes are arranged in the middles of the spinneret orifices;
reinforcing ropes are strung in the braided rope holes;
the spinneret orifice is provided with a hollow fiber membrane spinneret orifice, and the hollow fiber membrane spinneret orifice is sleeved with a core liquid hole.
In one embodiment, the spinneret is further provided with a core liquid inlet hole communicated with the core liquid hole.
In one embodiment, the inside of the spinneret is provided with a cavity, and the cavity is communicated with the spinneret holes of the hollow fiber membranes.
The fourth aspect of the present invention provides:
the preparation device of the reinforced hollow fiber membrane comprises the hollow fiber membrane spinneret.
In one embodiment, further comprising: the core liquid tank is communicated with the core liquid inlet hole.
In one embodiment, the wick liquid tank is connected to the wick liquid inlet via a second pump.
In one embodiment, further comprising: and the casting film liquid tank is communicated with the hollow fiber film spinneret orifice.
In one embodiment, the casting film liquid tank is connected with the hollow fiber film spinneret hole through a first pump.
In one embodiment, a first gas source is arranged on the casting film liquid tank; and a second gas source is arranged on the core liquid tank.
In one embodiment, further comprising: and a coagulation bath for performing coagulation bath treatment on the film filaments obtained in the spinneret.
In one embodiment, further comprising: and the circular ring is used for tightening the membrane wires and the reinforcing ropes obtained from the spinning nozzle.
In one embodiment, further comprising: and the winding device is used for winding the outside of the membrane tows obtained from the circular ring on a winding belt.
In one embodiment, the winding device comprises: the rotary disc is provided with a hole in the middle and is used for enabling the membrane silk bundle to pass through; the turntable is provided with a rubber belt bearing, and a winding belt is stringed in the rubber belt bearing; further comprising: the driving wheel is attached to the edge of the rotary disc and the driven wheel, and the driving wheel is driven to rotate through the motor.
In one embodiment, further comprising: and the pulling roller is used for pulling out the film tows obtained from the winding device.
In one embodiment, further comprising: and the rinsing liquid tank is used for rinsing the hollow fiber membrane filaments obtained from the spinning nozzle.
In one embodiment, further comprising: and the wire winding wheel is used for winding the membrane tows obtained in the traction roller.
Advantageous effects
The utility model provides a novel high-strength hollow fiber membrane preparation method, which is characterized in that a weaving rope is prepared by a special spinning nozzle to improve the tensile strength of the whole membrane yarn, so that the whole membrane yarn is not broken in the application process; membrane filaments distributed around the braided rope play a role in separation; the designed winding device enables the membrane bundle to be a whole, compared with the membrane yarn with the same outer diameter, the effective membrane area is increased by 20-50%, and the floor area of the same membrane component is reduced. Meanwhile, different types of casting solution can be prepared into wires with different properties, so that the application field of the novel high-strength membrane wire is greatly improved. Such as MBR, membrane aeration, submerged ultrafiltration, etc.
Drawings
FIG. 1 is a schematic view of the structure of a hollow fiber membrane obtained by the preparation,
FIG. 2 is a structural view of a hollow fiber membrane obtained by the preparation,
figure 3 is a diagram of a production plant,
FIG. 4 is a structural view of a spinneret,
FIG. 5 is a sectional view of the spinning nozzle,
figure 6 is a block diagram of a winding device,
figure 7 is a block diagram of a winding device,
FIG. 8 is a surface view of a hollow fiber membrane obtained by the preparation
FIG. 9 is a sectional view of a hollow fiber membrane obtained by the production
FIG. 10 is a view showing the interface of the hollow fiber membrane
FIG. 11 is a pore size distribution diagram of the hollow fiber membrane prepared in example 1
FIG. 12 is a pore size distribution diagram of a hollow fiber membrane prepared in example 2
Wherein, 1, spinneret; 2. a spinneret orifice; 3. weaving rope holes; 4. hollow fiber membrane filaments; 5. a wrapping tape; 6. a film casting liquid tank; 7. a core liquid tank; 8. a first pump; 9. a second pump; 10. a first gas source; 11. a second gas source; 12. a reinforcing cord; 13. a circular ring; 14. a coagulation bath; 15. a winding device; 16. a pulling roll; 17. a rinsing liquid tank; 18. a wire winding wheel; 19. a wick liquid inlet hole; 20. a bore; 21. a hollow fiber membrane spinneret orifice; 22. a cavity; 23. a wick tube; 24. a driving wheel; 25. a driven wheel; 26. a turntable; 27. a tape bearing; 28. an electric motor.
Detailed Description
The utility model provides a hollow fiber membrane is as shown in fig. 1 and fig. 2, including many hollow fiber membrane silks 4, hollow fiber membrane silk 4 arrange into the membrane silk bundle of bundle form to be equipped with reinforcing rope 12 in the middle of the membrane silk bundle, tied up winding area 5 in the outside of membrane silk bundle.
The material of the hollow fiber membrane is a polymer, for example, one of PS, PP, PES, PVDF, PAN, PVC, ECTFE. The hollow fiber membrane filaments have an inner diameter in the range of 0.1 to 3mm and an outer diameter in the range of 0.4 to 5 mm. The number of hollow fiber membrane filaments 4 in a bundle of membrane filaments may be between 10-800, such as 10-50, 10-100, 20-200, etc.
The membrane filaments of the hollow fiber membrane described above can be produced by using an apparatus shown in FIG. 3, in which the main component is a spinneret shown in FIG. 4. The spinning nozzle has a sealed circular through hole in the middle, the weaving tube passes through the circular through hole during spinning, the diameter of the used weaving rope can be in the range of 0.5mm-2.0mm, and the weaving rope with the proper diameter is selected according to the spun hollow fiber membrane yarn. The number of the spinneret holes can be between 20 and 60, and the diameter of the spinneret holes is between 0.7 and 1.3 mm. The spinning nozzle is provided with a film casting liquid feeding hole above, and the side surface of the spinning nozzle is provided with a core liquid inlet hole. The feed hole and the core liquid inlet hole are internally threaded by 2 parts. Simultaneously the utility model discloses still design a wind, become one whole with the membrane bundle winding.
A plurality of spinning nozzles 2 are distributed on the spinning nozzle 1, and weaving rope holes 3 are arranged in the middle of the spinning nozzles 2;
the reinforcing rope 12 is strung in the braided rope hole 3;
the spinneret 2 is provided with a hollow fiber film spinneret orifice 21, and the hollow fiber film spinneret orifice 21 is sleeved with a core liquid orifice 20.
In one embodiment, the braided rope can be made of terylene, aramid fiber, spandex, acrylic fiber and the like according to the system used by the membrane yarn, so as to achieve the effect of supporting the strength of the membrane yarn. Meanwhile, the braided rope is required to be made of 200-600 denier, so that the braided rope cannot have high elasticity in use.
In one embodiment, the spinneret 1 is further provided with a core liquid inlet hole 19 communicated with the core liquid hole 20.
In one embodiment, the spinneret 1 is provided with a cavity 22 therein, and the cavity 22 is communicated with the spinneret holes 21 of the hollow fiber membranes.
In the apparatus, further comprising: the core liquid tank 7, the said core liquid tank 7 communicates with liquid inlet hole 19 of the core; the core liquid tank 7 is connected with the core liquid inlet 19 through the second pump 9.
In the apparatus, further comprising: the casting film liquid tank 6 is communicated with the hollow fiber film spinneret orifice 21; the casting film liquid tank 6 is connected with the hollow fiber film spinneret orifice 21 through the first pump 8.
Firstly, the casting solution is pressed into a hollow fiber membrane spinneret orifice 21 by a first pump 8 and sprayed out, the core solution is pressed into a core solution inlet 19 by a second pump 9 and then is extruded from each core solution pipe 23 through a cavity 22, and further hollow fiber membrane yarns are obtained by extruding the hollow fiber membrane spinneret orifice 21 and the core solution pipe 23, and the obtained membrane yarns also surround the reinforcing cords 12 because each spinneret 1 surrounds the braided cord holes 3. The membrane yarn bundle is tightened by the circular ring 13.
Next, the membrane filament bundle enters into the middle hole of the winding device 15, and the winding device 15 comprises: a turntable 26 with a central opening for passing the membrane yarn bundle; the turntable 26 is provided with a tape bearing 27, and a winding tape 5 is stringed in the tape bearing 27; further comprising: a driving wheel 24 and a driven wheel 25 which are jointed with the edge of the turntable 26, wherein the driving wheel 24 is driven to rotate by a motor 28. Through the rotation of motor 28, can drive the rotation of carousel 26, pull out winding area 5 and membrane silk bundle simultaneously, tie winding area 5 in the surface of membrane silk bundle through the rotation effect, form the membrane silk bundle of high compactness, make its bulk strength improve. In one embodiment, the winding device consists essentially of two rings. The two rings are concentric circles with one larger and one smaller, and 4-6 rotatable rubber wheels are embedded between the rings. The two rings are fixed on the flat plate, 4-6 rubber ring wheels are arranged on the flat plate, the rubber ring wheels are distributed on one circumference, the large ring is just embedded into the rubber wheel, one of the rubber wheels between the two rings is driven by a motor to rotate, and thus the two rings respectively rotate clockwise and anticlockwise. The ring is respectively provided with 1 convex bearing rod, and the winding belt is arranged on the convex bearing rods. When the circular ring moves circularly, the winding belt can be uniformly wound around the membrane wire.
According to the environment of membrane silk, preparing corresponding hydrophilic membrane casting solution and hydrophobic membrane casting solution by using high molecular raw materials, a solvent, a hydrophilic agent or a hydrophobic agent according to a certain concentration ratio. The weight percentage of the polymer material in the casting solution is 5-30%, the weight percentage of the solvent is 40-60%, and the weight percentage of the hydrophilic agent/hydrophobic agent material is about 8-20%. The selected polymer raw materials can be polyvinylidene fluoride, polysulfone, polyethersulfone, polyetheretherketone and the like. The hydrophilic agent mainly comprises polyvinylpyrrolidone and polyethylene glycol, the hydrophobic material is mainly determined according to the environment of the membrane silk, and the membrane silk can be made into a hydrophilic or hydrophobic membrane. Hydrophilic membranes are mainly used in the fields of submerged ultrafiltration, MBR and the like. The hydrophobic membrane is mainly applied to the fields of membrane distillation, membrane crystallization, membrane aeration, membrane pervaporation and the like. The solvent used is mainly N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, tetrahydrofuran, N-methylpyrrolidone, etc.
In some exemplary embodiments:
the casting solution used herein is mainly used for forming a separation layer, the separation layer comprises a surface skin layer and a membrane sub-layer, the separation layer is a hollow fiber membrane formed by phase inversion after a spinning process, the material of the separation layer is PVDF, two layers, namely the surface skin layer and the membrane sub-layer from outside to inside, can appear on the appearance of the separation layer in the spinning preparation process, the material of the separation layer is PVDF, and the two layers are formed because: the cortex is firstly subjected to phase separation and is formed before the sub-layer, the diffusion of a non-solvent to the sub-layer is limited, and the sub-layer is subjected to delayed phase separation to form a porous structure; the diffusion rates of the solvent and the non-solvent in the nascent membrane are different, and the stronger the non-solvent in the gel bath, the faster the precipitation speed of the nascent membrane will be, and the more porous structure will appear in the membrane-forming sublayer.
The utility model discloses a preparation method is at hollow fiber membrane one shot forming's in-process for the polymer in the core chamber of hollow fiber membrane permeates to the membrane sublayer in, make the bottom of being mixed together by PVDF and polymer in the below of membrane sublayer formed, toughened polymer here, it is that cross-linking reaction is carried out by polymerizable reactant and cross-linking agent and obtains, this kind of polymer is at the internal surface of PVDF hollow fiber membrane, the infiltration is in the middle of PVDF, the bottom that the independent one deck was formed by PVDF and polymer mixture has been formed, this one deck can improve PVDF hollow fiber membrane's vertical tensile strength. In cross section, a bottom layer formed by mixing the surface skin layer, the membrane sub-layer, PVDF and the polymer from outside to inside is formed, and since the surface skin layer and the membrane sub-layer are separated and formed simultaneously during phase separation, the two layers are also defined as a separation layer in this patent as a whole. The thickness of the surface skin layer can be 0.1-3mm, the thickness of the film sub-layer is 1-50 mu m, and the thickness of the bottom layer is 0.1-5 mu m; the prepared hollow fiber membrane is a microfiltration membrane or an ultrafiltration membrane.
Both the polymerizable reactants and the crosslinking agent are water soluble, for example: the polymerizable reactant is selected from one or more of polyvinyl alcohol and chitosan; the cross-linking agent is one of formaldehyde, glutaraldehyde, glyoxal, maleic acid and fumaric acid.
The PVDF hollow fiber membrane is preferably prepared by the following method:
1. preparing homogeneous spinning dope containing crosslinkable polymer components;
2. preparing a PVDF membrane-making solution containing a cross-linking agent which is required by the cross-linking reaction of the cross-linkable polymer in the core solution;
3. the core solution and the PVDF membrane-making solution are coextruded through a spinneret and then contacted, cross-linking reaction is carried out on the inner surface of the PVDF hollow fiber membrane and the extension section of the inner surface facing the membrane sub-layer, and cross-linkable polymers are combined together through a covalent bond, so that the longitudinal tensile strength of the PVDF hollow fiber membrane is improved.
The core liquid is a water-based solution, the concentration of a polymerizable reactant is 0.5-5%, the temperature of the core liquid is 30-50 ℃, the pH concentration range of the core liquid is 2-4, the discharging speed of the core liquid is 12 mL/min, and the core liquid comprises the following components: the weight percentage of dimethylacetamide (DMAc), polymerizable reactants, water, dimethylacetamide (DMAc), the polymerizable reactants and water is 68-75%, 0.5-3% and 24-30%.
When polyvinyl alcohol is adopted, the core liquid is formed by combining one or more of Japanese Kohler PVA105 (with alcoholysis degree of 99-100%), PVA205 (with alcoholysis degree of 88-89%) and PVA117 (with alcoholysis degree of 99-100%), the pH concentration of the core liquid ranges from 2 to 4, the temperature of the core liquid ranges from 30 to 50 ℃, and the discharging speed of the core liquid is 12 mL/min. When chitosan is adopted, the chitosan is formed by one or two of the deacetylation degree of 91.7 percent and the molecular weight of 21 ten thousand or the deacetylation degree of 90 percent and the molecular weight of 30 ten thousand. The pH value range of the core liquid is 2-4, the temperature of the core liquid is 30-50 ℃, and the discharging speed of the core liquid is 12 mL/min.
The concentration of the cross-linking agent in the membrane-forming solution is 0.5-2%, and the membrane-forming solution comprises the following components: PVDF, polyvinylpyrrolidone (PVP) and dimethylacetamide (DMAc), wherein the weight percentage of the PVDF, the PVP and the DMAc is as follows: 10-20%, 4-14% and 70-80%, wherein the spinning temperature of the membrane making solution is 60-80 ℃, and the discharge speed of the membrane making solution is 26 mL/min.
In one embodiment, the casting solution is prepared at 60-90 deg.c, stirred for 1-6 hr, defoamed, pre-pressurized in nitrogen gas into metering pump, and extruded into spinning nozzle with certain frequency. The spinneret is covered with an electric heating jacket to heat the spinneret, and the heating temperature is usually 50-150 ℃. The heating aims to accelerate the volatilization of the solvent in the casting solution when the hollow fiber membrane wire enters the section of the air gap of the coagulating bath, so that the prepared hollow fiber membrane wire has a compact skin layer and the pollution resistance of the membrane wire in use is improved.
The core liquid and the membrane making liquid are crossed through a spinning nozzle, the core liquid and the membrane making liquid immediately enter a coagulating tank after running for 0-30 cm in an air section, the core liquid and the membrane making liquid move up and down for 3-8 min through a roller in the coagulating tank, a yarn receiving wheel is wound for 5-10 min, then a blade is used for cutting a produced PVDF hollow fiber membrane yarn, the PVDF hollow fiber membrane yarn is placed into a rinsing tank for soaking, the spinning process is completed, the cross-linking process occurs in the spinning process, the cross-linking reaction starts from the intersection of the core liquid and the membrane making liquid after the core liquid and the membrane making liquid are sprayed out of the spinning nozzle, and the polymer diffusion and cross-linking time period is the; the solution in the coagulating bath tank, the silk collecting tank and the rinsing tank is water or a mixture of DMAc and water, wherein the DMAc content in the mixture of DMAc and water is 30-60%; the temperature is 30-60 ℃; the temperature in the filament collecting groove is 30-60 ℃. In order to avoid the influence on the permeability of the membrane caused by the overlarge permeation rate of a polymerizable reactant in the core liquid into the membrane layer, a certain amount of inorganic salt can be added into the core liquid, so that the interfacial tension between the core liquid and the membrane-making liquid is improved, the permeation rate is properly reduced, the excessive polymer permeation is avoided, and the water flux is improved; the inorganic salt can be selected from sodium chloride, magnesium chloride, calcium chloride and the like, and the addition amount can be 3-6 wt% of the weight of the core liquid.
In one embodiment, the coagulation bath consists essentially of solvent and water, wherein the solvent consists essentially of solvent in the formulated casting solution. The mass fraction of the solvent in the coagulating bath is between 30 and 70 percent. The temperature of the coagulating bath and the rinsing bath is 20-90 ℃, the coagulating bath is used for carrying out liquid-liquid phase separation on the casting solution to solidify and form a film, and the rinsing bath is used for rinsing out a solvent and the like in the casting solution.
In one embodiment, further comprising: and a pulling roller 16 for pulling out the film tow obtained from the winding device 15.
In one embodiment, further comprising: and a rinsing liquid tank 17 for rinsing the hollow fiber membrane filaments obtained from the spinneret 2.
In one embodiment, further comprising: and a winding wheel 18 for winding the film tow obtained in the drawing roll 16.
Example 1
1) Preparing a casting solution: weighing 15% of PVDF (polyvinylidene fluoride), 18% of PVP-K90, 2% of PEG-200 and 75% of DMAC (dimethyl Acetylamide), stirring in a stirring kettle for 4-6 hours under the condition of a water bath at 80 ℃, dissolving uniformly, and then carrying out vacuum defoaming to prepare the polyvinylidene fluoride casting solution.
2) The casting solution and the core solution are extruded into a spinning nozzle by a metering pump, meanwhile, the weaving rope also enters the spinning nozzle, the primary membrane wire and the weaving rope enter a coagulation bath together under the drive of a filament winding roller of the coagulation bath, and the primary membrane wire and the weaving rope form a bundle under the action of a ceramic ring when the primary membrane wire is coagulated in the coagulation bath.
3) Under the action of the three rollers, the film bundle passes through the winding device. The winding device mainly comprises a circular ring. The ring outside contains the round rubber circle, and the ring vertical fixation contains 4 rubber circle wheels on a flat board on the flat board, and the rubber circle wheel distributes into on a circumference, and in the ring just in time imbed the rubber wheel, one of them has the motor to drive the rotation in 4 rubber wheels, and the ring can become circular motion like this. 3 raised bearing rods are uniformly distributed on the circular ring, and the winding belt is placed on the raised bearing rods. When the circular ring moves circularly, the winding belt can be uniformly wound around the membrane wire, and the winding belt is made of polyethylene material, and is acid-resistant, alkali-resistant and organic solvent-resistant. After passing through the winding device, the loose bundle of film is wound into a bundle of filaments by the winding tape.
4) After rinsing and bathing, the silk is collected by a silk collecting wheel and then cut into bundles of binding silk. Soaking in warm water at 40 deg.C for 8 hr, and adding into glycerol water solution.
Hydrophilic agents PVP and PEG are added in the formula of the membrane casting solution, so that the produced membrane wire is hydrophilic, and the contact angle is about 70 degrees. Can be used in ultra-micro filtration system. Such as submerged ultrafiltration, MBR, etc.
The pore size distribution of the hollow fiber membrane prepared in example 1 is shown in fig. 11, and it can be seen that the surface pore size is highly uniform, and 80% or more of the membrane surface is 25nm pore size membrane pores.
Example 2
1) Preparing a casting solution: weighing 20% of PVDF, 18% of PVP-K30, 2% of PEG-200 and 75% of DMAC, stirring in a stirring kettle for 4-6 hours under the condition of a water bath at 80 ℃, dissolving uniformly and then carrying out vacuum defoaming to prepare the polyvinylidene fluoride membrane casting solution.
2) The casting solution and the core solution are extruded into a spinning nozzle by a metering pump, meanwhile, the weaving rope also enters the spinning nozzle, the primary membrane wire and the weaving rope enter a coagulation bath together under the drive of a filament winding roller of the coagulation bath, and the primary membrane wire and the weaving rope form a bundle under the action of a ceramic ring when the primary membrane wire is coagulated in the coagulation bath.
3) Under the action of the three rollers, the film bundle passes through the winding device, and the film filaments are bundled into a bundle.
4) After rinsing and bathing, the silk is collected by a silk collecting wheel and then cut into bundles of binding silk. Soaking in warm water at 40 deg.C for 8 hr, adding into sodium hypochlorite aqueous solution of 5000ppm, rinsing to remove residual PVP in membrane pores, soaking in glycerol aqueous solution of 30% and air drying.
By adjusting the production process and the formula of the casting solution, the hydrophobic membrane with the membrane wire aperture of about 100nm can be prepared. Although the hydrophilic agent PVP-K30 is added in the formula of the casting solution, the PVDF material is hydrophobic, and PVP-K30 can be rinsed from membrane filaments in the rinsing process. The hydrophobic membrane can be used in the field of aeration and water purification of black and odorous water bodies, bubble-free aeration of aquaculture and the like.
The pore size distribution of the hollow fiber membrane prepared in example 1 is shown in fig. 12.
Claims (10)
1. The reinforced hollow fiber membrane is characterized by comprising a plurality of hollow fiber membrane filaments, wherein the hollow fiber membrane filaments are arranged into a bundle-shaped membrane filament bundle, a reinforcing rope is arranged in the middle of the membrane filament bundle, and a winding belt is tied outside the membrane filament bundle.
2. The reinforced hollow fiber membrane of claim 1, wherein the hollow fiber membrane is made of a polymer; the hollow fiber membrane filaments have an inner diameter in the range of 0.1 to 3mm and an outer diameter in the range of 0.4 to 5 mm.
3. A hollow fiber membrane spinneret, comprising:
a plurality of spinning nozzles (2) are distributed on the spinning nozzle (1), and weaving rope holes (3) are arranged in the middle of the spinning nozzles (2);
reinforcing ropes (12) are strung in the braided rope holes (3);
a hollow fiber membrane spinneret orifice (21) is arranged in the spinneret orifice (2), and a core liquid orifice (20) is sleeved in the hollow fiber membrane spinneret orifice (21).
4. The hollow fiber membrane spinneret according to claim 3, wherein the spinneret (1) is further provided with a core liquid inlet hole (19) communicated with the core liquid hole (20); the spinning nozzle (1) is internally provided with a cavity (22), and the cavity (22) is communicated with the hollow fiber membrane spinning holes (21).
5. A reinforced hollow fiber membrane production apparatus comprising the hollow fiber membrane spinneret according to claim 3.
6. The reinforced hollow fiber membrane production apparatus according to claim 5, further comprising: the core liquid tank (7), the core liquid tank (7) is communicated with the core liquid inlet hole (19); the core liquid tank (7) is connected with the core liquid inlet hole (19) through a second pump (9); further comprising: the casting film liquid tank (6), the casting film liquid tank (6) is communicated with the hollow fiber film spinneret orifice (21); the casting film liquid tank (6) is connected with a hollow fiber film spinneret orifice (21) through a first pump (8); a first gas source (10) is arranged on the casting film liquid tank (6); a second air source (11) is arranged on the core liquid tank (7).
7. The reinforced hollow fiber membrane production apparatus according to claim 6, further comprising: a coagulation bath (14) for performing coagulation bath treatment on the film filaments obtained in the spinneret (1); further comprising: a circular ring (13) for tightening the film filaments and the reinforcing cords (12) obtained from the spinneret (1); further comprising: and a winding device (15) for winding the outside of the film tows obtained from the circular ring (13) with a winding tape.
8. The reinforced hollow fiber membrane production apparatus according to claim 6, wherein the winding means (15) comprises: a turntable (26) with a central opening for passing the membrane yarn bundle; the turntable (26) is provided with a tape bearing (27), and a winding tape (5) is stringed in the tape bearing (27); further comprising: a driving wheel (24) and a driven wheel (25) which are attached to the edge of the turntable (26), wherein the driving wheel (24) is driven to rotate by a motor (28).
9. The reinforced hollow fiber membrane production apparatus according to claim 6, further comprising: and a pulling roller (16) for pulling out the film tow obtained from the winding device (15).
10. The reinforced hollow fiber membrane production apparatus according to claim 6, further comprising: a rinsing liquid tank (17) for rinsing the hollow fiber membrane filaments obtained from the spinneret (2); further comprising: and the winding wheel (18) is used for winding the film tows obtained in the drawing roller (16).
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| Application Number | Priority Date | Filing Date | Title |
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| CN201920604973.4U CN210934506U (en) | 2019-04-29 | 2019-04-29 | Enhancement mode hollow fiber membrane, spinning jet and preparation facilities thereof |
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| CN201920604973.4U CN210934506U (en) | 2019-04-29 | 2019-04-29 | Enhancement mode hollow fiber membrane, spinning jet and preparation facilities thereof |
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Effective date of registration: 20200720 Address after: 211808 Nanjing City, Jiangsu Province, Jiangbei new District Garden train of thought No. 1 Patentee after: NANJING JIUYING MEMBRANE TECHNOLOGIES Co.,Ltd. Address before: 211808 Nanjing City, Jiangsu Province, Jiangbei new District Garden train of thought No. 1 Patentee before: NANJING MEMBRANE MATERIAL INDUSTRY TECHNOLOGY INSTITUTE Co.,Ltd. |