CN112007519B - Oxygenation membrane, preparation method thereof and oxygenation assembly - Google Patents

Oxygenation membrane, preparation method thereof and oxygenation assembly Download PDF

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Publication number
CN112007519B
CN112007519B CN202010827760.5A CN202010827760A CN112007519B CN 112007519 B CN112007519 B CN 112007519B CN 202010827760 A CN202010827760 A CN 202010827760A CN 112007519 B CN112007519 B CN 112007519B
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membrane
layer
hollow fiber
raw material
film
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CN112007519A (en
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贾建东
陈梦泽
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Hangzhou Kebaite Technology Co ltd
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Hangzhou Kebaite Technology Co ltd
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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
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61M—DEVICES FOR INTRODUCING MEDIA INTO, OR ONTO, THE BODY; DEVICES FOR TRANSDUCING BODY MEDIA OR FOR TAKING MEDIA FROM THE BODY; DEVICES FOR PRODUCING OR ENDING SLEEP OR STUPOR
    • A61M1/00—Suction or pumping devices for medical purposes; Devices for carrying-off, for treatment of, or for carrying-over, body-liquids; Drainage systems
    • A61M1/36—Other treatment of blood in a by-pass of the natural circulatory system, e.g. temperature adaptation, irradiation ; Extra-corporeal blood circuits
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
    • B01D63/02—Hollow fibre modules
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
    • B01D63/02—Hollow fibre modules
    • B01D63/021—Manufacturing thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
    • B01D63/10—Spiral-wound membrane modules
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
    • B01D63/10—Spiral-wound membrane modules
    • B01D63/103—Details relating to membrane envelopes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0002—Organic membrane manufacture
    • 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
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/10—Biological treatment of water, waste water, or sewage

Abstract

The invention relates to an oxygenation membrane, which comprises a membrane layer consisting of a plurality of hollow fiber membrane filaments, wherein the membrane layer at least comprises two layers, and laminated membrane layers are formed by laminating different layers of membrane layers, wherein any hollow fiber membrane filament in the membrane layer is partially overlapped with at least one hollow fiber membrane filament in the adjacent membrane layer in the projection of the membrane layer in the lamination direction. The membrane layer comprises an inclined membrane layer, the edge connecting line of all hollow fiber membrane wires at the same end in the inclined membrane layer is a straight line, and at least one section of the hollow fiber membrane wires or the extension line of the hollow fiber membrane wires is arranged at an acute angle with the straight line. The invention aims to provide an oxygenation membrane with higher gas exchange efficiency and better oxygenation effect, a preparation method thereof and an oxygenation assembly.

Description

Oxygenation membrane, preparation method thereof and oxygenation assembly
Technical Field
The invention relates to a gas exchange membrane, in particular to an oxygenation membrane, a preparation method thereof and an oxygenation assembly.
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 ECMO mainly comprises an intravascular cannula, a connecting pipe, a power pump (artificial heart), an oxygenator (artificial lung), an oxygen supply pipe, a monitoring system and the like. The core parts are an oxygenator (artificial lung) for oxygen-carbon dioxide exchange and a powered pump (artificial heart) for providing hemodynamic flow.
The working principle is approximately as follows: the venous blood in the patient is led to the oxygenator, the venous blood exchanges oxygen and carbon dioxide in the oxygenator, after the blood flows out of the oxygenator, the oxygen content in the blood is increased, and the carbon dioxide content is reduced, so that the effect of changing the venous blood into arterial blood in vitro is realized, and the damaged lung of the patient is replaced, thereby maintaining the life of the patient. The core component in the oxygenator is an oxygenation film, and in order to improve the oxygenation effect and efficiency, the oxygenator and the oxygenation film need to be provided in a related manner.
In the prior art, the oxygenator is divided into a silica gel membrane type and a hollow fiber type, and in the case that the hollow fiber membrane is used as the oxygenation membrane, the main component of the oxygenation membrane which plays a role in oxygen-carbon dioxide exchange is the hollow fiber membrane. The method comprises the steps of taking a single hollow fiber membrane wire for analysis, continuously introducing air or oxygen or other related gases into a hollow tube inside the hollow fiber membrane wire in the working process, enabling blood to flow around the outside of the hollow fiber membrane wire, and enabling oxygen to diffuse into the blood from the inside of the hollow fiber membrane wire through the tube wall and carbon dioxide to diffuse into the inside of the hollow tube from the inside of the hollow fiber membrane wire due to the high oxygen content in the inside of the hollow tube and low carbon dioxide content in the blood in the flowing process, so that the gas exchange function is realized. In the oxygenator, an oxygenation membrane composed of a plurality of hollow fiber membrane filaments is included, and blood flows around between the hollow fiber membrane filaments. The conventional oxygenation film is set as follows: weaving a plurality of hollow fiber membrane wires into a single-layer reticular structure through weaving wires, wherein the hollow fiber membrane wires and the weaving wires form right angles, and winding a hollow fiber membrane layer of the reticular structure to enable the whole hollow fiber membrane layer to be columnar, wherein one end is an air inlet end and the other end is an air outlet end, and using the hollow fiber membrane layer; it is apparent that this way, each of the hollow fiber membrane filaments is arranged in parallel, and thus the blood flow paths formed between the hollow fiber membrane filaments are also parallel and uniform flow paths, as shown in fig. 11, in which the arrows point in the direction of blood flow. In the figure, the column space surrounded by the dotted line is the blood near the center of the flow channel, and the flow channel space between the dotted line and the hollow fiber membrane wires is the part of the blood near the hollow fiber membrane wires. Because the whole blood flow channel is approximately in a long column shape, the flow channel does not have the effect of making the blood turbulent flow, the blood near the hollow fiber membrane wire part can quickly and efficiently exchange gas, the blood in the column-shaped flow channel space in the center dotted line cannot be well contacted with the hollow fiber membrane wire, and thus when the blood flow speed is high, the part of the blood does not exchange gas yet, and flows out of the oxygenator along the blood flow channel, so that the exchange of oxygen and carbon dioxide is influenced. Meanwhile, because the blood flows in the flow channel and is contacted with the hollow fiber membrane wires, the blood in the front half part of the flow channel is firstly flowed in the blood, and the blood near the position of the hollow fiber membrane wires can perform good gas exchange (namely, the blood at the position of the area A in fig. 11), and because the flow channel is basically free from turbulence, when the blood continues to flow in the flow channel, the blood which is subjected to gas exchange is still at the position near the position of the hollow fiber membrane wires (namely, the blood at the position of the area B in fig. 11), so that the gas exchange efficiency of the blood in the rear half part of the flow channel is reduced, and the gas exchange cannot be performed efficiently.
Disclosure of Invention
The invention aims to provide an oxygenation membrane with higher gas exchange efficiency and better oxygenation effect, a preparation method thereof and an oxygenation assembly.
In order to achieve the above purpose, the invention adopts the following technical scheme: the utility model provides an oxygenation membrane, includes the rete of constituteing by a plurality of hollow fiber membrane silk, the rete includes two-layer at least, and stacks up between the different rete retes and form the range upon range of rete, arbitrary one hollow fiber membrane silk in the rete is got in the rete, with at least one hollow fiber membrane silk in the adjacent rete in the projection of range upon range of orientation, partly overlaps.
By adopting the technical scheme, at least two film layers are adopted as the minimum unit of the oxygenation film for winding; and, when at least two-layer rete is opened and is spread, the hollow fiber membrane silk in the adjacent two-layer rete is nonparallel, overlaps in the projection on range upon range of orientation partially, and such setting compares among the prior art among the hollow fiber membrane silk parallel arrangement, can make to form slope, crisscross runner between the hollow fiber membrane silk, can increase the disorder degree of the inside blood flow of oxygenation membrane. The advantage of this is that it ensures that the blood in the central part of the blood flow channel can contact the surface of the hollow fiber membrane wire when flowing, thereby performing gas exchange, i.e. relatively increasing the contact area between the blood and the surface of the hollow fiber membrane wire and improving the gas exchange efficiency. The more complex the structure of the blood flow channel formed between the hollow fiber membrane wires, the greater the turbulence degree, and the blood can be ensured to be fully contacted with the surfaces of the hollow fiber membrane wires.
Furthermore, the membrane layer comprises an inclined membrane layer, the edge connecting line of all the hollow fiber membrane filaments at the same end in the inclined membrane layer is a straight line, and at least one section of the hollow fiber membrane filaments or the extending line of the hollow fiber membrane filaments is arranged at an acute angle with the straight line.
By adopting the technical scheme, the direction of the hollow fiber membrane filaments in the inclined membrane layer is limited. When the oxygenation membranes are unfolded and paved, the single hollow fiber membrane wires are not vertically arranged, but are inclined to a certain degree, so that when the plurality of membrane layers are stacked, a certain angle is formed between the hollow fiber membrane wires and the hollow fiber membrane wires, and the turbulence degree of blood is increased.
Furthermore, the hollow fiber membrane wires in the membrane layer are linear.
By adopting the technical scheme, the linear hollow fiber membrane wires are the most common hollow fiber membrane wires, and the structural design of the weaving and subsequent oxygenation assembly is convenient.
Further, an included angle formed between the hollow fiber membrane wires and a straight line formed by connecting edges of the hollow fiber membrane wires at the same end is set between 45 degrees and 90 degrees.
Further, the laminated film layer is formed by laminating two inclined film layers, and the included angle between the hollow fiber membrane wires in the two inclined film layers is 5-90 degrees.
By adopting the technical scheme, the inclination angle of the hollow fiber membrane wires in the inclined membrane layers and the included angle between the hollow fiber membrane wires in the two inclined membrane layers are limited; too large an inclination angle can elongate the length of the hollow fiber membrane filaments, and too large an inclination can cause too large resistance in the flow channel to affect the blood flow velocity, and too small an inclination angle can not realize a better turbulence effect.
Further, the membrane layer further comprises a vertical membrane layer, the edge connecting line of the hollow fiber membrane wires at the same end in the vertical membrane layer is a straight line, the hollow fiber membrane wires are in a straight line shape, and the hollow fiber membrane wires and the straight line are arranged at right angles.
Further, the laminated film layer is formed by laminating three layers of film layers, the middle is arranged to be a vertical film layer, the two sides are arranged to be inclined film layers, and the included angle between the hollow fiber film wires in the adjacent film layers is 5-90 degrees.
Through adopting above-mentioned technical scheme, realized a three-layer membrane layer's lamination structure, set up the intermediate level into perpendicular rete, both sides are the slope rete and can increase the turbulent flow degree in the oxygenation membrane to the maximum extent to can not make turbulent unbalance, can all keep the same or similar turbulent flow state in perpendicular rete both sides, reduce to minimum to the influence of membrane structure.
Further, bonding points are arranged between different film layers in the laminated film layers.
By adopting the technical scheme, the arrangement of the bonding points shows that the different layers of the film are bonded through the positions of some characteristics, and the bonding points include, but are not limited to, bonding points formed by heat sealing, bonding, electrostatic attraction and the like.
Further, the hollow fiber membrane filaments in the same membrane layer are fixed by braiding through braiding wires.
Through adopting above-mentioned technical scheme, inject through the braided wire between the hollow fiber membrane silk and weave fixedly, can increase the holistic structural strength of rete to the preparation of rete of being convenient for.
Further, a fixing groove is formed at the weaving fixing position of the hollow fiber membrane wires and the weaving wires.
Further, the depth of the fixing groove is set between 10 μm and 100 μm, and the width of the fixing groove is set between 90 μm and 110 μm.
Further, the depth of the fixing groove increases with the decrease of the included angle between the hollow fiber membrane wires and the braided wire.
Through adopting above-mentioned technical scheme, the structural strength between hollow fiber membrane silk and the braided wire can be increased to the setting of fixed slot for braided wire and hollow fiber membrane silk surface can not take place to slide easily, thereby produces harmful effect to membrane silk surface structure. If the inclination angle of the inclined membrane layer is large, namely the included angle between the hollow fiber membrane wires and the braided wires is small, the depth of the fixing groove needs to be made deeper so as to prevent the braided wires from slipping out of the fixing groove.
Further, the outer diameter of the hollow fiber membrane wire is set between 0.3mm and 0.4mm, and the inner diameter is set between 0.2mm and 0.28 mm.
Further, the interval between the hollow fiber membrane wires is set between 0.5mm and 0.75 mm.
By adopting the technical scheme, the number of the hollow fiber membrane wires in the oxygenation membrane and the gas exchange effect of the single membrane wire can be ensured. If the outer diameter of the hollow fiber membrane filaments is too large and the inner diameter is too small, the diffusion rate of oxygen and carbon dioxide is very low; if the outer diameter of the hollow fiber membrane wires is too large and the inner diameter is too large, most of air or oxygen in the hollow can be wasted; if the outer diameter of the hollow fiber membrane wire is too small and the inner diameter is too large, blood can easily permeate the tube wall of the hollow fiber membrane wire to cause the hollow fiber membrane wire to fail; if the outer diameter of the hollow fiber membrane wire is too small and the inner diameter is too small, the difficulty of the production process is increased, and the production cost is increased. If the number of hollow fiber membrane filaments in the oxygenation membrane is excessive, the blood flow rate is reduced so that the amount of blood that can be subjected to gas exchange at the same time is reduced; if the number is too small, a part of the blood cannot exchange gas, and then flows through the oxygenation membrane, and does not perform the function of oxygen-carbon dioxide exchange.
Further, the hollow fiber membrane filaments include a porous layer on the inside and a dense layer on the outside.
Further, the dense layer has a thickness of 0.1 μm to 3 μm and the loose layer has a thickness of 47 μm to 99 μm.
Further, the oxygen mass transfer efficiency of the hollow fiber membrane wire is 15-400L/(min.m) 2 Bar).
Through adopting above-mentioned technical scheme, the dense layer in the hollow fiber membrane silk outside can guarantee that blood is when flowing through the hollow fiber membrane silk outside, and the speed of infiltration is very slow to this effective life who increases the oxygenation membrane. If the thickness of the dense layer is too large, although the speed of blood penetration into the hollow fiber membrane filaments can be reduced, the exchange rate of oxygen-carbon dioxide can be affected at the same time; if the thickness of the dense layer is too small, the exchange rate of oxygen-carbon dioxide is fast, but the speed of penetration of the hollow fiber membrane filaments by blood is also fast, so that the effective service life is very low.
Further, the braided wire includes but is not limited to PP, PET, N6, N66 and their blends, with a gauge selected between 10F-100F, 10D-60D.
By adopting the technical scheme, the material and thickness of the braided wire are limited, so that the structural strength of the whole oxygenated film after braiding is ensured, and the oxygenated film is not easy to break and damage.
The invention also provides a preparation method of the oxygenated membrane, which comprises the following steps: s1: providing a membrane layer consisting of at least two layers of hollow fiber membrane filaments; s2: laminating the film layers prepared in the step S1 to form laminated film layers, wherein any hollow fiber film yarn in any one film layer is partially overlapped with at least one hollow fiber film yarn in the adjacent film layer in the projection of the lamination direction; s3: shaping; s4: and (5) rolling, namely rolling the laminated film layer.
By adopting the technical scheme, the mode of lamination among different membrane layers is controlled, so that the hollow fiber membrane wires in the adjacent membrane layers form a staggered structure after lamination, the turbulence degree of blood flowing through the outside of the hollow fiber membrane wires is increased, and the oxygen-carbon dioxide exchange efficiency is improved.
Further, the membrane layer provided in the step S1 is formed by weaving between a woven wire and hollow fiber membrane filaments.
By adopting the technical scheme, the membrane layer is formed by weaving the hollow fiber membrane wires through the weaving wires, so that the structural strength of the whole oxygenation membrane can be improved. Of course, the hollow fiber membrane layer can also be formed by braiding without braiding wires, namely, the hollow fiber membrane wires are simply laid in a layer according to a certain regular position, then a layer of hollow fiber membrane wires are laid in a layer according to a certain regular position on the surface of the hollow fiber membrane wires, and then the steps of shaping and rolling are carried out.
Further, the membrane layer woven in the step S1 is a vertical membrane layer formed by mutually perpendicular hollow fiber membrane filaments and woven wires.
Further, between the step S1 and the step S2, a step of obliquely pulling the vertical film layer into an inclined film layer may be further included.
By adopting the technical scheme, the membrane layers with two different structures are provided, so that turbulence is generated in blood outside the hollow fiber membrane wires during lamination.
Further, the specific operation of the oblique pulling can be that a rectangular vertical membrane layer is unfolded and laid, opposite sides of the vertical membrane layer are respectively fixed by using a fixing device, acting force is applied to enable an oblique angle to be generated between hollow fiber membrane wires and braided wires in the membrane layer, and an oblique membrane layer is formed; or alternatively, the process may be performed,
the vertical film layer is wound on the surface of the raw material roller to form a raw material roll, the raw material roll is opened, one end of the vertical film layer is fixed on a winding roller, the relative positions of the raw material roll and the winding roller are adjusted to be intersected in the axial direction, and the winding of the winding roller is performed while the raw material roll is unreeled to form the inclined film layer.
By adopting the technical scheme, two different methods for forming the inclined film layer by obliquely pulling the vertical film layer are provided, and the two methods can be considered as the preferred modes for considering the convenience and the cost of the process flow.
Further, the step S2 specifically includes S2-1: taking a first rectangular inclined film layer, and opening and paving; s2-2: taking a second rectangular inclined film layer, and opening and paving; s2-3: laminating a first film layer and a second film layer to form a double-layer film layer, wherein the inclination angles of the first inclined film net and the second inclined film net are different; or alternatively, the process may be performed,
s2-1: taking a first rectangular vertical film layer, and opening and paving; s2-2: taking a second rectangular inclined film layer, and opening and paving; s2-3: laminating the first film layer and the second film layer to form a double-layer film layer; or alternatively, the process may be performed,
s2-1: taking a rectangular vertical film layer, and opening and paving; s2-2: taking the other two rectangular inclined film layers, and opening and paving; s2-3: and respectively placing the inclined film layers on two sides of the vertical film layer to laminate to form three film layers.
By adopting the technical scheme, a laminated structure scheme of two double-layer film layers and one three-layer film layer is provided. In the double-layer film scheme, two layers can be formed by inclined film layers, or one layer can be an inclined film layer and the other layer can be a vertical film layer; in the scheme of three layers of film layers, one layer in the middle is a vertical film layer, and two layers on two sides are inclined film layers. In both of these arrangements, interlacing of the hollow fiber membrane filaments can be achieved, thereby increasing the turbulence effect of the blood as it flows through the oxygenation membranes.
Further, the step S2 further includes S2-4: and (5) using a hot air gun to blow and heat-seal the double-layer film layer or the three-layer film layer.
Further, the temperature of the hot air gun in the step S2-4 is set between 60 ℃ and 140 ℃.
Through adopting above-mentioned technical scheme, can make bilayer rete or three-layer rete heat seal, guarantee to fix between the different retes. The relative sliding can not occur, so that the relative positions of the hollow fiber membrane wires among different layers are changed, the effect of blood turbulence is weakened, and meanwhile, the structural strength of an oxygenation membrane can be ensured, and the oxygenation membrane is not easy to break up.
Further, the step S2 specifically includes S2-1: the method comprises the steps of providing a first raw material roll, a second raw material roll and a winding roller, wherein the axis of the first raw material roll and the axis of the winding roller are arranged in parallel, and the different surfaces of the axis of the second raw material roll and the axis of the winding roller are intersected; s2-2: unreeling the film layers on the first raw material roll and the second raw material roll, and flatly laying and laminating the end parts of the film layers on the surfaces of the winding rollers; s2-3: the winding roller is used for winding while the first raw material roll and the second raw material roll are unreeled; or alternatively, the process may be performed,
s2-1: providing a first raw material roll, a second raw material roll and a winding roller, wherein the axis of the first raw material roll is intersected with the different surface between the axis of the winding roller, and the axis of the second raw material roll is intersected with the different surface between the axis of the winding roller; s2-2: unreeling the film layers on the first raw material roll and the second raw material roll, and flatly laying and laminating the end parts of the film layers on the surfaces of the winding rollers; s2-3: the winding roller is used for winding while the first raw material roll and the second raw material roll are unreeled; or alternatively, the process may be performed,
s2-1: providing a first raw material roll, a second raw material roll, a third raw material roll and a winding roller, wherein the axis of the first raw material roll is intersected with the axis of the winding roller by different surfaces, the axis of the second raw material roll is intersected with the axis of the winding roller by different surfaces, and the axis of the third raw material roll is arranged in parallel with the axis of the winding roller; s2-2: unreeling film layers on the first raw material roll, the second raw material roll and the third raw material roll, flatly laying and laminating the end parts of the film layers on the first raw material roll, the second raw material roll and the third raw material roll, and fixing the film layers on the third raw material roll on the surface of the winding roll, wherein the film layers unreeled on the third raw material roll are arranged on the middle layer; s2-3: and the winding roller is used for winding while the first raw material roll, the second raw material roll and the third raw material roll are unreeled.
By adopting the technical scheme, a laminated structure scheme of two double-layer film layers and one three-layer film layer is provided. In the double-layer film scheme, two layers can be formed by inclined film layers, or one layer can be an inclined film layer and the other layer can be a vertical film layer; in the scheme of three layers of film layers, one layer in the middle is a vertical film layer, and two layers on two sides are inclined film layers. In both of these arrangements, interlacing of the hollow fiber membrane filaments can be achieved, thereby increasing the turbulence effect of the blood as it flows through the oxygenation membranes. In this scheme, can go on simultaneously perpendicular rete to one side, range upon range of and the rolling between the different retes, simplified the loaded down with trivial details degree of whole process step, improved the production efficiency of oxygenation membrane.
Further, the step S2 further includes S2-4: and rolling and compounding the laminated film layers by using a hot-pressing roller while unreeling the raw material roll and reeling the winding roller.
Further, the temperature of the hot press roller in the step s2-4 is set between 60 ℃ and 140 ℃.
Through adopting above-mentioned technical scheme, can make bilayer rete or three-layer rete carry out the heat seal when the rolling, guarantee to fix between the different retes. The relative sliding can not occur, so that the relative positions of the hollow fiber membrane wires among different layers are changed, the effect of blood turbulence is weakened, and meanwhile, the structural strength of an oxygenation membrane can be ensured, and the oxygenation membrane is not easy to break up. Of course, the bonding can be performed in a mode of not selecting hot pressing, and other modes of adhesive bonding, electrostatic bonding and the like can be adopted.
Further, in the step s2-2, the different surfaces of the axis of the first raw material roll and the axis of the second raw material roll are intersected.
Through adopting above-mentioned technical scheme, guaranteed from the rete of first raw materials roll unreeling and the rete inclination and/or incline direction difference of second raw materials roll unreeling, improved the oxygenation membrane whole turbulent flow effect to blood.
The invention also provides an oxygenation assembly, which comprises a shell, wherein the shell is provided with a liquid inlet, a liquid outlet, an air inlet and an air outlet, an air passage is formed in the air inlet, the air outlet and the hollow fiber membrane wires of the oxygenation membrane, a cavity is formed between the outer side wall of the hollow fiber membrane wires and the shell, the liquid inlet, the cavity and the liquid outlet form a flow passage, the single hollow fiber membrane wires are spirally arranged around the winding axis of the oxygenation membrane, and spiral inclination angles of the hollow fiber membrane wires in adjacent membrane layers in the oxygenation membrane are different.
Further, the hollow fiber membrane wires are provided with sealing members at positions close to two ends for sealing the space between the hollow fiber membrane wires and the space between the hollow fiber membrane wires and the shell.
Further, the air inlet is opposite to one end opening of the hollow fiber membrane wire, and the air outlet is opposite to the other end opening of the hollow fiber membrane wire.
By adopting the technical scheme, the air passage and the flow passage in the oxygenation component are relatively isolated, blood flows through the outer surface of the hollow fiber membrane wire in the flow passage, and meanwhile, air passes through the inside of the hollow fiber membrane wire, so that oxygen-carbon dioxide gas exchange occurs. The air inlet and the air outlet are arranged so as to facilitate air or oxygen to smoothly enter the hollow fiber membrane filaments.
Compared with the prior art, the oxygenation membrane and the oxygenation assembly using the oxygenation membrane have the advantages that: 1. has stronger blood turbulence effect, so that the exchange efficiency of oxygen and carbon dioxide is higher. 2. The structure is relatively simple and easy to realize. 3. The structural strength between the hollow fiber membrane wires and the braided wires is stronger, and the relative sliding is not easy to occur, so that the surface structure of the hollow fiber membrane is damaged.
Compared with the prior art, the preparation method of the oxygenation film has the following advantages: 1. the preparation process is simple. 2. Several steps in the process can be performed simultaneously, so that the production time is saved.
Drawings
The invention is further described below with reference to the accompanying drawings:
FIG. 1 is a schematic view of an oxygenation assembly according to the invention;
FIG. 2 is a schematic view of a film structure of the present invention without knitting yarns 1;
FIG. 3 is a schematic view of a film structure of the present invention without knitting yarns;
FIG. 4 is a schematic view of a woven film layer according to the present invention 1;
FIG. 5 is a schematic view of a woven film layer according to the present invention;
FIG. 6 is a schematic diagram of a flow 1 test apparatus in an embodiment;
FIG. 7 is a schematic diagram of a flow 2 testing apparatus in an embodiment;
FIG. 8 is a schematic diagram of a method of pulling a cable 1;
FIG. 9 is a schematic diagram of a method of pulling a cable 2;
FIG. 10 is a schematic diagram of a method of pulling a cable 3;
FIG. 11 is a schematic view of a prior art blood flow path;
FIG. 12 is a schematic view of the structure of a layer of the rolled end of an oxidized film according to the present invention.
In the figure: 1. an air inlet; 2. an air outlet; 3. a liquid inlet; 4. a liquid outlet; 5. hollow fiber membrane filaments; 6. a seal; 7. braiding wires; 8. a test tube; 9. a fixing device; 10. a raw material roller; 11. and (5) a wind-up roller.
Detailed Description
In order that the above-recited objects, features and advantages of the present invention will be more clearly understood, a more particular description of the invention will be rendered by reference to the appended drawings and appended detailed description. It should be noted that, in the case of no conflict, the embodiments of the present application and the features in the embodiments may be combined with each other.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, however, the present invention may be practiced in other ways than those described herein, and therefore the scope of the present invention is not limited to the specific embodiments disclosed below.
Embodiment one:
a method of preparing an oxygenated membrane comprising the steps of:
s1: a membrane layer consisting of two layers of hollow fiber membrane filaments 5 is provided. Each layer of film layer is woven by a weaving device through a weaving line 7, and the weaving line 7 and the hollow fiber membrane filaments 5 are arranged at 90 degrees. Of course, in other embodiments, the membrane layer provided herein may also be a membrane layer formed by arranging a plurality of single hollow fiber membrane filaments 5 in the same plane through a support, that is, a membrane layer solution (as shown in fig. 2-3) without the braided wire 7.
S2: the two film layers provided in S1 are laminated at different angles. The different angles herein specifically mean that the arrangement direction of the hollow fiber membrane filaments 5 in one layer of the membrane layer and the arrangement direction of the hollow fiber membrane filaments 5 in the other layer of the membrane layer are different. Which partially overlap in projection in the stacking direction. I.e. the arrangement of the hollow fiber membrane filaments 5 in the two membrane layers cannot be exactly the same. In the present embodiment, the hollow fiber membrane filaments 5 themselves are also provided in a linear shape, but in other embodiments, the hollow fiber membrane filaments 5 themselves may be curved, broken lines, or other irregular shapes, etc. (as shown in fig. 4 to 5).
S3: and (3) shaping, namely blowing the laminated film layers through a hot air gun, and relatively fixing the two film layers through bonding points. And the temperature of the hot air defining the heat gun is set between 60 deg.c and 140 deg.c, in this embodiment the temperature of the heat gun is selected to be 60 deg.c. The bonding point is a point of fixed connection between two film layers, and in other embodiments, the shaping between different film layers can be performed by glue bonding, electrostatic adsorption bonding, or the like.
S4: and (5) rolling, namely rolling the laminated film layer.
The mode is a preparation method of an oxygenation film formed by laminating two layers of vertical films. If the film is three-layered, only three layers of films are provided in the step S1, and the operation is performed in a similar manner.
In this embodiment, the membrane layer provided in step S1 has an outer diameter of 0.4mm, an inner diameter of 0.2mm, and a pitch of 0.5mm of the hollow fiber membrane filaments 5 within the membrane layer. And a fixing groove for fixing the braided wire 7 was formed in the surface of the hollow fiber membrane filament 5, and the depth of the fixing groove was set to 100 μm and the width was set to 105 μm. Further, the inner side of the hollow fiber membrane filaments 5 is provided with a dense layer, the outer layer is a loose layer, the thickness of the loose layer is set to 55 μm, the thickness of the dense layer is set to 0.5 μm, and the oxygen mass transfer efficiency of the hollow fiber membrane filaments 5 is 15L/(min.m.bar). Further, in this embodiment, the film layers are woven by PP woven wires 7, and the specification thereof is selected to be 10F10D.
Embodiment two:
s1: a membrane layer consisting of two layers of hollow fiber membrane filaments 5 is provided. Each layer of film layer is woven by a weaving device through a weaving line 7, and the weaving line 7 and the hollow fiber membrane filaments 5 are arranged at 90 degrees.
And (3) carrying out oblique pulling operation on the film layer to form an inclined film layer. The specific diagonal-pulling operation is as follows: a rectangular vertical membrane layer is unfolded and paved, opposite sides of the vertical membrane layer are respectively fixed by using a fixing device 9, and acting force is applied to enable an inclined angle to be generated between the hollow fiber membrane filaments 5 and the braided wires 7 in the membrane layer, so that an inclined membrane layer is formed. The inclination angle of the inclined film layer can be controlled by controlling the degree of inclined pull, and the specific inclination angle is set between 45 degrees and 60 degrees, as shown in fig. 8. In this embodiment, the two film layers are both operated by oblique pulling, and the inclination angles are all set to 45 °. In other embodiments, the tilt angle may be 50 °, 55 °, 60 °, and so on.
S2-1: taking a first rectangular inclined film layer with an inclination angle of 45 degrees, and opening and paving;
s2-2: taking a second rectangular inclined film layer with an inclination angle of 45 degrees, and opening and paving;
s2-3: and laminating the first film layer and the second film layer to form a double-layer film layer. It should be noted here that, although the first inclined film layer and the second inclined film layer are each inclined at an angle of 45 °, the first inclined film layer and the second inclined film layer are stacked one on top of the other, so as to ensure that the hollow fiber membrane filaments 5 in the first film layer and the hollow fiber membrane filaments 5 in the second film layer do not overlap completely. It is thus understood that the oblique angle of the oblique film layers is 45 ° and 135 °.
S3: and (3) shaping, namely blowing the laminated film layers through a hot air gun, and relatively fixing the two film layers through bonding points. And the hot air temperature defining the heat gun is set between 60 deg.c and 140 deg.c, in this embodiment the specific temperature of the heat gun is selected to be 80 deg.c.
S4: and (5) rolling, namely rolling the laminated film layer.
The method is a preparation method of the oxygenation membrane, wherein two perpendicular membrane layers are firstly inclined and then laminated. If the film is three-layer, only three layers of films are needed to be provided in the step S1, and the operation can be performed in a similar way, in the scheme of the three layers of films, the middle layer is preferably a vertical film, and the two sides of the vertical film are inclined films, and the inclination angles are the same.
In this embodiment, the membrane layer provided in step S1, whose outer diameter of the hollow fiber membrane filaments 5 constituting the membrane layer is 0.38mm, whose inner diameter is 0.28mm, and the pitch of the hollow fiber membrane filaments 5 within the membrane layer is set to 0.62mm. And a fixing groove for fixing the braided wire 7 is formed in the surface of the hollow fiber membrane wire 5, and the depth of the fixing groove is set to 80 μm and the width is set to 105 μm. Further, the inner side of the hollow fiber membrane filaments 5 was provided as a dense layer, the outer layer was a porous layer, the thickness of the porous layer was set to 47 μm, the thickness of the dense layer was set to 3 μm, and the oxygen mass transfer efficiency of the hollow fiber membrane filaments 5 was 104L/(min·m·bar). Further, in this embodiment, the film layers are woven by PP woven wires 7, and the specification thereof is selected to be 50F20D.
Embodiment III:
s1: a membrane layer consisting of two layers of hollow fiber membrane filaments 5 is provided. Each layer of film layer is woven by a weaving device through a weaving line 7, and the weaving line 7 and the hollow fiber membrane filaments 5 are arranged at 90 degrees.
And (3) carrying out oblique pulling operation on the film layer to form an inclined film layer. The specific diagonal-pulling operation is as follows: a rectangular vertical membrane layer is unfolded and paved, opposite sides of the vertical membrane layer are respectively fixed by using a fixing device 9, and acting force is applied to enable an inclined angle to be generated between the hollow fiber membrane filaments 5 and the braided wires 7 in the membrane layer, so that an inclined membrane layer is formed. The inclination angle of the inclined film layer can be controlled by controlling the degree of oblique pulling, and the specific inclination angle is set between 45 degrees and 60 degrees. In this embodiment, only one of the two film layers is selected for the cable-stayed operation, and the inclination angle is set to 45 °. In other embodiments, the tilt angle may be 50 °, 55 °, 60 °, and so on.
S2-1: taking a first rectangular vertical film layer, and opening and paving;
s2-2: taking a second rectangular inclined film layer with an inclination angle of 45 degrees, and opening and paving;
s2-3: and laminating the first film layer and the second film layer to form a double-layer film layer. It should be noted here that, although the first inclined film layer and the second inclined film layer are each inclined at an angle of 45 °, the first inclined film layer and the second inclined film layer are stacked one on top of the other, so as to ensure that the hollow fiber membrane filaments 5 in the first film layer and the hollow fiber membrane filaments 5 in the second film layer do not overlap completely. It is thus understood that the oblique angle of the oblique film layers is 45 ° and 135 °.
S3: and (3) shaping, namely blowing the laminated film layers through a hot air gun, and relatively fixing the two film layers through bonding points. And the temperature of the hot air defining the heat gun is set between 60 deg.c and 140 deg.c, in this embodiment the temperature of the heat gun is selected to be 100 deg.c.
S4: and (5) rolling, namely rolling the laminated film layer.
The preparation method is that one vertical film layer is firstly inclined and then is laminated with the vertical film layer to form an oxygenated film. If the film is three-layered, only three layers of films are provided in the step S1, and the operation is performed in a similar manner.
In this embodiment, the membrane layer provided in step S1 has an outer diameter of 0.3mm, an inner diameter of 0.2mm, and a pitch of 0.75mm of the hollow fiber membrane filaments 5 constituting the membrane layer. And a fixing groove for fixing the braided wire 7 is formed in the surface of the hollow fiber membrane wire 5, and the depth of the fixing groove is set to be 60 μm in depth and 100 μm in width. Further, the inner side of the hollow fiber membrane filaments 5 was provided with a dense layer, the outer layer was a porous layer, and the thickness of the porous layer was set to 99 μm, the thickness of the dense layer was set to 0.1 μm, and the oxygen mass transfer efficiency of the hollow fiber membrane filaments 5 was 234L/(min·m·bar). Further, in this embodiment, the film layers are woven by PET woven wires 7, and the specification thereof is selected to be 100F40D.
Embodiment four:
s1: a membrane layer consisting of two layers of hollow fiber membrane filaments 5 is provided. Each layer of film layer is woven by a weaving device through a weaving line 7, and the weaving line 7 and the hollow fiber membrane filaments 5 are arranged at 90 degrees.
The oblique stretching operation is performed on the film layer to form an inclined film layer, and a single-layer vertical film net oblique stretching operation schematic diagram is shown in fig. 9. The specific diagonal-pulling operation is as follows: the raw material roll 10 is provided, a vertical film layer is wound on the surface of the raw material roll 10 to form a raw material roll, the raw material roll is opened, one end of the vertical film layer is fixed on a winding roll 11, the relative positions of the raw material roll and the winding roll 11 are adjusted to be intersected in the axial direction, and the winding of the winding roll 11 is performed while the unreeling of the raw material roll is performed, so that an inclined film layer roll is formed. Because of the double layer, two stock rolls 10 and one take-up roll 11 need to be provided for operation in this embodiment. In the present embodiment, the angle between one raw material roll 10 and the wind-up roll 11 is set to 45 °, and the angle between the other raw material roll 10 and the wind-up roll 11 is set to 50 °. Of course, in other embodiments, this angle may be chosen according to different needs, preferably in the range 45 ° -60 °. In order to adjust the inclination angle of the inclined film layer, besides one way of adjusting the angle between the raw material roll and the wind-up roll 11, in other embodiments, the inclined angle may be adjusted by adjusting the position where the end of the raw material roll pulled out from the vertical film layer is fixed at the wind-up roll 11, as shown in fig. 10, or two ways of mixing may be used to adjust the inclined angle.
The laminated film layers are rolled and compounded by using a hot-pressing roller, and the temperature of the hot-pressing roller is set between 60 ℃ and 140 ℃, preferably 120 ℃. In a specific arrangement, the hot pressing roller can be arranged by attaching an inclined film layer roll, or can be rolled between a raw material roll and the inclined film layer roll.
In this example, a method for producing a two-layer film laminate was used. Compared with the first embodiment to the third embodiment, the method is equivalent to combining the step S2, the step S3 and the step S4 at the same time, and improves the production efficiency.
In this embodiment, the membrane layer provided in step S1 has an outer diameter of 0.3mm, an inner diameter of 0.2mm, and a pitch of 0.55mm of the hollow fiber membrane filaments 5 constituting the membrane layer. And a fixing groove for fixing the braided wire 7 is formed on the surface of the hollow fiber membrane wire 5, and the depth of the fixing groove is set to 80 μm and the width is set to 110 μm. Further, the inner side of the hollow fiber membrane filaments 5 was provided as a dense layer, the outer layer was a loose layer, and the thickness of the loose layer was set to 60 μm, the thickness of the dense layer was set to 2 μm, and the oxygen mass transfer efficiency of the hollow fiber membrane filaments 5 was 349L/(min·m·bar). Further, in this embodiment, the film layers are woven by the N6 woven wire 7, and the specification thereof is selected to be 10F60D.
Fifth embodiment:
s1: a membrane layer consisting of three layers of hollow fiber membrane filaments 5 is provided. Each layer of film layer is woven by a weaving device through a weaving line 7, and the weaving line 7 and the hollow fiber membrane filaments 5 are arranged at 90 degrees.
And (3) carrying out oblique pulling operation on the film layer to form an inclined film layer. The specific diagonal-pulling operation is as follows: the raw material roll 10 is provided, a vertical film layer is wound on the surface of the raw material roll 10 to form a raw material roll, the raw material roll is opened, one end of the vertical film layer is fixed on a winding roll 11, the relative positions of the raw material roll and the winding roll 11 are adjusted to be intersected in the axial direction, and the winding of the winding roll 11 is performed while the unreeling of the raw material roll is performed, so that an inclined film layer roll is formed. Since three laminated film layers are prepared in this embodiment, three raw material rolls 10 and one wind-up roll 11 are required to be provided for operation. In this embodiment, the angle between one raw material roll 10 and the wind-up roll 11 is set to 50 °, the angle between the other raw material roll 10 and the wind-up roll 11 is set to 55 °, and the remaining raw material roll 10 and wind-up roll 11 are arranged in parallel. Further, the film pulled out by the raw material roller 10 parallel to the wind-up roller 11 is a vertical film, and is used as the middle layer of the three-layer film. Of course, in other embodiments, this angle may be chosen according to different needs, preferably in the range 45 ° -60 °. In order to adjust the inclination angle of the inclined film layer, in addition to one way of adjusting the angle between the raw material roll 10 and the wind-up roll 11, in other embodiments, the adjustment may be performed by adjusting the position where the end of the raw material roll pulled out from the vertical film layer is fixed at the wind-up roll 11, or by mixing two ways.
The laminated film layers are rolled and compounded by using a hot-pressing roller, and the temperature of the hot-pressing roller is set between 60 ℃ and 140 ℃, preferably 140 ℃. In a specific arrangement, the hot pressing roller can be arranged by attaching an inclined film layer roll, or can be rolled between a raw material roll and the inclined film layer roll.
In this embodiment, the membrane layer provided in step S1 has an outer diameter of 0.4mm, an inner diameter of 0.2mm, and a pitch of 0.6mm of the hollow fiber membrane filaments 5 within the membrane layer. And a fixing groove for fixing the braided wire 7 is formed on the surface of the hollow fiber membrane wire 5, and the depth of the fixing groove is set to 100 μm and the width is set to 90 μm. Further, the inner side of the hollow fiber membrane filaments 5 was provided as a dense layer, the outer layer was a porous layer, the thickness of the porous layer was set to 70 μm, the thickness of the dense layer was set to 1 μm, and the oxygen mass transfer efficiency of the hollow fiber membrane filaments 5 was 395L/(min·m·bar). Further, in this embodiment, the film layers are woven by the N66 woven wire 7, and the specification thereof is selected to be 100F40D.
It should be noted that, when the vertical film layer is inclined, two different modes are disclosed in the application, and the film layers with the same size and shape can be prepared by two different modes of a user, and the related performance parameters are not different.
In the present application, as shown in fig. 1, there is further provided an oxygenation assembly including a housing disposed in a column shape, and an oxygenation film wound in the housing. The top of the shell is provided with an air inlet 1, the air inlet 1 is communicated with the hollow part of the hollow fiber membrane wire 5, gas enters the oxygenation assembly from the air inlet 1, passes through the inside of the hollow fiber membrane wire 5 from one end of the hollow fiber membrane wire 5, is discharged from the other end of the hollow fiber membrane wire 5, and is discharged from the oxygenation assembly through an air outlet 2 arranged on the side wall of the oxygenation assembly, namely, the air inlet 1, the inside of the hollow fiber membrane wire 5 and the air outlet form an air passage. The hollow fiber membrane web prepared by the present invention is wound and then integrally put into an oxygenation module in a columnar form to achieve the above-described structure. As shown in fig. 12, the double-layered film layer is a top view (one layer is taken for illustration) of the laminated oxide film after winding, and in the illustration, the inclination directions of the double-layered film layers are opposite, and in other embodiments, the inclination directions may be the same, and the inclination angles may be different; it may be a three-layer film or a multi-layer film. It can be seen from fig. 12 that the blood flow channel formed outside the hollow fiber membrane filament 5 is distinct from the blood flow channel formed in the prior art (in fig. 11), in which the inclined and simultaneously rotating blood flow channel is formed, which can increase the turbulence effect of blood flowing inside the blood flow channel, ensure that the blood near the center of the blood flow channel can better contact the outer wall of the hollow fiber membrane filament 5, avoid the situation that the blood flows out of the flow channel through gas exchange, and ensure that the part of the blood does not directly flow out of the oxygenation membrane, thus improving the gas exchange efficiency of the blood in the flow channel as a whole.
Meanwhile, the side wall of the oxygenation component is also provided with a liquid inlet 3, the bottom of the oxygenation component is provided with a liquid outlet 4, blood flowing in from the liquid inlet 3 flows through a cavity formed between the outside of the hollow fiber membrane wires 5 and the shell, and then flows out from the bottom of the oxygenation component, namely, the liquid inlet 3, the liquid outlet 4 and the cavity form a flow channel. And further, the hollow fiber membrane wires 5 are provided with sealing members 6 for sealing between the hollow fiber membrane wires 5 and between the hollow fiber membrane wires 5 and the housing at positions near both ends, and the specific sealing members 6 may be adhesive layers, i.e., formed by curing glue. Further in the oxygenation assembly, the air inlet 1 and the air outlet 2 are arranged opposite to openings at two ends of the hollow fiber membrane filaments 5.
The method of the fourth embodiment and the fifth embodiment are used for preparing laminated film layers with different layers, controlling relative angles in the process steps to realize the inclined angle of the inclined film layers, and manufacturing experimental samples. And winding the manufactured laminated film layer, preparing an oxygenation assembly shown in figure 1, performing relevant performance test, and recording test results.
In Table one, all samples were PMP oxygenation membranes with double layers, hollow fiber membrane wires 5 with inner diameter of 0.2mm and outer diameter of 0.4mm were selected, PP woven wires 7 with 10F10D were selected, hollow fiber membrane layers with interval of 0.5mm between woven membrane wires were selected, the depth of the fixing groove was 10 μm and the width was 90 μm, and the dense layer thickness of single hollow fiber membrane wire 5 was set to 1 μm, and the loose layer was set to 90 μm. The difference is that the inclination angle of each layer of the double-layer membrane layer is different, and the inclination angle formed by the hollow fiber membrane filaments 5 between the membrane layers is different. The inclination angle of the film layer in table one refers to an included angle formed between the hollow fiber membrane filaments 5 and the horizontal direction when the film layer is laid in the horizontal direction, the included angle ranges from 45 degrees to 60 degrees, namely, the included angle on the other side of the hollow fiber membrane filaments 5 ranges from 120 degrees to 135 degrees, and in all tables of the application, the opposite direction means that the inclination angle of the second film layer is opposite to the inclination direction of the first film layer. In the present application, the degrees of the included angle are the degrees of the included angle of the hollow fiber membrane filaments 5 and the right side in the horizontal direction.
Table one:
inclination angle of first layer film Inclination angle of second layer film Included angle between the first layer and the second layer Flow 1 (ml/m 2 min cmHg) Flow 2 (ml/m 2 min cmHg) Flow 3 (mL/min)
Sample 1 45 51 6 442 530 397
Sample 2 45 57 12 445 529 392
Sample 3 45 63 18 448 529 388
Sample 4 45 69 24 452 526 383
Sample 5 50 80 30 455 527 377
Sample 6 50 86 36 458 525 374
Sample 7 50 88 (reverse direction) 42 460 524 369
Sample 8 55 77 (reverse direction) 48 466 525 366
Sample 9 55 71 (reverse direction) 54 469 523 361
Sample 10 60 60 (reverse direction) 60 472 522 355
Sample 11 48 66 (reverse direction) 66 477 520 352
Sample 12 48 60 (reverse direction) 72 481 521 348
Sample 13 53 49 (reverse direction) 78 487 519 343
Sample 14 46 50 (reverse direction) 84 494 519 337
Sample 15 45 45 (reverse direction) 90 501 518 334
Comparative example 1 45 45 0 436 532 405
Comparative example 2 90 90 0 439 537 412
Flow 1 in table one, the specific test set up is shown in fig. 6: the sample with the film area of 0.1 square meter is rolled into a film column, the film column is arranged in a test tube 8, the outer surface of the film column is abutted against the inner surface of the test tube 8, one end of the test tube 8 is sealed, the other end of the test tube is opened, and an air outlet is formed in one side wall of the test tube 8. When in test, firstly, 1 kilogram of air pressure is applied to the open end of the test tube 8, oxygen is introduced into the test tube, the gas flow is detected and related data is recorded at the gas outlet of the test tube 8, and the larger the flow 1 is, the higher the gas mass transfer efficiency is, and the easier the gas mass transfer efficiency is to pass through the side wall of the membrane wire.
The flow rate 2 in table one, the specific test apparatus, is shown in fig. 7: at 25 ℃, a sample with the membrane area of 0.1 square meter is rolled into a membrane column, the membrane column is placed in a test tube 8, the outer surface of the membrane column is abutted against the inner surface of the test tube 8, and openings at two ends of the test tube 8 are arranged. During testing, 1 kg of air pressure is applied to one end of the existing test tube 8, oxygen is introduced into the test tube, the other end of the test tube 8 is used for monitoring the air flow and recording related data, and the smaller the flow 2 is, the higher the turbulence degree of the oxygen when the oxygen passes through the hollow fiber membrane filaments 5 is.
Flow 3 in table one, the specific test set up is shown in fig. 1: the oxygenation films with the film area of 0.1 square meter and different inclination angles are wound to prepare an oxygenator, bovine blood is introduced into the oxygenator at the temperature of 37 ℃, and the bovine blood flow of the liquid outlet 4 is detected under the condition that the ratio of the introduced gas flow to the introduced bovine blood flow is 1:1.
In Table two, all samples were PMP oxygenation films with double layers, hollow fiber membrane wires 5 with inner diameter of 0.2mm and outer diameter of 0.3mm were selected, PP material braided wires 7 with 100F40D were selected, hollow fiber membrane layers with interval of 0.6mm between braided membrane wires were selected, the depth of the fixing groove was 30 μm, the width was 95 μm, and the dense layer thickness of single hollow fiber membrane wire 5 was set to 2.5 μm, and the loose layer was set to 65 μm. The difference is that the inclination angle of each layer of the double-layer membrane layer is different, and the inclination angle formed by the hollow fiber membrane filaments 5 between the membrane layers is different.
And (II) table:
in the first layer of film Inclination angle Second layer film layer is inclined inwards Oblique angle A first layer and a second layer of film Included angle between Flow 1 (ml/m 2 min) cmHg） Flow 2 (ml/m 2 min) cmHg） Flow 3 (mL- min）
Sample 31 45 51 6 442 532 399
Sample 32 45 57 12 443 531 395
Sample 33 45 63 18 448 529 383
Sample 34 45 69 24 450 528 378
Sample 35 50 80 30 453 526 375
Sample 36 50 86 36 460 527 371
Sample 37 50 88 (reverse direction) 42 460 524 362
Sample 38 55 77 (reverse direction) 48 466 525 360
Sample 39 55 71 (reverse direction) 54 469 523 356
Sample 40 60 60 (reverse direction) 60 473 522 353
Sample 41 48 66 (reverse direction) 66 475 522 349
Sample 42 48 60 (reverse direction) 72 481 520 346
Sample 43 53 49 (reverse direction) 78 484 521 341
Sample 44 46 50 (reverse direction) 84 494 519 337
Sample 45 45 45 (reverse direction) 90 503 518 332
Comparative example 5 45 45 0 434 533 404
Comparative example 6 90 90 0 439 537 412
In Table two, the test method of the relevant performance parameters is the same as that in Table one.
In Table three, all samples were PMP oxygenation films with three film layers, hollow fiber film wires 5 with an inner diameter of 0.2mm and an outer diameter of 0.3mm were selected, PET material knitting wires 7 with a 10F10D were selected, hollow fiber film layers with a spacing of 0.7mm between the knitting film wires were selected, the depth of the fixing groove was 50 μm, the width was 100 μm, and the dense layer thickness of a single hollow fiber film wire 5 was set to 1.5 μm, and the loose layer was set to 55 μm. In the three-layer film layer of the oxygenated film, the second film layer of the middle layer is a vertical film layer. The difference is that the inclination angles of the first membrane layer and the second membrane layer are different, and the inclination angles formed by the hollow fiber membrane filaments 5 between the first membrane layer and the second membrane layer are different.
Table three:
inclination angle of first layer film Third layerInclination angle of film layer Included angle between the first layer and the third layer Flow 1 (ml/m 2 min cmHg) Flow 2 (ml/m 2 min cmHg) Flow 3 (mL/min)
Sample 46 45 51 6 443 531 380
Sample 47 45 57 12 444 529 373
Sample 48 45 63 18 449 530 366
Sample 49 45 69 24 451 528 359
Sample 50 50 80 30 452 527 353
Sample 51 50 86 36 461 526 348
Sample 52 50 88 (reverse direction) 42 459 524 342
Sample 53 55 77 (reverse direction) 48 465 525 336
Sample 54 55 71 (reverse direction) 54 467 525 331
Sample 55 60 60 (reverse direction) 60 471 522 327
Sample 56 48 66 (reverse direction) 66 474 523 322
Sample 57 48 60 (reverse direction) 72 483 521 318
Sample 58 53 49 (reverse direction) 78 486 522 311
Sample of59 46 50 (reverse direction) 84 491 520 305
Sample 60 45 45 (reverse direction) 90 504 518 301
Comparative example 7 45 45 0 435 533 385
Comparative example 8 90 90 0 442 539 394
In Table three, the test patterns of the relevant performance parameters are the same as those in Table one.
In Table four, all samples were PMP oxygenation films with three film layers, hollow fiber film wires 5 with an inner diameter of 0.2mm and an outer diameter of 0.4mm were selected, PET material knitting wires 7 with a 50F25D were selected, hollow fiber film layers with a spacing of 0.75mm between the knitting film wires were selected, the depth of the fixing groove was 70 μm, the width was 105 μm, and the dense layer thickness of the single hollow fiber film wire 5 was set to 1.2 μm, and the loose layer was set to 65 μm. In the three-layer film layer of the oxygenated film, the second film layer of the middle layer is a vertical film layer. The difference is that the inclination angles of the first membrane layer and the second membrane layer are different, and the inclination angles formed by the hollow fiber membrane filaments 5 between the first membrane layer and the second membrane layer are different.
Table four:
inclination angle of first layer film Inclination angle of third layer film Included angle between the first layer and the third layer Flow 1 (ml/m 2 min cmHg) Flow 2 (ml/m 2 min cmHg) Flow 3 (mL/min)
Sample 61 45 51 6 445 532 381
Sample 62 45 57 12 443 530 372
Sample 63 45 63 18 450 531 365
Sample 64 45 69 24 450 529 357
Sample 65 50 80 30 451 528 352
Sample 66 50 86 36 462 527 347
Sample 67 50 88 (reverse direction) 42 458 525 343
Sample 68 55 77 (reverse direction) 48 466 526 335
Sample 69 55 71 (reverse direction) 54 464 526 332
Sample 70 60 60 (reverse direction) 60 473 524 326
Sample 71 48 66 (reverse direction) 66 472 523 321
Sample 72 48 60 (reverse direction) 72 484 521 317
Sample 73 53 49 (reverse direction) 78 487 522 311
Sample 74 46 50 (reverse direction) 84 492 520 306
Sample 75 45 45 (reverse direction) 90 501 519 302
Comparative example 9 45 45 0 434 533 385
Comparative example 10 90 90 0 442 539 394
In Table IV, the test method of the relevant performance parameters is the same as that in Table I.
In Table five, all samples were PMP oxygenation films with three film layers, hollow fiber film wires 5 with an inner diameter of 0.28mm and an outer diameter of 0.38mm were selected, PET material knitting wires 7 with a 50F25D were selected, hollow fiber film layers with a spacing of 0.6mm between the knitting film wires were selected, the depth of the fixing groove was 100 μm, the width was 110 μm, and the dense layer thickness of a single hollow fiber film wire 5 was set to 2.5 μm, and the loose layer was set to 75 μm. In the three-layer film layer of the oxygenated film, the second film layer of the middle layer is a vertical film layer. The difference is that the inclination angles of the first membrane layer and the second membrane layer are different, and the inclination angles formed by the hollow fiber membrane filaments 5 between the first membrane layer and the second membrane layer are different.
Table five:
inclination angle of first layer film Inclination angle of third layer film Included angle between the first layer and the third layer Flow 1 (ml/m 2 min cmHg) Flow 2 (ml/m 2 min cmHg) Flow 3 (mL/min)
Sample 76 45 51 6 446 530 383
Sample 77 45 57 12 442 529 374
Sample 78 45 63 18 449 529 368
Sample 79 45 69 24 452 527 356
Sample 80 50 80 30 450 528 352
Sample 81 50 86 36 461 526 346
Sample 82 50 88 (reverse direction) 42 459 524 343
Sample 83 55 77 (reverse direction) 48 467 525 334
Sample 84 55 71 (reverse direction) 54 463 523 330
Sample 85 60 60 (reverse direction) 60 471 523 327
Sample 86 48 66 (reverse direction) 66 472 522 323
Sample 87 48 60 (reverse direction) 72 483 520 316
Sample 88 53 49 (reverse direction) 78 488 522 310
Sample 89 46 50 (reverse direction) 84 493 521 304
Sample 90 45 45 (reverse direction) 90 500 518 299
Comparative example 11 45 45 0 435 533 385
Comparative example 12 90 90 0 442 539 394
In Table five, the test patterns of the relevant performance parameters are the same as those in Table one.
By observing tables one through five above, it can be derived that: in any of the oxygenic membranes, under the condition of a certain size, the inclination angle of the single-layer membrane net has little influence on the turbulence effect, but the larger the inclination angle of the membrane net is, the deeper and wider the depth and width of the fixing groove are, the contact area between the braided wire 7 and the hollow fiber membrane wire 5 is increased, the friction force is increased, and the strength of the whole membrane net is larger and is not easy to scatter. The larger the included angle between the hollow fiber membrane filaments 5 in the adjacent membrane layers is, the higher the mass transfer efficiency is, and the better the turbulence effect is.
While the preferred embodiments of the present invention have been described in detail, it will be appreciated that those skilled in the art, upon reading the above teachings, may make various changes and modifications to the invention. Such equivalents are also intended to fall within the scope of the claims appended hereto.

Claims (27)

1. An oxygenation membrane comprising a membrane layer consisting of a plurality of hollow fiber membrane filaments, characterized in that: the membrane layer at least comprises two layers, laminated membrane layers are formed by laminating different membrane layers, and any hollow fiber membrane wire in the membrane layer is partially overlapped with at least one hollow fiber membrane wire in the adjacent membrane layer in the projection of the membrane layer in the lamination direction;
the membrane layer comprises an inclined membrane layer, wherein the edge connecting line of all hollow fiber membrane wires at the same end in the inclined membrane layer is a straight line, and at least one section of hollow fiber membrane wires or an extension line of the hollow fiber membrane wires is arranged at an acute angle with the straight line;
the hollow fiber membrane wires in the membrane layer are linear; an included angle formed between the hollow fiber membrane wires and a straight line formed by connecting edges of the same end is set between 45 degrees and 90 degrees;
the hollow fiber membrane filaments in the same membrane layer are fixed by braiding through braiding wires; a fixing groove is formed at the weaving fixing position of the hollow fiber membrane wires and the weaving wires;
The depth of the fixing groove is between 10 and 100 mu m, and the width of the fixing groove is between 90 and 110 mu m.
2. The oxygenated membrane of claim 1, wherein the laminated membrane layer is formed by laminating two inclined membrane layers, and an included angle between the hollow fiber membrane filaments in the two inclined membrane layers is set between 5 ° and 90 °.
3. The oxygenation membrane of claim 1, wherein the membrane layer further comprises a vertical membrane layer, wherein the edge connection line of the hollow fiber membrane filaments at the same end in the vertical membrane layer is a straight line, the hollow fiber membrane filaments are in a straight line shape, and a right angle is arranged between the hollow fiber membrane filaments and the straight line.
4. An oxygenated membrane according to claim 3, wherein the laminated membrane layer is formed by laminating three membrane layers, the middle is arranged as a vertical membrane layer, the two sides are arranged as inclined membrane layers, and the included angle between the hollow fiber membrane filaments in the adjacent membrane layers is set between 5 ° and 90 °.
5. The oxygenated film of claim 2 or 4, wherein bonding points are provided between different ones of the laminated film layers.
6. The oxygenation membrane of claim 1 wherein the depth of the fixation groove increases as the angle between the hollow fiber membrane filaments and the braid wires decreases.
7. The oxygenation membrane of claim 1, wherein the hollow fiber membrane filaments have an outer diameter of between 0.3mm and 0.4mm and an inner diameter of between 0.2mm and 0.28 mm.
8. The oxygenation membrane of claim 7 wherein the spacing between the hollow fiber membrane filaments is between 0.5mm and 0.75 mm.
9. The oxygenation membrane of claim 7 wherein the hollow fiber membrane filaments comprise a porous layer on the inside and a dense layer on the outside.
10. The oxygenated film of claim 9, wherein the dense layer is provided with a thickness between 0.1 μm and 3 μm and the loose layer is provided with a thickness between 47 μm and 99 μm.
11. The oxygenated membrane of claim 7, wherein the oxygen mass transfer efficiency of the hollow fiber membrane filaments is 15-400L/(min-m) 2 Bar).
12. The oxygenated film of claim 1, wherein the braided wire includes, but is not limited to PP, PET, N6, N66 and blends thereof, with a gauge selected between 10F-100F, 10D-60D.
13. A method of making the oxygenated film of claim 1, comprising the steps of:
S1: providing a membrane layer consisting of at least two layers of hollow fiber membrane filaments;
s2: laminating the film layers prepared in the step S1 to form laminated film layers, wherein any hollow fiber film yarn in any one film layer is partially overlapped with at least one hollow fiber film yarn in the adjacent film layer in the projection of the lamination direction;
s3: shaping;
s4: and (5) rolling, namely rolling the laminated film layer.
14. The method of claim 13, wherein the membrane layer provided in step S1 is woven between a woven wire and a hollow fiber membrane filament.
15. The method for preparing an oxygenated membrane according to claim 14, wherein the membrane layer woven in step S1 is a perpendicular membrane layer formed by mutually perpendicular hollow fiber membrane filaments and woven wires.
16. The method of claim 15, further comprising the step of pulling the vertical membrane layer to an inclined membrane layer between the step S1 and the step S2.
17. The method for preparing an oxygenated membrane according to claim 16, wherein the specific operation of the diagonal draw is,
a rectangular vertical membrane layer is unfolded and paved, opposite sides of the vertical membrane layer are respectively fixed by using a fixing device, acting force is applied to enable an inclined angle to be generated between hollow fiber membrane wires and braided wires in the membrane layer, and an inclined membrane layer roll is formed;
Or alternatively, the process may be performed,
the vertical film layer is wound on the surface of the raw material roller to form a raw material roll, the raw material roll is opened, one end of the vertical film layer is fixed on a winding roller, the relative positions of the raw material roll and the winding roller are adjusted to be intersected in the axial direction, and the winding of the winding roller is performed while the raw material roll is unreeled to form the inclined film layer.
18. The method for producing an oxygenated film according to claim 17, wherein the step S2 specifically comprises,
s2-1: taking a first rectangular inclined film layer, and opening and paving;
s2-2: taking a second rectangular inclined film layer, and opening and paving;
s2-3: laminating a first film layer and a second film layer to form a double-layer film layer, wherein the inclination angles of the first inclined film net and the second inclined film net are different;
or alternatively, the process may be performed,
s2-1: taking a first rectangular vertical film layer, and opening and paving;
s2-2: taking a second rectangular inclined film layer, and opening and paving;
s2-3: laminating the first film layer and the second film layer to form a double-layer film layer;
or alternatively, the process may be performed,
s2-1: taking a rectangular vertical film layer, and opening and paving;
s2-2: taking the other two rectangular inclined film layers, and opening and paving;
s2-3: and respectively placing the inclined film layers on two sides of the vertical film layer to laminate to form three film layers.
19. The method for producing an oxygenated film according to claim 18, wherein the step S2 further comprises,
s2-4: and (5) using a hot air gun to blow and heat-seal the double-layer film layer or the three-layer film layer.
20. The method of producing an oxygenated film according to claim 19, wherein the temperature of the heat gun in the S2-4 step is set between 60 ℃ and 140 ℃.
21. The method for producing an oxygenated film according to claim 17, wherein the step S2 specifically comprises,
s2-1: the method comprises the steps of providing a first raw material roll, a second raw material roll and a winding roller, wherein the axis of the first raw material roll and the axis of the winding roller are arranged in parallel, and the different surfaces of the axis of the second raw material roll and the axis of the winding roller are intersected;
s2-2: unreeling the film layers on the first raw material roll and the second raw material roll, and flatly laying and laminating the end parts of the film layers on the surfaces of the winding rollers;
s2-3: the winding roller is used for winding while the first raw material roll and the second raw material roll are unreeled;
or alternatively, the process may be performed,
s2-1: providing a first raw material roll, a second raw material roll and a winding roller, wherein the axis of the first raw material roll is intersected with the different surface between the axis of the winding roller, and the axis of the second raw material roll is intersected with the different surface between the axis of the winding roller;
s2-2: unreeling the film layers on the first raw material roll and the second raw material roll, and flatly laying and laminating the end parts of the film layers on the surfaces of the winding rollers;
s2-3: the winding roller is used for winding while the first raw material roll and the second raw material roll are unreeled;
or alternatively, the process may be performed,
s2-1: providing a first raw material roll, a second raw material roll, a third raw material roll and a winding roller, wherein the axis of the first raw material roll is intersected with the axis of the winding roller by different surfaces, the axis of the second raw material roll is intersected with the axis of the winding roller by different surfaces, and the axis of the third raw material roll is arranged in parallel with the axis of the winding roller;
s2-2: unreeling film layers on the first raw material roll, the second raw material roll and the third raw material roll, flatly laying and laminating the end parts of the film layers on the first raw material roll, the second raw material roll and the third raw material roll, and fixing the film layers on the third raw material roll on the surface of the winding roll, wherein the film layers unreeled on the third raw material roll are arranged on the middle layer;
s2-3: and the winding roller is used for winding while the first raw material roll, the second raw material roll and the third raw material roll are unreeled.
22. The method of claim 21, wherein the step S2 further comprises S2-4: and rolling and compounding the laminated film layers by using a hot-pressing roller while unreeling the raw material roll and reeling the winding roller.
23. The method for producing an oxygenated film according to claim 22, wherein the temperature of the hot press roller in s2-4 step is set between 60 ℃ and 140 ℃.
24. The method of claim 23, wherein the axes of the first roll and the second roll intersect at a different plane in step s 2-2.
25. An oxygenation assembly using the oxygenation membrane prepared according to claim 13, comprising a shell and the oxygenation membrane wound in the shell, wherein the shell is provided with a liquid inlet, a liquid outlet, an air inlet and an air outlet, an air passage is formed in the air inlet, the air outlet and the inner part of the hollow fiber membrane wire of the oxygenation membrane, a cavity is formed between the outer side wall of the hollow fiber membrane wire and the shell, the liquid inlet, the cavity and the liquid outlet form a flow passage, a single hollow fiber membrane wire is spirally arranged around the winding axis of the oxygenation membrane, and the spiral inclination angles of the hollow fiber membrane wires in adjacent membrane layers in the oxygenation membrane are different.
26. The oxygenation assembly of claim 25, wherein the hollow fiber membrane filaments are provided with seals proximate both ends for sealing between the hollow fiber membrane filaments and the housing.
27. The oxygenation assembly of claim 25 or 26, wherein the gas inlet is opposite one end opening of the hollow fiber membrane filaments and the gas outlet is opposite the other end opening of the hollow fiber membrane filaments.
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