CN116099378B - Preparation method and system of hollow fiber membrane type oxygenation membrane - Google Patents
Preparation method and system of hollow fiber membrane type oxygenation membrane Download PDFInfo
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- CN116099378B CN116099378B CN202310381950.2A CN202310381950A CN116099378B CN 116099378 B CN116099378 B CN 116099378B CN 202310381950 A CN202310381950 A CN 202310381950A CN 116099378 B CN116099378 B CN 116099378B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/08—Hollow fibre membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D11/0292—Treatment of the solvent
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0011—Casting solutions therefor
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D67/0088—Physical treatment with compounds, e.g. swelling, coating or impregnation
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- B01D69/08—Hollow fibre membranes
- B01D69/085—Details relating to the spinneret
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D2323/42—Details of membrane preparation apparatus
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Abstract
The invention discloses a preparation method and a system of a hollow fiber membrane type oxygenation membrane, wherein the preparation method comprises the following steps: melt mixing a polymer and a diluent to obtain a casting solution; extruding the casting solution from the annular spinneret, and feeding the casting solution into a coagulating liquid for curing to obtain nascent hollow fiber membrane filaments, wherein the nascent hollow fiber membrane filaments are collected by a receiving roller positioned in the coagulating liquid; then the first extraction device is transmitted to a first extraction device through a traction roller, wherein the first extraction device comprises a first extraction tank, a spray head, an adsorption device and a pump; the primary hollow fiber membrane filaments are transferred to a filament winding wheel which is partially positioned in an extracting agent through a traction roller for winding and collecting, and in the winding and collecting process, a spray head performs online spray washing on the filament winding wheel to obtain secondary hollow fiber membrane filaments wound on the filament winding wheel; offline extraction is carried out on the secondary hollow fiber membrane filaments, so as to obtain tertiary hollow fiber membrane filaments; and drying the three-time hollow fiber membrane filaments to obtain the hollow fiber membrane type oxygenation membrane. The invention can obviously improve the extraction efficiency.
Description
Technical Field
The invention relates to the technical field of medical instruments, in particular to a preparation method and a system of a hollow fiber membrane type oxygenation membrane.
Background
External membrane oxygenation (Extracorporeal Membrane Oxygenation, ECMO) is mainly used to provide sustained in vitro respiration and circulation to critically ill cardiopulmonary failure patients to sustain patient life. The main components of the device comprise an oxygenator, a blood pump, a monitoring system and the like. Wherein, the membrane material in the oxygenator oxidizes the membrane to be a key structure for determining the exchange efficiency of qi and blood.
The oxygenation membrane, also called artificial lung membrane, is sequentially subjected to a reel type oxygenation membrane, a flat plate type oxygenation membrane and a hollow fiber membrane type oxygenation membrane according to the technological development process, wherein the hollow fiber membrane type oxygenation membrane is provided with a cavity along the axial direction, the cross section of the hollow fiber membrane type oxygenation membrane is of a porous structure, and the porous structure can selectively permeate/adsorb fluid, so that the mixed fluid is separated and enriched.
In the prior art, the preparation method of the hollow fiber membrane type oxygenation membrane comprises the following steps:
1) Forming a homogeneous molten casting film solution by using a polymer, a diluent and the like at a high temperature;
2) Extruding the molten film casting liquid by a double-screw extruder, conveying to an annular spinneret, extruding by the spinneret, and then cooling and shaping in a coagulating bath to obtain nascent hollow fiber film filaments;
3) Immersing the primary hollow fiber membrane filaments into an extractant, and replacing the diluent by the extractant to form a microporous structure, thereby obtaining secondary hollow fiber membrane filaments;
4) And drying the extracted secondary hollow fiber membrane filaments, and removing the extractant to obtain a finished product of the hollow fiber membrane type oxygenated membrane.
In the preparation method, the primary hollow fiber membrane filaments are collected by the filament winding wheel, a membrane layer with the thickness of a few millimeters or even a few centimeters can be formed, the primary hollow fiber membrane filaments collected by the filament winding wheel are completely extracted for 3 days to 1 week or even longer, and the extraction efficiency is far lower than the production efficiency of the primary hollow fiber membrane filaments, so that an off-line extraction mode is generally adopted, namely, the primary hollow fiber membrane filaments are extracted after being wound and collected by the filament winding wheel.
Problems arising from the above-described preparation methods include: 1. long extraction times result in low production efficiency; 2. the nascent hollow fiber membrane filaments which are just prepared have not formed a porous structure, and the product performance is easily influenced by environment (such as the interval time from preparation to extraction, the ambient temperature and humidity, etc.); 3. the coiled diluent is extracted again, the viscosity of the diluent is increased at normal temperature, the diluent is in a viscous or semi-solid form, and the diluent can be removed after the extractant is extracted for a longer time; 4. the nascent hollow fiber membrane filaments are wound layer by layer on a filament winding wheel to form a membrane layer with the thickness of a few millimeters or even a few centimeters, and the overlapped membrane layers are not beneficial to the subsequent extraction links.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a preparation method and a system of a hollow fiber membrane type oxygenated membrane, which improve the extraction efficiency and the performance of the prepared oxygenated membrane finished product.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
the preparation method of the hollow fiber membrane type oxygenation membrane comprises the following steps:
melt mixing a polymer and a diluent to obtain a casting solution;
extruding the casting solution from an annular spinneret, and feeding into a coagulating liquid for curing to obtain nascent hollow fiber membrane filaments, wherein the nascent hollow fiber membrane filaments are collected by a receiving roller positioned in the coagulating liquid;
the primary hollow fiber membrane filaments collected by the receiving roller are transferred to a first extraction device through a traction roller for online extraction, the first extraction device comprises a first extraction tank, a spray head, an adsorption device and a pump, the first extraction tank is internally provided with an extractant, the spray head is arranged above the first extraction tank, the adsorption device, the pump and the spray head are sequentially connected through a pipeline, the extractant in the first extraction tank is sprayed out of the spray head through the adsorption device and the pump and returns to the first extraction tank again, and the adsorption device comprises an adsorption material for adsorbing the diluent in the extractant; the primary hollow fiber membrane filaments are transferred to a filament winding wheel which is partially positioned in the extractant through the traction roller for winding and collecting, in the winding and collecting process, the nozzle performs online spray washing on the filament winding wheel, the diluent in the primary hollow fiber membrane filaments is removed by the extractant to form a micropore structure, and the secondary hollow fiber membrane filaments wound on the filament winding wheel are obtained;
performing off-line extraction on the secondary hollow fiber membrane filaments to obtain tertiary hollow fiber membrane filaments;
and drying the three-time hollow fiber membrane filaments to obtain the hollow fiber membrane type oxygenation membrane.
The invention also discloses a preparation system of the hollow fiber membrane type oxygenation membrane, which comprises the following steps:
the melt extrusion device comprises a stirrer, a screw extruder and an annular spinneret which are sequentially connected;
the forming device comprises a solidification groove, a receiving roller and a traction roller, wherein the solidification groove is positioned below the annular spinneret, the receiving roller is arranged in the solidification groove, the traction roller is arranged outside the solidification groove, and the solidification groove is used for containing solidification liquid; extruding through the annular spinneret, and curing through an air gap into the coagulation tank to obtain nascent hollow fiber membrane filaments, wherein the nascent hollow fiber membrane filaments are received by the receiving roller and transferred through the traction roller;
the device comprises a first extraction device, a spray head, an adsorption device, a pump and a wire winding wheel, wherein an extractant is contained in the first extraction device, the wire winding wheel is partially arranged in the extractant, the spray head is arranged above the first extraction device, the adsorption device, the pump and the spray head are sequentially connected through a pipeline, the extractant in the first extraction device is sprayed out of the spray head through the adsorption device and the pump and returns to the first extraction device again, and the adsorption device comprises an adsorption material for adsorbing the diluent in the extractant; the primary hollow fiber membrane filaments transferred by the traction roller reach the filament winding wheel to be wound and collected, in the winding and collecting process, the spray head performs online spray washing on the filament winding wheel, and the diluent in the primary hollow fiber membrane filaments is removed by the extractant to form a microporous structure, so that the secondary hollow fiber membrane filaments wound on the filament winding wheel are obtained;
the second extraction device performs off-line extraction on the secondary hollow fiber membrane filaments to obtain tertiary hollow fiber membrane filaments;
and the drying device is used for drying the three-time hollow fiber membrane filaments to obtain the hollow fiber membrane type oxygenation membrane.
The implementation of the embodiment of the invention has the following beneficial effects:
according to the embodiment of the invention, the adsorption device is arranged to separate the diluent in the extractant in real time, and the high-purity extractant adsorbed with the diluent is used for online extraction, so that the online extraction efficiency can be improved; immersing the wire winding wheel part into an extractant, spraying and washing the wire winding wheel by a spray head, efficiently extracting the primary hollow fiber membrane wires wound on the wire winding wheel above the liquid level of the extractant by the high-purity extractant sprayed by the spray head after absorbing the diluent, further soaking and extracting the primary hollow fiber membrane wires wound on the wire winding wheel below the liquid level of the extractant by the extractant, prolonging the contact time of the primary hollow fiber membrane wires and the extractant, extracting more diluent, and further improving the extraction efficiency; the higher the extraction efficiency is, the higher the content of the extracted diluent is, so that more microporous structures can be formed by on-line extraction, the specific surface area of membrane filaments is increased, the contact area and the space of the diluent and extractant molecule exchange in the subsequent off-line extraction process are increased, and the microporous structures also provide extraction channels for overlapped membrane layers, so that the extraction efficiency of off-line extraction can be remarkably improved, and the extraction efficiency is remarkably improved as a whole.
Compared with the offline extraction, the online dynamic online extraction method can shorten the extraction time from three days to seven days to less than 24 hours by adding the online dynamic online extraction (about 30 minutes), and can remarkably improve the overall extraction efficiency.
According to the invention, the diluent in the extracting agent is separated and recycled in real time by arranging the adsorption device, so that the extracting agent can be recycled, the consumption of the extracting agent is reduced, the diluent is synchronously separated and recycled, and the generation of the extracting agent waste liquid mixed with the diluent is avoided.
The invention improves the productivity through on-line extraction, avoids the influence of the product structure caused by off-line extraction, and improves the stability of the product performance.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, it being obvious that the drawings in the following description are only some embodiments of the invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
Wherein:
FIG. 1 is a schematic flow chart of a method for preparing a hollow fiber membrane type oxygenation membrane according to an embodiment of the invention.
Fig. 2 is a schematic structural diagram of an adsorption apparatus according to an embodiment of the present invention.
Fig. 3 is a schematic structural diagram of an adsorption module according to an embodiment of the invention.
Fig. 4 is a schematic representation of the membrane filaments after extraction.
Fig. 5 is a schematic representation of membrane filaments prior to extraction.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention discloses a preparation method of a hollow fiber membrane type oxygenation membrane, which is characterized by comprising the following steps:
1) And (3) carrying out melt mixing on the polymer and the diluent to obtain the casting solution.
The polymer is a bulk polymer forming a hollow fiber membrane type oxygenating membrane, and poly-4-methyl-1-pentene (PMP) is gradually becoming a major membrane material of the oxygenator due to high oxygen permeability, chemical resistance, excellent biocompatibility and hygienic safety, but of course, the polymer may be other polyolefin compounds such as polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ethylene-acrylic acid (ester) copolymer, poly-1-butene, poly-1-pentene-1-hexene, poly-1-octene, polycycloolefin, etc. Of course, the polymer may also be a fluoropolymer, a silicon-containing polymer or polyester, and the like.
The polymer and the diluent form a homogeneous solution at high temperature, phase separation occurs in the process of cooling, the diluent is removed by the extractant, and a porous structure along the cross section direction can be formed, and the porous structure is used for selectively penetrating/adsorbing the fluid, so that the mixed fluid is separated and enriched. Specifically, in a specific embodiment, the diluent may include one or more of diethyl phthalate (DEP), dibutyl phthalate (DBP), di-n-octyl phthalate (DOP), di (2-ethylhexyl) phthalate (DEHP), dibutyl terephthalate (DOTP), diphenyl ether phthalate (DPE), and the like.
2) Extruding the casting solution from the annular spinneret, and feeding the casting solution into a coagulating liquid for curing to obtain nascent hollow fiber membrane filaments, wherein the nascent hollow fiber membrane filaments are collected by a receiving roller positioned in the coagulating liquid.
3) The primary hollow fiber membrane filaments collected by the receiving roller are transferred to a first extraction device for extraction through a traction roller, the first extraction device comprises a first extraction tank, a spray head, an adsorption device and a pump, the first extraction tank is internally provided with an extractant, the spray head is arranged above the first extraction tank, the adsorption device, the pump and the spray head are sequentially connected through a pipeline, the extractant in the first extraction tank is sprayed out of the spray head through the adsorption device and the pump and returns to the first extraction tank again, and the adsorption device comprises an adsorption material for adsorbing the diluent in the extractant; and the primary hollow fiber membrane filaments are transferred to a filament winding wheel which is partially positioned in the extractant through a traction roller for winding and collecting, in the winding and collecting process, the filament winding wheel is subjected to online spray washing by a spray head, the diluent in the primary hollow fiber membrane filaments is removed by the extractant, and a microporous structure is formed, so that the secondary hollow fiber membrane filaments wound on the filament winding wheel are obtained.
The process is continuous online dynamic extraction, the diluent in the extracting agent is separated in real time by arranging the adsorption device, and the high-purity extracting agent with the diluent separated is adopted for online extraction, so that the online extraction efficiency can be improved; immersing the wire winding wheel part into an extractant, spraying and washing the wire winding wheel by a spray head, efficiently extracting the primary hollow fiber membrane wires wound on the wire winding wheel above the liquid level of the extractant by the high-purity extractant sprayed by the spray head after separating the diluent, further soaking and extracting the primary hollow fiber membrane wires wound on the wire winding wheel below the liquid level of the extractant by the extractant, prolonging the contact time of the hollow fiber membrane wires and the extractant, extracting the diluent more, and further improving the extraction efficiency; the higher the extraction efficiency is, the higher the content of the extracted diluent is, so that the microporous structure formed by on-line extraction is more, the pore diameter is larger, the specific surface area of the membrane filaments is increased, the contact area and the space of the diluent and the extractant molecule exchange in the subsequent off-line extraction process are increased, the microporous structure also provides an extraction channel for overlapped membrane layers, and the extraction efficiency of off-line extraction can be obviously improved, so that the extraction efficiency is obviously improved as a whole.
Compared with the offline extraction, the online dynamic online extraction method can shorten the extraction time from three days to seven days to less than 24 hours by adding the online dynamic online extraction (about 30 minutes), and can remarkably improve the overall extraction efficiency.
The process can separate and recycle the diluent in the extractant in real time by arranging the adsorption device, so that the extractant can be recycled, the consumption of the extractant is reduced, the diluent is synchronously separated and recycled, and the generation of the waste liquid of the extractant mixed with the diluent is avoided.
The process is characterized in that the primary hollow fiber membrane yarn is wound and collected, and meanwhile, on-line extraction is carried out, extraction is carried out under the condition that the diluent is not completely solidified and cooled, so that the diluent is easier to remove, the production efficiency is improved, the influence on the product structure caused by off-line extraction is avoided, and the stability of the product performance is improved.
In a specific embodiment, the extractant comprises one or more of diethyl ether, propyl ether, butyl ether, methanol, ethanol, isopropanol, ethyl acetate, propyl acetate, butyl acetate, amyl acetate, acetone, butanone, cyclohexanone, ethylene glycol dimethyl ether, ethylene glycol butyl ether, tetrahydrofuran, dichloromethane, chloroform, DMF and DMAc.
In one embodiment, in order to further increase the extraction efficiency, it is preferable to use a heated extractant for extraction, and the temperature of the extractant may be room temperature to 90 ℃.
In a specific embodiment, the rotation speed of the wire winding wheel is 20 r/min-90 r/min, the diameter of the wire winding wheel is 20 cm-100 cm, the length of the secondary hollow fiber membrane wires wound on the wire winding wheel is 0.1 km-10 km, and the time of online extraction can be calculated through the parameters.
In a specific embodiment, the flow rate of the spray head is 50 mL/min-5000 mL/min, so that the on-line extraction with high extraction rate can be realized, and meanwhile, the adsorption material can adsorb and separate most of the diluent, and the extractant can be continuously recycled.
In a specific embodiment, the thickness of the secondary hollow fiber membrane filaments wound on one filament winding wheel is 0.01-2 cm, so that the membrane filaments positioned inside after winding are also fully extracted and dried, and the hollow fiber membrane type oxygenation membrane with stable quality can be obtained.
In one embodiment, the mass ratio of the adsorbent material to the extractant is 1/100-1/10, and 50% -80% of the diluent can be separated, so that the extractant can be continuously recycled.
4) And (3) performing off-line extraction on the secondary hollow fiber membrane filaments to obtain the tertiary hollow fiber membrane filaments.
In this step, any existing method may be used for off-line extraction, and in a specific embodiment, the whole roll wire winding wheel around which the secondary hollow fiber membrane wire is wound is placed in the second extraction tank to perform soaking extraction.
Of course, in order to further improve the extraction efficiency, the first extraction device may also be used for off-line extraction.
5) And drying the three-time hollow fiber membrane filaments, and removing the extractant to obtain the hollow fiber membrane type oxygenation membrane.
In one embodiment, the hollow fiber membrane oxygenating membrane has an average pore size of 50nm or less, a pore size of far less than 100nm, and high selectivity to oxygen and carbon dioxide, and can be applied to an oxygenator.
Referring to fig. 1, the invention also discloses a preparation system of the hollow fiber membrane type oxygenation membrane, which sequentially comprises: a melt extrusion apparatus 10, a molding apparatus 20, a first extraction apparatus 30, a second extraction apparatus 40, and a drying apparatus 50.
The melt extrusion apparatus 10 includes a stirrer 11, a screw extruder 12 and an annular spinneret 13 which are sequentially connected, and the polymer and the diluent are uniformly mixed in the stirrer 11, melt-extruded through the screw extruder 12 to obtain a molten state homogeneous casting solution, and then the molten state homogeneous casting solution is extruded through the annular spinneret 13.
The forming device 20 comprises a solidification tank 21 positioned below the annular spinneret 13, a receiving roller 22 arranged in the solidification tank 21 and a traction roller 23 arranged outside the solidification tank 21, wherein the solidification tank 21 is used for containing solidification liquid, casting liquid extruded by the annular spinneret 13 enters the solidification tank 21 through an air gap to be solidified, primary hollow fiber membrane filaments are obtained, the primary hollow fiber membrane filaments are received by the receiving roller 22, and the primary hollow fiber membrane filaments are transferred to the next process through the traction roller 23.
The first extraction device 30 comprises a first extraction tank 31, a spray head 32, an adsorption device 33, a pump 34 and a wire winding wheel 35, wherein the first extraction tank 31 contains an extractant, the wire winding wheel 35 is partially arranged in the extractant, the spray head 32 is arranged above the first extraction tank 31, the adsorption device 33, the pump 34 and the spray head 32 are sequentially connected through pipelines, the extractant in the first extraction tank 31 is sprayed out of the spray head 32 through the adsorption device 33 and the pump 34 and returns to the first extraction tank 31 again, and the adsorption device 33 is used for adsorbing and separating the diluent in the extractant; the primary hollow fiber membrane filaments transferred by the traction roller 23 reach the winding wheel 35 for winding and collecting, in the winding and collecting process, the nozzle 32 performs online spray washing on the winding wheel 35, the diluent in the primary hollow fiber membrane filaments is removed by the extractant, and a microporous structure is formed, so that the secondary hollow fiber membrane filaments wound on the winding wheel 35 are obtained.
The second extraction device 40 performs off-line extraction on the secondary hollow fiber membrane filaments to obtain tertiary hollow fiber membrane filaments. Specifically, in one embodiment, the second extraction device 40 includes a second extraction tank 41, and the whole-roll filament winding wheel 35 around which the secondary hollow fiber membrane filaments are wound is placed in the second extraction tank 41 for soaking extraction.
The drying device 50 dries the tertiary hollow fiber membrane filaments to obtain a hollow fiber membrane type oxygenation membrane.
In a specific embodiment, the adsorption device 33 includes one or more adsorption modules 331, and when the number of adsorption modules 331 is more than two, the adsorption modules 331 are used in series or in parallel to realize multistage adsorption, so as to improve the separation efficiency of the diluent, and to obtain a high-purity extractant, so that the diluent in the nascent hollow fiber membrane filaments can be extracted more efficiently. In addition, the adsorption module 331 can be replaced according to the use time and the adsorption effect as required, and is convenient to replace.
Referring to fig. 2, the adsorption device 33 further includes a bell mouth 332 connected with the adsorption module 331 and a connector 333, the connector 333 is connected with the pump 34 through a pipeline, the bell mouth 332 is used for allowing the extractant to enter, and the bell mouth 332 is beneficial for collecting the extractant.
Referring to fig. 3, in a specific embodiment, the adsorption module 331 includes a housing and an adsorption material 3311 filled in the housing, the housing is provided with a liquid inlet and a liquid outlet, and the liquid inlet and the liquid outlet are respectively provided with a filter assembly 334, and the filter assembly 334 is used for preventing the adsorption material 3311 from leaking into the extraction tank 31. The shell can be made of polypropylene, glass fiber reinforced plastic, stainless steel and the like. When the adsorbent 3311 is filled, the adsorbent 3311 having a larger particle size is preferably filled near the filter assembly 334, and the smaller particle size adsorbent 3311 is filled in the middle, so that the small particle size adsorbent 3311 is prevented from entering the extraction tank 31.
In a specific embodiment, the adsorbing material 3311 may include one or more of activated carbon particles, activated carbon fibers, activated carbon powder, carbon nanotubes, multi-walled carbon nanotubes, fly ash, graphene, zeolite, hydroxyapatite, rice hull ash, bentonite, montmorillonite, and the like. In the present invention, the adsorbing material 3311 can be reused, which is more environment-friendly.
In one embodiment, the filter assembly 334 includes a sponge 3341, a screen 3342, and a porous filter plate 3343 stacked in this order, the sponge 3341 being attached to an adsorbent material 3311.
In one embodiment, the pump 34 may be a pneumatic diaphragm pump, peristaltic pump, or the like, and may provide power to direct the extractant sequentially through the inlet and outlet to enhance contact between the extractant and the porous substance and increase extraction efficiency.
The water outlet mode of the spray head 32 is adjustable, and comprises a rainwater type, a single-strand type, a multi-strand type and the like.
In one embodiment, the first extraction tank 31 has a heating function, and can be used for heating the extractant to improve the extraction efficiency of the extractant.
In one embodiment, the first extraction device 30 further includes a valve 36, the valve 36 being disposed in the line between the adsorption device 33 and the pump 34.
The following are specific examples.
Example 1
A system for preparing a hollow fiber membrane type oxygenating membrane as shown in fig. 1 is provided. Wherein, adsorption material in the adsorption equipment is activated carbon, and the extractant in first extraction groove and the second extraction groove is isopropanol, and the temperature is 40 ℃, and the mass ratio of activated carbon to extractant in the first extraction groove is 1:25, the flow rate of the spray head is 1000mL/min, the diameter of the wire winding wheel is 40cm, and the rotating speed of the wire winding wheel is 70 r/min.
The preparation method of the hollow fiber membrane type oxygenation membrane comprises the following steps:
600g of poly-4-methyl-1-pentene (PMP) and 1400g of di-n-octyl phthalate (DOP) are mixed and then heated to a molten state by a double screw extruder, the mixture is extruded by an annular spinneret at a speed of 2mL/min and enters a first solidification tank to be solidified, so as to obtain primary hollow fiber membrane filaments, the primary hollow fiber membrane filaments are received by a receiving roller, are transmitted forward to a second solidification tank by a traction roller to be continuously solidified, and are continuously transmitted forward to a winding wheel to be wound and collected by the traction roller, and a nozzle sprays an extractant to the winding wheel to extract and replace DOP in the primary hollow fiber membrane filaments while the winding and collection is carried out, so that secondary hollow fiber membrane filaments are obtained, the length of the membrane filaments wound on the winding wheel reaches 3km to be stopped, at the moment, the thickness of the membrane filaments on the winding wheel is about 5mm, and the wire collecting time of the winding wheel is 34min. And then, placing the wire winding wheel and the membrane wires together in a second extraction tank for soaking extraction, monitoring the content of the diluent in the membrane wires, and when the content of the diluent in the membrane wires is less than 1%, considering that the extraction is complete, stopping the soaking extraction, wherein the soaking extraction time is 48 hours, taking out the wire winding wheel, placing the wire winding wheel in a drying device for drying, and removing the extractant to obtain the hollow fiber membrane type oxygenated membrane. When the membrane filaments are not extracted, the membrane filaments are transparent, see fig. 5, in the extraction process, the transparent membrane filaments can be observed to gradually appear white, the more complete the extraction is, the lower the transparency of the membrane filaments is, and the transparent membrane filaments are uniformly white after the extraction, see fig. 4.
Example 2
Example 2 differs from example 1 only in that: the mass ratio of the adsorption material to the extractant is different, and the rest is the same.
The hollow fiber membrane type oxygenation membrane preparation system shown in fig. 1 is still adopted. Wherein, the mass ratio of the active carbon to the extractant is 1:10, the remainder being the same as in example 1.
The preparation method of the hollow fiber membrane type oxygenation membrane comprises the following steps:
600g of poly-4-methyl-1-pentene (PMP) and 1400g of di-n-octyl phthalate (DOP) are mixed and then heated to a molten state by a double screw extruder, the mixture is extruded by an annular spinneret at a speed of 2mL/min and enters a first solidification tank to be solidified, so as to obtain primary hollow fiber membrane filaments, the primary hollow fiber membrane filaments are received by a first receiving roller, are transmitted forward to a second solidification tank by a traction roller to be continuously solidified, and are continuously transmitted forward to a filament winding wheel to be wound and collected by the traction roller, and a nozzle sprays an extractant to the filament winding wheel to extract and replace DOP in the primary hollow fiber membrane filaments while winding and collecting, so that the secondary hollow fiber membrane filaments are obtained, the film filament length wound on the filament winding wheel is up to 3km, at the moment, the film filament thickness on the filament winding wheel is about 5mm, and the wire winding time of the filament winding wheel is 34min. And then, placing the wire winding wheel and the membrane wires together in a second extraction tank for soaking extraction, monitoring the content of the diluent in the membrane wires, and when the content of the diluent in the membrane wires is less than 1%, considering that the extraction is complete, stopping the soaking extraction, wherein the soaking extraction time is 24 hours, taking out the wire winding wheel, placing the wire winding wheel in a drying device for drying, and removing the extractant to obtain the hollow fiber membrane type oxygenated membrane.
Comparative example 1
Comparative example 1 differs from example 1 only in that the first extraction apparatus only includes a first extraction tank in which an extraction liquid is present, and includes no spray head, adsorption apparatus, and pump, and the wire winding wheel is disposed. When the length of the film wire wound on the wire winding wheel reaches 3km, the film wire on the wire winding wheel is about 5mm in thickness, and the wire winding time of the wire winding wheel is 34min. After 48h of off-line extraction, the diluent residue in the membrane filaments was 30%. On-line and off-line extraction, and the membrane silk is difficult to achieve a better extraction effect.
Comparative example 2
Comparative example 2 differs from example 1 only in that the first extraction device in comparative example 2 includes a first extraction tank, a shower head, and a pump, excluding an adsorption device, the pump circulates the extractant, and stops when the length of the film wire wound on the wire winding wheel reaches 3km, at which time the film wire thickness on the wire winding wheel is about 5mm, and the wire take-up time of the wire winding wheel is 34min. And then, placing the wire winding wheel and the film wire together into a second extraction tank for soaking and extracting, monitoring the content of the diluent in the film wire, and carrying out off-line extraction for 48 hours, wherein the residual diluent in the film wire accounts for 15%.
Comparative example 3
Comparative example 3 is a prior art using off-line extraction, and compared with example 1, only the second extraction device is included, the first extraction device is not included, the nascent hollow fiber membrane filaments are collected by the filament winding wheel, and stop when the length of the membrane filaments wound on the filament winding wheel reaches 3km, at this time, the thickness of the membrane filaments on the filament winding wheel is about 5mm, and the take-up time of the filament winding wheel is 34min. And then, placing the wire winding wheel and the film wire together into a second extraction tank for soaking and extracting, monitoring the content of the diluent in the film wire, and carrying out off-line extraction for 48 hours, wherein the residual diluent in the film wire accounts for 40%.
Test example 1
The adsorption capacity of the activated carbon was tested. Specifically, the first extraction device shown in fig. 1 is adopted, the mixed solution of the extractant and the diluent is contained in the extraction tank, the mass ratio of the active carbon to the extractant is 1:25, the pump is started for circulation for 5min, the concentration of the diluent in the extraction tank is reduced by 1000ppm, and the fact that the adsorbent materials of porous materials such as the active carbon can separate the diluent is explained.
Test example 3
Pore diameter parameters of cross sections of the hollow fiber membrane type oxygenated membranes produced in each example and comparative example were tested. Specifically, the pore size distribution of the membrane filaments was measured by a liquid-liquid displacement method using a pore size analyzer, and the results are shown in table 1. Table 1 also shows the on-line extraction time, on-line extraction rate and soak extraction time, and diluent residue in the final film wire for each of the examples and comparative examples. The method for testing the extraction rate of the on-line extraction comprises the following steps: detecting the content of the diluent in the secondary hollow fiber membrane filaments obtained after on-line extraction, and calculating the extraction rate by using the following formula:
extraction ratio = (diluent addition amount-diluent content in film wire)/diluent addition amount
In the above formula, the diluent content in the membrane filaments is obtained by continuing the extraction and detecting the extracted diluent content.
The adsorption rate of the adsorbent device to the diluent is also given in table 1.
Table 1: extraction time and pore size parameters of the final membrane filaments of each example and comparative example
From table 1 it can be seen that: first, when the first extraction device of the present invention is used for on-line extraction, the time for the second extraction can be significantly reduced, as compared with the comparative examples 1 to 3, although the comparative examples 1 and 2 also include on-line extraction, the time for the second extraction cannot be significantly reduced due to the low on-line extraction efficiency. Secondly, compared with comparative example 3, the online extraction is added in examples 1-2 and comparative examples 1-2, the maximum distribution of aperture ratio is narrower, and the cross section diameter of the prepared membrane wire is more uniform and the morphological structure of the membrane wire is more stable; it can also be seen that: the greater the efficiency of on-line extraction, the narrower the maximum distribution of the aperture ratio of the membrane silk, the more stable the morphological structure of the membrane silk, i.e. the greater the extraction rate of on-line extraction, the more stable the preliminary shaping, and the less the influence of the environment during the subsequent off-line treatment. Thirdly, comparative example 3 does not have on-line extraction, and compared with examples 1-2 and comparative examples 1-2, the average pore diameter is obviously smaller, which is caused by easy collapse of membrane pores which are not extracted in time, and the more timely the extraction, the more stable the shaping of the membrane pores. Fourth, the membrane silk prepared by the method has smaller average pore diameter, less than 50nm and good selectivity, and is suitable for an oxygenator.
The extraction rate of the diluent in the mixed solution in the first extraction tank after the on-line extraction is measured, and the adsorption rate of the diluent can be calculated through the on-line extraction rate and the concentration and the volume of the diluent remained in the first extraction tank. Through calculation, the method can be obtained: 50% -80% of the extractant extracted on line is separated by the adsorption device. After the on-line extraction is finished, the content of the diluent in the mixed solution of the first extraction tank is 1000 mg/L-2000 mg/L, and the diluent in the extracting agent exceeds 8000mg/L and cannot be continuously recycled through verification, so that the extracting agent with the diluent content of 1000 mg/L-2000 mg/L still has strong extraction capacity and can be continuously recycled.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the claims. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (10)
1. The preparation method of the hollow fiber membrane type oxygenation membrane is characterized by comprising the following steps:
melt mixing a polymer and a diluent to obtain a casting solution;
extruding the casting solution from an annular spinneret, and feeding into a coagulating liquid for curing to obtain nascent hollow fiber membrane filaments, wherein the nascent hollow fiber membrane filaments are collected by a receiving roller positioned in the coagulating liquid;
the primary hollow fiber membrane filaments collected by the receiving roller are transferred to a first extraction device through a traction roller for online extraction, the first extraction device comprises a first extraction tank, a spray head, an adsorption device and a pump, the first extraction tank is internally provided with an extractant, the spray head is arranged above the first extraction tank, the adsorption device, the pump and the spray head are sequentially connected through a pipeline, the extractant in the first extraction tank is sprayed out of the spray head through the adsorption device and the pump and returns to the first extraction tank again, and the adsorption device comprises an adsorption material for adsorbing the diluent in the extractant; the primary hollow fiber membrane filaments are transferred to a filament winding wheel which is partially positioned in the extractant through the traction roller for winding and collecting, in the winding and collecting process, the nozzle performs online spray washing on the filament winding wheel, the diluent in the primary hollow fiber membrane filaments is removed by the extractant to form a micropore structure, and the secondary hollow fiber membrane filaments wound on the filament winding wheel are obtained;
performing off-line extraction on the secondary hollow fiber membrane filaments to obtain tertiary hollow fiber membrane filaments;
and drying the three-time hollow fiber membrane filaments to obtain the hollow fiber membrane type oxygenation membrane.
2. The method for preparing a hollow fiber membrane type oxygenated membrane according to claim 1, comprising at least one of the following technical features a to i:
a. the linear speed of the wire winding wheel is 20-90 r/min, the diameter of the wire winding wheel is 20-100 cm, and the length of the secondary hollow fiber membrane wire wound on the wire winding wheel is 0.1-10 km;
b. the flow rate of the spray head is 50 mL/min-5000 mL/min;
c. the mass ratio of the adsorption material to the extractant is 1/100-1/10;
d. the thickness of the secondary hollow fiber membrane filaments wound on the filament winding wheel is less than or equal to 2 cm;
e. the temperature of the extractant is room temperature to 90 ℃;
f. the extractant comprises one or more than two of diethyl ether, propyl ether, butyl ether, methanol, ethanol, isopropanol, ethyl acetate, propyl acetate, butyl acetate, amyl acetate, acetone, butanone, cyclohexanone, ethylene glycol dimethyl ether, ethylene glycol butyl ether, tetrahydrofuran, dichloromethane, chloroform, DMF and DMAc;
g. the polymer comprises one or more than two of polyolefin compounds, fluorine-containing polymers, silicon-containing polymers and polyesters;
h. the diluent comprises one or more than two of diethyl phthalate, dibutyl phthalate, di-n-octyl phthalate, di (2-ethylhexyl) phthalate, dibutyl terephthalate and diphenyl ether phthalate;
i. the hollow fiber membrane type oxygenation membrane has an average pore diameter of 50 to nm.
3. A system for preparing a hollow fiber membrane type oxygenation membrane, comprising:
the melt extrusion device comprises a stirrer, a screw extruder and an annular spinneret which are sequentially connected;
the forming device comprises a solidification groove, a receiving roller and a traction roller, wherein the solidification groove is positioned below the annular spinneret, the receiving roller is arranged in the solidification groove, the traction roller is arranged outside the solidification groove, and the solidification groove is used for containing solidification liquid; extruding the casting solution through the annular spinneret, and allowing the casting solution to enter the coagulation tank through an air gap for solidification to obtain nascent hollow fiber membrane filaments, wherein the nascent hollow fiber membrane filaments are received by the receiving roller and are transmitted through the traction roller;
the device comprises a first extraction device, a spray head, an adsorption device, a pump and a wire winding wheel, wherein an extractant is contained in the first extraction device, the wire winding wheel is partially arranged in the extractant, the spray head is arranged above the first extraction device, the adsorption device, the pump and the spray head are sequentially connected through a pipeline, the extractant in the first extraction device is sprayed out of the spray head through the adsorption device and the pump and returns to the first extraction device again, and the adsorption device comprises an adsorption material for adsorbing the diluent in the extractant; the primary hollow fiber membrane filaments transferred by the traction roller reach the filament winding wheel to be wound and collected, in the winding and collecting process, the spray head performs online spray washing on the filament winding wheel, and the diluent in the primary hollow fiber membrane filaments is removed by the extractant to form a microporous structure, so that the secondary hollow fiber membrane filaments wound on the filament winding wheel are obtained;
the second extraction device performs off-line extraction on the secondary hollow fiber membrane filaments to obtain tertiary hollow fiber membrane filaments;
and the drying device is used for drying the three-time hollow fiber membrane filaments to obtain the hollow fiber membrane type oxygenation membrane.
4. A system for preparing a hollow fiber membrane oxygenating membrane according to claim 3, characterized in that the adsorption device comprises one or more adsorption modules, and when the adsorption modules are two or more, the adsorption modules are used in combination by being connected in series or in parallel.
5. The system for preparing a hollow fiber membrane type oxygenated membrane according to claim 4, wherein the adsorption device further comprises a horn mouth connected with the adsorption module and a connector, the connector is connected with the pump through a pipeline, and the horn mouth is used for the extractant to enter.
6. The preparation system of a hollow fiber membrane type oxygenation membrane according to claim 4 or 5, wherein the adsorption module comprises a housing and the adsorption material filled in the housing, the housing is provided with a liquid inlet and a liquid outlet, and the liquid inlet and the liquid outlet are respectively provided with a filter assembly, and the filter assembly is used for preventing the adsorption material from leaking.
7. The system for producing a hollow fiber membrane type oxygenated membrane according to claim 6, wherein the adsorbent comprises one or more of activated carbon particles, activated carbon fibers, activated carbon powder, carbon nanotubes, multi-walled carbon nanotubes, fly ash, graphene, zeolite, hydroxyapatite, rice hull ash, bentonite, and montmorillonite.
8. The system for preparing a hollow fiber membrane oxygenating membrane according to claim 6, wherein the filtration assembly comprises a sponge, a screen and a porous filter plate laminated in this order, the sponge being connected with the adsorbent material.
9. The preparation system of the hollow fiber membrane type oxygenated membrane according to claim 3, wherein the pump is a pneumatic diaphragm pump or a peristaltic pump, provides power, guides the extractant to sequentially pass through the liquid inlet and the liquid outlet, strengthens the contact between the extraction liquid and the porous substance, and improves the extraction efficiency.
10. A system for preparing a hollow fiber membrane oxygenating membrane according to claim 3, characterized in that the first extraction tank has a heating function.
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