JPH0253524B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to polysulfone hollow fiber membranes. BACKGROUND ART In recent years, the technology of using membranes having permselectivity in separation operations has been making remarkable progress and is being put into practical use in many fields. In particular, hollow fiber membranes are advantageous because the membrane area per occupied volume can be overwhelmingly larger than that of flat membranes, and have been extensively researched and developed, and some are even commercially available. In addition, cellulose-based polymers have traditionally been mainly used as membrane materials, but cellulose-based polymers deteriorate as the operating conditions such as the temperature and pH of the liquid to be treated become more severe, so various synthetic polymers are also being considered. ing. Among these, polysulfone polymers are considered to be promising materials with excellent heat resistance, acid resistance, alkali resistance, oxidation resistance, and microbial resistance, and various studies are being conducted. For example, JP-A-54-
No. 145379 has 10
It has ~100Å micropores (essentially a skin layer),
A polysulfone hollow fiber membrane is disclosed that has a sloped structure inside the membrane. Also, JP-A-56-
No. 115602 discloses a polysulfone hollow fiber membrane having skin layers on both surfaces and a tube bundle-like structure inside the membrane. Polysulfone hollow fiber membranes with a skin layer on the inner surface and micropores of 1 μm or more on the outer surface are also commercially available from Amicon under the name HP series. Furthermore, JP-A-56-
No. 86941 discloses polysulfone flat membranes and hollow fiber membranes having a specific structure made of a mixed polymer of aromatic polysulfone manufactured by Union Carbide Co., USA and polyether sulfone manufactured by ICI Co., UK. However, since all of these polysulfone membranes have a skin layer on the inner and/or outer surface of the membrane, the molecular weight cut-off is as low as 500,000 or less, and the water permeability of hollow fiber membranes is 1000/ ^m2・hr・
As low as Kg/ ^cm2 . These inventions were made to reduce the molecular weight cut-off as much as possible, that is, to make dextran with a molecular weight of 500,000, for example, almost impermeable, and to increase the water permeability. A dense layer is provided on either side, and if there were no dense layer, there would be a serious defect. In contrast, in the present invention, micropores are actively provided on any part of the outer surface, inner surface, and internal structure for the purpose of increasing the water permeability as much as possible. Such membranes are called precision membranes, but polysulfone-based hollow fiber membranes have not been known so far. The above-mentioned JP-A-56-86941 discloses both flat membranes and hollow fiber membranes, and as is clear from the examples, flat membranes
1500/m ²・hr・Kg/cm ² are also seen, but for hollow fiber membranes, the polymer concentration in the stock solution must be higher than that of flat membranes from the viewpoint of spinnability and pressure resistance.
At most, water permeability of 420/m ²・hr・Kg/cm ² has been obtained. There is a major difference between flat membranes and hollow fiber membranes, and what is possible with flat membranes is often difficult to achieve with hollow fiber membranes. A typical example is water permeability expressed on a membrane area basis. Therefore, it would be of industrial value if a hollow fiber shape with a water permeability expressed on a membrane area basis of 2000/ ^m2・hr・Kg/cm2 ^{or more} could be obtained from polysulfone, which has extremely excellent physical properties as a polymer itself. seems to be extremely large. In addition, with conventional polysulfone hollow fiber membranes, only permeate backwashing and chemical washing can be used as a means of restoring membrane performance when clogging occurs due to excessive air flow, but this is easier if the ventilation pressure is low. Air backwashing with less loss can also be used, which is very preferable. Furthermore, if you want to remove suspended solids and microorganisms from a polymer solution containing various insoluble suspended solids and microorganisms, the permeation method allows most of the dissolved polymer to permeate and blocks the suspended solids and microorganisms. membranes are required, which is not possible with conventional polysulfone hollow fiber membranes. In view of the above circumstances, the present inventors adopted a hollow fiber membrane shape that allows for an overwhelmingly large membrane area per occupied volume, and a membrane material of heat-resistant, acid-resistant, alkali-resistant, and oxidation-resistant polysulfone. It has extremely high water permeability and blocks particles and microorganisms with a diameter of 4000Å or more.
In addition, the present invention was achieved through extensive research into a membrane that has a ventilation pressure low enough to allow air backwashing and that allows most of the dissolved polymer to pass through. In other words, the present invention has a porosity of micropores with an average pore diameter of 0.1 to 5μ on the outer surface.
The membrane has a ratio of 10 to 70%, has a microporous structure inside and on the membrane surface, and has a water permeability of 2000/ ^m2 .
This is a polysulfone hollow fiber membrane that exhibits hr·Kg/cm ² or more and a rejection rate of 90% or more for polystyrene latex (particle size 3800 Å). In addition to the above structure and characteristics, other polysulfone hollow fiber membranes of the present invention have a ventilation pressure of 0.5 to 5 Kg/cm 2 and a molecular weight of 0.5 to 5 Kg/cm ² .
It shows a rejection rate of 10% or less for a standard polyethylene oxide aqueous solution of 660,000. The polysulfone referred to in the present invention is a polymer having the following general formula (A) or (B) as a repeating unit. However, X, X', Y, and Y' represent substituents on the benzene ring, such as hydrogen, methyl, halogen, nitro, sulfonic acid (or its salt), carboxylic acid (or its salt), quaternary ammonium (or the salt)
etc. a, b, c, and d represent integers of 0 to 4. R represents a divalent organic residue, for example

[Formula] etc. Z represents O or _SO2 . Generally, in formula (A), a, b, c, d are 0, and R is

[Formula] Those in which Z is O are easily available. In addition, formula (B) in which a and b are 0 is easily available and convenient. In particular, "Udel" manufactured by Union Carbide is the easiest to use industrially. Furthermore, the hollow fiber membrane referred to in the present invention has an inner diameter of 100 to 3000μ, preferably 200 to 3000μ.
1000μ, and the outer diameter is 200~5000μ, preferably
It is a tubular tubule of 400-1500μ. Micropores with an average pore diameter of 0.1 to 5 microns must exist on the outer surface of the hollow fiber membrane at a porosity of 10 to 70%. In the present invention, what is the average pore diameter of the micropores on the outer surface? Here: average pore diameter D ₁ ; actual measured diameter of the first micropore D _o ; actual measured diameter of the n-th micropore Note that the actual measured diameters of D ₁ and D _o are the diameters when the micropore is close to circular. If the micropore is not circular, indicate the diameter of a circle with the same area as the micropore. This is shown in . Average pore size on outer surface is 0.1μ
If it is less than that, the water permeability becomes too small. Furthermore, if the average pore diameter is small, the water permeability will be low and the ventilation pressure will be too high. In particular, there is a close relationship between the outer surface pore diameter and the ventilation pressure, and it is preferable that the average pore diameter of the outer surface is 0.3μ or more because the ventilation pressure will be low and air backwashing will be possible. When the average pore diameter exceeds 5μ, the outer surface becomes rough and the strength tends to be weak. In addition, in the case of external pressure overload, large slag enters into the membrane, and not only does the permeation rate drop quickly, but the membrane also tends to be unable to be regenerated sufficiently even by backwashing or chemical washing. , undesirable. It is more preferable that the average pore diameter is 2μ or less.
In the case of the present invention, micropores with a diameter of 0.05μ or less are not included in the calculation of the average pore diameter. However, fine pores of 0.05 μm or less may be present to the extent that the objects and effects of the present invention are not impaired. Further, although it is preferable that the micropores on the outer surface have a uniform diameter, they do not need to be particularly uniform and may be non-uniform. The porosity referred to in the present invention is the ratio of the total pore area of micropores opened on the outer surface to the outer surface area, expressed as a percentage. If the porosity is less than 10%, the water permeability will be low, which is not preferable. If the porosity exceeds 70%, the surface strength will decrease and the membrane will be easily damaged during handling, which is not preferable. A porosity of 20 to 50% is more preferable in terms of the balance between membrane permeability and mechanical performance. In the present invention, the inside of the membrane has a microporous structure, and the microporous structure here includes a network structure, a honeycomb structure, a microporous structure, and the like. Furthermore, although there may be a finger-like structure or a macrovoid structure inside the membrane, it is preferable from the viewpoint of strength that there be no cavities larger than 20 μm or larger than 10 μm. It is preferable that micropores with the same pore size as the outer surface exist inside the membrane and on the inner surface of the membrane. Although it is preferable that the pore diameter be more uniform, it is not particularly necessary to be uniform and may be non-uniform. Further, when external pressure is applied, relatively large holes of about 1 to 8 microns may be randomly provided on the inner surface without any problem. Furthermore, as is clear from the structure of the polysulfone hollow fiber membrane obtained in Example 1 (Figs. 2 to 5), which will be described later, the inner surface of the membrane has pores (slits) smaller than the pores inside the membrane and on the outer surface of the membrane. It may have a microporous structure with micropores (slit-like micropores) of approximately the same size as the micropores inside and on the outer surface of the membrane, and the above-mentioned small micropores (slit-like micropores). It may also have a microporous structure in which voids are mixed. Further, the microporous structure inside the membrane has the function of supporting the inner and outer surfaces of the membrane, and also has the function of determining the rejection rate, water permeability, and ventilation pressure. The polysulfone hollow fiber membrane of the present invention has the above-mentioned structure and has a water permeability of 2000/ ^m2 .
hr·Kg/cm ² or more, and shows a rejection rate of 90% or more for polystyrene latex (particle size 3800 Å). The permeability (K) here refers to the effective length 10
cm, using a new hollow fiber membrane module with a membrane area of Am ² based on the inner diameter, circulating pure water at 25°C under internal pressure, with an inlet pressure of P ₁ Kg/cm ² (adjusted to approximately 0.5 Kg/cm ² ) and an outlet pressure of P _2kg / ^cm2
Then, measure the amount of water permeation per hour, and calculate Q(/
hr) is the value calculated using the following formula. K=2Q/(P ₁ + P ₂ )A Note that when the water permeability is extremely high as in the present invention, if the effective length of the hollow fiber membrane is long, the membrane will not exhibit its original water permeability due to pressure drop, etc., so be careful. There is a need to. Therefore, in the case of the present invention, the effective length of the hollow fiber membrane is measured under relatively short conditions of 10 cm. In the case of conventional polysulfone hollow fiber membranes, the water permeability is mostly
It is less than 1000 to 2000/ ^m2・hr・Kg/ ^cm2 . On the other hand, flat membranes called so-called precision membranes (MF) are commercially available, and in this case, depending on the pore size, the pore size exceeds 1000/ ^m2・hr・Kg/ ^cm2 at around 0.2μ. is commercially available, but it has a hollow fiber membrane shape that allows the membrane area per occupied volume to be overwhelmingly larger than that of a flat membrane, and it is made of polysulfone, which is an extremely superior membrane material, and has a membrane area of 2000/m ² hr.
It is truly significant to be able to obtain extremely high water permeability of Kg/cm ² or more. Furthermore, the water permeability is 6000
Preferably, it has a revolutionary high water permeability of ~50,000/m ² ·hr·Kg/cm ² . The polystyrene latex (particle size
The rejection rate (R) of 3800 Å) is measured by the following method.
According to the polymerization method of "Run number S-1497" described on page 1732 of Volume 20 of Journal of Abright Polymer Chemistry, pages 1725-1733 (published in 1976), the particle size was 3800 ű.
A highly uniform soap-free polystyrene latex of 70 Å was obtained. For reference, this electron micrograph is shown in Figure 1. A 1% diluted solution of this latex was prepared at a temperature of 25°C, an inlet pressure of 0.5 kg/cm ² , and a linear velocity of 30
External pressure filtration is carried out under the filtration condition of cm/sec using the hollow fiber membrane module used in the water permeability measurement described above.
The latex concentration of the permeate was measured using a turbidity meter,
Calculate using the following formula. R = (1-C _P /C _F ) x 100 where R is the rejection rate _CF is the concentration of latex in the stock solution _CP is the concentration of latex in the permeate The hollow fiber membrane of the present invention is the inhibition of polystyrene latex with a particle size of 3800 Å. rate is 90% or more. 90%
If it is less than 0.4μ, a hole with a diameter of 0.4μ will penetrate through the hollow fiber membrane wall, resulting in poor overaccuracy, which is not preferable. In the case of the present invention, when the rejection rate of polystyrene latex with a particle size of 2000 Å is 90% or more,
It is even more preferable because it further improves overaccuracy and does not allow most microorganisms to pass through. Particle size referred to here
As the 2000 Å polystyrene latex, a styrene-butadiene latex ("Dow Latex-636" manufactured by Dow Chemical Company) is used, and the rejection rate R is measured in the same manner as described above. When comparing the polysulfone hollow fiber membrane of the present invention and a flat membrane type with a pore size of 0.45μ or 0.2μ in terms of modules occupying the same volume, the hollow fiber membrane of the present invention usually packs a membrane area five times or more larger. The flat membrane type has a higher water permeability per membrane area, but the overspeed per module is the same.
Rather, the hollow fibers of the present invention can be made larger. Furthermore, when carrying out filtration, the overspeed decreases due to clogging with slag, but the hollow fiber membrane of the present invention has the advantage that the decrease in overspeed is smaller than that of the hollow fiber membrane of the present invention. The reason for this is presumed to be that the hollow fiber membrane has a large membrane area, so the thickness of the slag that accumulates even if the same amount is passed through is thin. As well as overaccuracy and overspeed, slag trapping ability is a fundamentally important factor for a filter, and being excellent in this is important from a practical standpoint. Furthermore, due to the modular structure and other factors, flat membrane types are difficult to regenerate through backwashing and/or chemical washing, so they have no choice but to be disposable, and the membrane must be replaced many times. , in the case of the hollow fiber membrane of the present invention, backwashing or/
It can be used repeatedly by chemical washing and is superior to the flat membrane type in this respect as well. As described above, the polysulfone hollow fiber membrane of the present invention has micropores of 0.1μ or more, which are serious defects in conventional polysulfone hollow fiber membranes having a skin layer, on the inner surface, inside the membrane, and on the outer surface. The main feature is that the polysulfone hollow fiber membrane is made to exist actively and in large quantities, thereby creating a polysulfone hollow fiber membrane with an epoch-makingly higher water permeability than before. Therefore, the membrane structure and membrane performance are different from conventional polysulfone hollow fiber membranes having a skin layer. Furthermore, it has many features compared to the flat membrane type. The polysulfone hollow fiber membrane of the present invention has a ventilation pressure of
Gas backwashing is possible when it is 0.5-5Kg/ ^cm2 ,
More preferred. The ventilation pressure referred to in the present invention is 1%
It was immersed in an aqueous solution of sodium lauryl sulfate for 24 hours at 25°C, and then washed under running water at 25°C for more than 1 hour to completely wet the hollow fiber membrane with water, which means that the pores in the thin walls of the membrane wall were sufficiently filled with water. The air pressure required to obtain an air permeation rate of 400 Hl/m ² hr by applying air pressure to the inside of the hollow fiber membrane while it is immersed in water to cause bubbling. If the ventilation pressure is less than 0.5 Kg/cm ² , large voids often exist in the membrane, and the strength tends to be brittle. On the other hand, the ventilation pressure is 5Kg/
If it exceeds cm ² , the air backwash pressure is too high and there are many problems. It is more preferable that the ventilation pressure is 1 to 4 Kg/ ^cm2 ,
A range of 1.5 to 3.5 Kg/cm ² is most preferable in terms of balance of strength, air pressure, membrane life, etc. Generally, over-operation will cause clogging, which will eventually make over-operation impossible. If clogging occurs, the hollow fibers may be conveniently able to be easily removed by applying reverse pressure (backwashing). Generally, backwashing is carried out using a liquid such as permeate. However, if a certain amount of clogged matter accumulates, this liquid backwashing method is often unable to remove the clogged matter sufficiently and the permeation rate does not recover, so methods such as frequently repeating backwashing are not recommended. Must be. When using permeated liquid as a backwash liquid, the permeated liquid must be returned to its original state.
There is no meaning unless the amount of backwashing liquid is reduced relative to the total amount of permeate, but if the amount of backwashing liquid is small, the backwashing effect will be reduced, which poses a dilemma. If water or the like is used as a backwash liquid other than the permeate, more serious problems arise, such as dilution of the treatment liquid. A gas backwashing method has been proposed as a means to solve these problems. In particular, a filtration system that combines external pressure filtration and internal pressure air backwashing using a hollow fiber membrane module with one end free is characterized by the fact that each hollow fiber vibrates during air backwashing, which has the added effect of shaking off clogging materials, and flattening the air. The backwashing effect is so great that you wouldn't expect it from the membrane type. Moreover, it is an excellent filtration system with very little loss of permeate and no dilution. Up until now, a type of hollow fiber made from polyvinyl alcohol, a hydrophilic material, that can be air-backwashed has been considered, but with hydrophobic polymers such as polysulfone, once they are completely dry, their water permeability will be zero if they are simply immersed in water. Therefore, the fibers must be immersed in a water-miscible solvent (for example, ethanol) or an aqueous surfactant solution to sufficiently fill the micropores in the membrane wall of the fibers with water. There was a concern that the water permeability would be zero even after air backwashing, but I was wondering if air backwashing could be done with the hollow fibers immersed in the liquid.
Alternatively, if it is carried out in the air, it is carried out in a closed container in an atmosphere with a relative humidity of 90% or more, preferably almost 100%, and for a relatively short period of time (for example, within 10 minutes).
Moreover, it has been found that by flowing an excessive amount of air (for example, 2000 Hl/m ² ·hr or more), the same permeation rate as that of a hydrophilic polymer can be obtained even after air backwashing.
It is further preferable that the humidity of the backwash air used is 60% or more. It has also been found that depending on the properties of the slag, polysulfone may have a smaller interaction with the slag than a hydrophilic polymer, and therefore may be easier to peel off by air backwashing. As mentioned above, one of the important points of the present invention is the discovery of a polysulfone hollow fiber membrane that can be air-backwashed. Further, the hollow fiber membrane of the present invention preferably has a rejection rate of 10% or less for a standard polyethylene oxide aqueous solution having a molecular weight of 660,000. What is the rejection rate of a standard polyethylene oxide aqueous solution with a molecular weight of 660,000?
Standard polyethylene oxide with a sharp molecular weight distribution of 660,000 (SE-70 made by Toyo Soda) is 0.5
% ethanol aqueous solution at a temperature of 25°C, an inlet pressure of 0.5 Kg/cm ² , and a linear velocity of 30
The polyethylene oxide concentration of the permeate was measured using a differential birefringence meter under external pressure filtration using a new hollow fiber membrane module of the present invention with the same specifications as those used to measure the water permeability described above under the turbulence condition of cm/sec. This is the value calculated using the following formula. R = (1-C _P /C _F ) x 100 where R is the rejection rate C _F is the concentration of polyethylene oxide in the stock solution C _P is the concentration of polyethylene oxide in the permeate The rejection rate of an aqueous solution of polyethylene oxide with a molecular weight of 660,000 is 10%. If it exceeds it, the molecular weight cut-off becomes too small, which is not preferable. The conventional polysulfone hollow fiber membrane with a skin layer is designed to block polymers with a molecular weight of 660,000. The polysulfone hollow fiber membrane of the present invention is also very different in this respect. In order to more completely separate dissolved polymers from suspended solids and microorganisms, the rejection rate of a standard polyethylene oxide aqueous solution with a molecular weight of 1.2 million is required.
More preferably, it is 10% or less. The rejection rate here refers to polyethylene oxide with a sharp molecular weight distribution (manufactured by Toyo Soda Co., Ltd.) with a molecular weight of 1.2 million.
Measure in the same way using SE-150). Next, a method for producing the polysulfone hollow fiber membrane of the present invention will be described. When manufacturing a hollow fiber membrane by extruding a spinning dope consisting of polysulfone, a pore-forming agent, and a polysulfone solvent through an annular nozzle, [1] a micropore-forming agent that is insoluble in the polysulfone solvent and having an average particle size of 0.01 to 5μ; A polysulfone characterized by using fine powder, [2] dry-wet spinning, and [3] bringing the spun hollow fiber membrane into contact with a solvent for the pore-forming agent to extract and remove the pore-forming agent. This is a method for producing hollow fiber membranes. By this manufacturing method, it is possible to obtain a polysulfone hollow fiber membrane having the structure as described above and the membrane performance as described above. Fine powders that are insoluble in polysulfone solvents include metal oxides such as silicon oxide, zinc oxide, and aluminum oxide, inorganic compounds such as sodium chloride, sodium acetate, sodium phosphate, calcium carbonate, and calcium hydroxide, calcium lactate, There are organic compounds such as zinc stearate. Fine powder of silicon oxide (silica powder), so-called white carbon, is best because it has a small powder particle size, is commercially available in various particle sizes, and is easily dispersed. These fine powders function as a pore-forming agent for the membrane. As a solvent for polysulfone, 10g (polysulfone)/100c.c. (solvent) at a temperature in the range of 0 to 120℃
Polar solvents having the above-mentioned dissolving ability are used, and specific examples include dimethylformamide (DMF), dimethylacetamide (DMA), and N-methylpyrrolidone (NMP). A fine powder pre-addition method involves adding fine powder to this solvent, mixing and stirring to form a dispersion of the fine powder, and then dissolving the polysulfone. A simultaneous addition method involves adding the fine powder and polysulfone at the same time, mixing and stirring, and a further method after dissolving the polysulfone in the solvent. Although any post-addition method of adding, mixing and dispersing fine powder may be used, the pre-addition method is often better in terms of dispersibility. It is also possible to replace water with an organic solvent in an aqueous dispersion of colloidal silica or colloidal aluminum by a solvent substitution method to obtain a dispersion of these organic solvents, and then dissolve polysulfone to obtain a spinning dope. In the method for producing a spinning dope, the average dispersed particle size of the fine powder must be 0.01 to 5μ. If it is less than 0.01μ, it is too small to obtain the desired air permeability or membrane structure. Moreover, if it exceeds 5μ, it is too large and only a heterogeneous product with large voids can be obtained. More preferably 0.1 to 3.5μ, most preferably 0.1 to 3.5μ
2μ is superior in terms of homogeneity of membrane structure and air permeability.
Note that the dispersed shape of the fine powder may be spherical, but there is no problem even if it is not spherical. If the shape is not spherical, the particle size is considered to be the diameter of a sphere with the same volume. In some cases, it may be better to disperse the particles in a bead shape rather than in a spherical shape. The amount of fine powder added is 15 to 400% by weight/
Polysulfone is preferred, more preferably 50 to 150% by weight/polysulfone. Simply stirring with a stirring blade is sufficient to disperse fine powder, but in order to improve dispersibility, more advanced mixing methods such as high-speed stirring, homomixer, ultrasonic dispersion, pipeline agitator, and static mixer are required. Preferably, dispersion means are used. The fine powder-dispersed polysulfone solution thus obtained is usually defoamed to obtain a spinning stock solution. On the other hand, it is also possible to separately prepare a solvent dispersion of fine powder and a polysulfone solution, quantitatively and continuously mix and disperse them in-line in an airtight manner, and then immediately spin. Further, it is essential that the fine powder is insoluble in the polysulfone solvent. Therefore, when using a certain fine powder, it is necessary to choose a solvent that does not dissolve it, and when using a certain solution, it is necessary to choose a fine powder that does not dissolve in it. Insoluble herein refers to a dissolving ability of 0.1 g (fine powder)/100 c.c. (solvent) or less at the dissolution temperature of the stock solution. The desired polysulfone hollow fiber membrane can only be obtained by using a fine powder of polysulfone that is insoluble in a solvent. The purpose cannot be achieved by using a fine powder that dissolves in a solvent. The concentration of polysulfone is 10-30% by weight, preferably 12-25% by weight. The concentration here refers to polysulfone weight/(polysulfone + solvent + fine powder) weight x 100. If the polysulfone concentration is less than 10%, the strength of the hollow fiber membrane obtained will be low, and if it exceeds 30%, it will not be possible to obtain a membrane having the above-mentioned membrane structure and performance, which is not preferable. The spinning dope thus obtained must be subjected to dry-wet spinning through an annular nozzle. By the commonly used wet spinning method, the desired pores are not formed on the outer surface, and the hollow fiber of the present invention cannot be obtained. The dry-wet spinning referred to herein refers to a method in which the spinning stock solution is once extruded into gas (air in most cases) and then introduced into a coagulating liquid, that is, a method in which the nozzle is not immersed in the coagulating liquid. If we define the distance between the nozzle discharge surface and the coagulating liquid surface, that is, the air travel distance, as the dry zone length, then the dry zone length is 0.1 to 200 cm.
Good. If the length is shorter than 0.1 cm, even slight ripples in the coagulating liquid will cause the nozzle to be immersed in the coagulating liquid, making wet-dry spinning practically impossible. If the length exceeds 200 cm, the yarn will swing too much and normal spinning will not be possible.
The more suitable dry zone length is 0.3 to 50 cm, and 1 to 50 cm.
30cm is the best balance between spinnability and membrane performance. Conventionally, wet-dry spinning is often used to reduce the diameter of hollow fiber membranes and increase spinning speed, or to evaporate solvents in a dry zone to form a skin layer on the surface, but the present invention In this case, rather than forming a skin layer on the surface, micropores are formed on the surface, which is clearly different from the purpose and effect of conventional dry-wet spinning. The effect of wet-dry spinning of the present invention is also unique in that even though the dry zone length is very short, 0.1 cm, it shows a clear difference from wet spinning, where the dry zone length is 0 cm. The pore size of the outer surface can be controlled by this dry zone length. The coagulating liquid is not particularly limited as long as it is miscible with the polysulfone solvent and is a non-solvent for the polysulfone. Generally, water or a mixture of a solvent and water is used. Additionally, it may be advantageous to add surfactants and the like. The internal coagulating fluid to be flowed into the needle of the annular nozzle is not particularly limited to a coagulable liquid, an incompatible liquid, a gas (air, nitrogen), etc., but a coagulable liquid such as water is preferable. Among these, in order to form pores on the inner surface of the hollow fiber membrane, a mixture of solvent and water, solvent/
A material having a water weight ratio of 60/40 to 95/5 and exhibiting a slow coagulation effect is excellent. Solvent/water ratio is 75/25
A ratio of ~90/10 is optimal in terms of balance between spinnability and membrane performance. Since the hollow fiber membrane thus formed contains a large amount of fine powder, it will not exhibit the desired performance as it is. Therefore, it is necessary to extract and remove the fine powder by bringing the hollow fiber membrane into contact with a solvent for the fine powder during the spinning process or once it is wound up. Extraction conditions vary depending on the type of fine powder and solubility of the solvent, but
Since the fine powder is in the polysulfone matrix, it is necessary to make the dissolution conditions much stricter than those for the fine powder alone, that is, to increase the extraction temperature and solvent concentration, and to lengthen the extraction time. For example, when fine silica powder is extracted with an aqueous solution of caustic soda, the concentration of caustic soda in the extract is 2 to 50% by weight, preferably 8 to 20% by weight. Further, the extraction temperature is 5 to 120°C, preferably 40 to 100°C. Further, the extraction time is 0.1 to 1000 minutes, preferably 1 to 100 minutes. Extraction at high temperatures is usually advantageous because heat treatment can be carried out at the same time as extraction. Further, extraction may be performed by static immersion alone, but in order to perform extraction quickly, it is better to stir the extract or move the hollow fiber membrane in the extract. In particular, when the extraction time is short, such as 5 minutes or less, it is possible to perform the extraction process continuously during the spinning process and then roll it up to produce a product all at once. By making the membrane of the present invention into a module, it can be suitably used in a filtration method that involves external pressure filtration. , water, wastewater, and various liquids, water, wastewater, etc. in the medical field. It is especially suitable for oxidizing liquids such as sodium hypochlorite and hydrogen peroxide, acidic or alkaline liquids such as sulfuric acid and alkali, high-temperature liquids such as various sugar solutions, and even tap water. Next, the present invention will be explained by examples. Example 1 Udel polysulfone (Union Carbide Company (UCC) "P-1700" 15 parts by weight, average particle size 1.0μ
15 parts by weight of finely powdered silica (Fine Seal T-32 manufactured by Tokuyama Soda Co., Ltd.) and 70 parts by weight of dimethylformamide (DMF) were stirred and dissolved at 40°C to prepare a slurry-like spinning stock solution in which finely powdered silica was uniformly dispersed. did. The viscosity of the spinning dope was measured using a B-type viscometer at a rotation speed of 12 rpm and a temperature of 40°C, and found to be 96 poise. Using a ring nozzle, the spun fibers were degassed by standing overnight at 40℃, and the internal coagulation liquid was DMF/water in a weight ratio.
Wet-dry spinning was performed while injecting an 80/20 aqueous solution. At this time, the dry zone length was 10 cm, the atmosphere of the dry zone was 25°C, and the relative humidity was 60%, and the external coagulation liquid was water at 20°C. The obtained hollow fiber membrane was washed with water to complete coagulation and to remove DMF. Then in a 15% by weight aqueous solution of caustic soda.
The silica was extracted and removed by immersion treatment at 100°C for 2 hours for a fixed length. The obtained polysulfone hollow fiber membrane had an outer diameter of 800μ,
The inner diameter was 500μ. In addition, as a result of observing the inner and outer surfaces and cross section of the hollow fiber membrane using a scanning electron microscope (SEM), it was found that the outer surface has micropores with an average pore diameter of 0.8μ, the porosity is 40%, and the cross-sectional structure is microporous. The inner surface had a microporous structure with slit-like micropores. SEM photographs are shown in Figures 2 to 5. The water permeability of this hollow fiber membrane is 20000/
The rejection rate of polystyrene latex with m ² · hr · Kg/cm ² and particle size of 3800 Å is 100%, and the ventilation pressure is
The rejection rate of polyethylene oxide having a weight of 2.6 kg/cm ² and a molecular weight of 1.2 million was 5%. This hollow fiber membrane had revolutionary water permeability and was also capable of gas backwashing. Example 2 15 parts by weight of finely powdered silica ("Fine Seal-B" manufactured by Tokuyama Soda Co., Ltd., manufactured by Tokuyama Soda Co., Ltd.) with an average particle size of 3.5 μm was added to 65 parts by weight of DMF with stirring to obtain a rough dispersion of silica in DMF. Ultrasonic waves were applied for 20 minutes to completely disperse the dispersion. 20 parts by weight of Udel polysulfone powder ("P-1800" manufactured by UCC) was added to the dispersion and dissolved at 40°C to form a uniform slurry with a viscosity of 185 poise. A stock solution was prepared, and the stock solution was defoamed overnight and then subjected to dry-wet spinning using a 12-hole annular nozzle.At this time, it was stirred and dispersed through a 12-element static mixer just before the nozzle, and DMF/DMF was added as an internal coagulation liquid. Inject an aqueous solution with a weight ratio of 80/20,
The length of the dry zone was 10 cm, and the atmosphere in the dry zone was adjusted by flowing air at room temperature and relative humidity of 50% into the nozzle at a rate of 5 Nl/minute. Furthermore, water at 12°C was used as a coagulation bath. The obtained hollow fiber membrane was washed with water and then
Silica was extracted and removed by immersion treatment in a 10% by weight aqueous sodium hydroxide solution at 80°C for 30 minutes. As a result of observing the inner and outer surfaces and cross-section of the obtained polysulfone hollow fiber membrane by SEM, it was found that micropores with an average pore diameter of 1.2μ existed on the outer surface with a porosity of 35%.
It was observed that the inner surface had a microporous structure with many slit-like micropores of 0.1μ or more, and the inside of the membrane had a sponge structure with no voids of 10μ or more. Also, the water permeability is 9800/m ²・hr・Kg/
The rejection rate of styrene-butadiene latex particles having a particle diameter of 2000 Å ^and an average diameter of 2000 Å was 98%. The ventilation pressure was 2.4 Kg/cm ² and the rejection rate of polyethylene oxide having a molecular weight of 660,000 was 0%. Example 3 Using the same stock solution as in Example 2, spinning and washing were carried out in the same manner as in Example 2 except that the dry zone length was 1 cm, and the obtained hollow fiber membrane was soaked in 10% by weight of caustic soda at 100°C. Silica was extracted and removed by immersion treatment for 5 minutes. As a result of observing the obtained hollow fiber membrane with SEM,
It was confirmed that micropores with an average pore diameter of 0.25μ existed on the outer surface with a porosity of 15%, that the inside of the membrane had a microporous structure, and the inner surface had a microporous structure with slit-like micropores. Also, the water permeability is 6500/m ²・hr・Kg/
cm ² and the rejection rate of styrene-butadiene latex with a particle size of 2000 Å was 100%. Further, the ventilation pressure was 3.4 Kg/cm ² and the rejection rate of polyethylene oxide having a molecular weight of 660,000 was 0%. Comparative Example 1 Using the same stock solution as in Example 1, spinning, water washing, and silica extraction were performed under all the same conditions as in Example 1, except that the annular nozzle was immersed in a coagulation bath and the dry zone length was 0 cm. . The obtained hollow fiber membrane
As a result of observation with SEM, it was found that there were no micropores larger than 0.05μ on the outer surface, and a skin layer was present. Figure 6 shows a SEM photograph of the outer surface. Example 4 17.5 parts by weight of finely powdered silica (Fine Seal-B) having an average particle size of 3.5 μm was added to 65 parts by weight of DMF, and the mixture was stirred and dispersed for 20 minutes using a homomixer. Add 17.5 parts by weight of polyether sulfone ("Victrex 200P" manufactured by ICI) to the dispersion, stir and dissolve at 40°C,
A uniform slurry stock solution with a viscosity of 125 poise at 40°C was prepared. The stock solution was subjected to spinning in the same manner as in Example 1, and alkali extraction was performed. When this hollow fiber membrane was observed using a SEM, micropores with an average pore diameter of 1.5 μm were present on the outer surface with a porosity of 35%. Also, the water permeability is 7900/m ²・hr・Kg/cm ²
The rejection rate of the 2000 Å styrene-butadiene latex was 100%. Furthermore, the ventilation pressure is 2.1Kg/
cm ² and the rejection rate of polyethylene oxide with a molecular weight of 660,000 was 0%.

[Brief explanation of the drawing]

FIG. 1 shows a transmission electron micrograph (magnification: 33150) of polystyrene latex used in measuring the rejection rate of the hollow fiber membrane of the present invention. 2 to 6 are scanning electron micrographs of the hollow fiber membranes obtained in Example 1 and Comparative Example 1, and
The figure shows the cross-sectional structure of the hollow fiber membrane of Example 1 (magnification
500), Figure 3 shows the structure of the central part of the hollow fiber membrane in Figure 2 (magnification 5000), Figure 4 shows the structure of the outer surface of the hollow fiber membrane in Figure 2 (magnification 5000), and Figure 5 shows the structure in Figure 2. The structure of the inner surface of the hollow fiber membrane (magnification: 5000) is shown, and FIG. 6 also shows the structure of the outer surface of the hollow fiber of Comparative Example 1 (magnification: 5000).

Claims (1)

[Claims] 1. Micropores with an average pore diameter of 0.1 to 5μ on the outer surface, porosity rate 10
The inside of the membrane has a microporous structure, and the inner surface of the membrane has a microporous structure with slit-like micropores that are smaller than the micropores inside the membrane and on the outer surface of the membrane.
A polysulfone hollow fiber membrane exhibiting a water permeability of 2000/m ² ·hr·Kg/cm ² or more and a rejection rate of polystyrene latex (particle size 3800 Å) of 90% or more. 2. The polysulfone hollow fiber membrane according to claim 1, wherein the average pore diameter of the micropores on the outer surface is 0.3 to 2μ. 3. The polysulfone hollow fiber membrane according to claim 1 or 2, wherein the porosity of the micropores on the outer surface is 20 to 50%. 4. The polysulfone hollow fiber membrane according to any one of claims 1 to 3, which has a rejection rate of 90% or more for polystyrene latex (particle size 2000 Å). 5 Water permeability is 6000/m ²・hr・Kg/cm ² ~50000
/m ²・hr・Kg/cm ² Claims 1 to 2
The polysulfone hollow fiber membrane according to any one of item 4. 6. The polysulfone hollow fiber membrane according to any one of claims 1 to 5, which has a ventilation pressure of 0.5 to 5 Kg/cm ² . 7. The polysulfone hollow fiber membrane according to claim 6, which has a ventilation pressure of 1 to 4 Kg/cm ² . 8. The polysulfone hollow fiber membrane according to claim 6, which has a ventilation pressure of 1.5 to 3.5 Kg/cm ² . 9. The polysulfone hollow fiber membrane according to any one of claims 1 to 8, which exhibits a rejection rate of 10% or less for a standard polyethylene oxide aqueous solution having a molecular weight of 660,000. 10. The polysulfone hollow fiber membrane according to any one of claims 1 to 8, which exhibits a rejection rate of 10% or less for a standard polyethylene oxide aqueous solution having a molecular weight of 1.2 million.