JP5126155B2 - Manufacturing method of composite semipermeable membrane - Google Patents

Description

  The present invention relates to a method for producing a high performance composite semipermeable membrane used to selectively separate solute components from a liquid mixture. In particular, the present invention relates to a method for producing a composite semipermeable membrane having high durability in addition to high desalination and high water permeability useful for desalination treatment of brine and seawater.

  There are various techniques for removing a substance (for example, salts) dissolved in a solvent (for example, water) with respect to the separation treatment of the liquid mixture, but there is no change in the phase of the solvent and an additional driving force for separation. Due to advances in pressure technology, membrane separation methods are widely used as a process for saving energy and resources. Separation membranes used in membrane separation methods include microfiltration (MF) membranes, ultrafiltration (UF) membranes, and reverse osmosis (RO) membranes. In recent years, loose RO membranes and NF (Nano-Filtration) membranes have been developed as separation performance at the boundary between reverse osmosis (RO) membranes and ultrafiltration (UF) membranes. In the case of obtaining drinking water from water containing harmful substances, it has been used for the production of industrial ultrapure water, wastewater treatment, recovery of valuable resources, and the like.

  Many of the reverse osmosis membranes, loose RO membranes, and NF membranes currently on the market are composite semipermeable membranes. Among these, a composite semipermeable membrane obtained by coating a porous support membrane with a separation functional layer made of a crosslinked polyamide obtained by a polycondensation reaction of a polyfunctional amine and a polyfunctional acid derivative has a permeability and a selective separation property. Widely used as a high reverse osmosis membrane.

  Here, in order to improve the desalting performance and water permeation performance of the composite semipermeable membrane, a method of treating the polyamide separation functional layer with various reagents has been proposed. For example, contact treatment or immersion treatment with ammonia, alkylamines, alcohols, hydrochloric acid, organic acids, or inorganic salts has been proposed (see Patent Documents 1 to 5). Processing by these methods can improve the performance of the composite separation membrane, but there are problems with the membrane performance improvement effect, workability and safety of the processing method, etc., with a simpler and safer processing method. A technique for improving the membrane performance efficiently is desired.

  On the other hand, a method for producing a composite semipermeable membrane has been proposed in which an ultra-thin layer of a crosslinked aromatic polyamide formed by interfacial polycondensation is treated with an aqueous persulfate compound solution to improve the oxidation resistance of the membrane (patent) Reference 6). However, even if the membrane is modified by this manufacturing method, it is difficult to sufficiently improve the water permeability, and there is a problem that the water permeability is low.

  Furthermore, a method for producing a semipermeable composite membrane in which an ultra-thin film made of a crosslinked aromatic polyamide is brought into contact with a chlorine-containing aqueous solution and a method for treating a reverse osmosis membrane separation device in which a reverse osmosis separation device is treated with a chlorine-containing aqueous solution have been proposed. (Patent Documents 7 and 8). This improves the performance by bringing an aqueous solution containing free chlorine into contact with the polyamide. However, since free chlorine is unstable in water, there is a problem that it is difficult to control the reaction.

  Moreover, the preservation | save method which contacts the aqueous solution containing chlorine dioxide suitable for preserve | saving a semipermeable membrane for a long period of time without a performance change is proposed (patent document 9). This is to keep the performance stable by bringing it into contact with chlorine dioxide for a long time without breeding microorganisms such as fungi, but it has only been effective in offsetting the performance change due to the propagation of microorganisms.

  Thus, the composite semipermeable membrane obtained by the conventional manufacturing method still has problems, has more stable operability and simple operability in various water treatments, and further pursues low cost by reducing the frequency of membrane replacement. It is required to have durability.

Special Table 2000-504270 JP-A-6-327953 JP 2000-237559 A JP 2003-117360 A JP 2003-117361 A JP-A-5-96140 JP-A 63-54905 Japanese Patent Laid-Open No. 7-80261 Japanese Patent Laid-Open No. 62-234508

  The present invention can produce a composite semipermeable membrane having high solute removal property, high water permeability and high durability, and at the same time, high productivity can be realized by a simple and safe method. It is an object of the present invention to provide a method capable of manufacturing the above.

To achieve the above object, the present invention forms a polyamide separation functional layer by polycondensation on a microporous support membrane, modifies the polyamide separation functional layer by contacting with chlorine dioxide, and improves the membrane performance. Is specified as follows.
(1) A method for producing a composite semipermeable membrane, the step of forming a polyamide separation functional layer by polycondensation reaction of a polyfunctional amine and a polyfunctional acid halide on a microporous support membrane, and then the composite semipermeable membrane A step of reducing the amount of unreacted substances in the membrane to 0.5 g / m ² or less, and then a modification treatment step of bringing the polyamide separation functional layer into contact with chlorine dioxide for 1 second to 24 hours. A method for producing a composite semipermeable membrane.
(2) The modification treatment step is to bring the polyamide separation functional layer into contact with a solution containing chlorine dioxide, and the solution containing chlorine dioxide is an aqueous solution having a pH of 6 or more and 10 or less. A method for producing a composite semipermeable membrane.

  According to the production method of the present invention, the improvement of the membrane performance by the modification of the composite semipermeable membrane, in particular, the improvement of the water permeability can be achieved by a simpler and safer method, from the river water by the reverse osmosis membrane. A composite semipermeable membrane having suitable performance in purified water production or the like can be produced.

  The composite semipermeable membrane in the present invention comprises a separation functional layer having substantially separation performance coated on a microporous support membrane having substantially no separation performance, and the separation functional layer is a polyfunctional amine. And a cross-linked polyamide obtained by reaction of a polyfunctional acid halide. Here, as the polyfunctional amine, there are an aliphatic polyfunctional amine and an aromatic polyfunctional amine, and at least one amine component contained in these is used.

  The aliphatic polyfunctional amine is an aliphatic amine having two or more amino groups in one molecule, and is preferably a piperazine-based amine and a derivative thereof. For example, piperazine, 2,5-dimethylpiperazine, 2-methylpiperazine, 2,6-dimethylpiperazine, 2,3,5-trimethylpiperazine, 2,5-diethylpiperazine, 2,3,5-triethylpiperazine, 2- Examples thereof include n-propylpiperazine and 2,5-di-n-butylpiperazine, and piperazine and 2,5-dimethylpiperazine are particularly preferable from the viewpoint of stability of performance.

  The aromatic polyfunctional amine is an aromatic amine having two or more amino groups in one molecule, and is not particularly limited, but includes metaphenylene diamine, paraphenylene diamine, 1, 3, 5 -Triaminobenzene and the like, and N-alkylated products thereof include N, N-dimethylmetaphenylenediamine, N, N-diethylmetaphenylenediamine, N, N-dimethylparaphenylenediamine, N, N-diethylparaphenylenediamine, etc. In view of the stability of performance, metaphenylenediamine and 1,3,5-triaminobenzene are particularly preferable.

  The polyfunctional acid halide is an acid halide having two or more carbonyl halide groups in one molecule, and is not particularly limited as long as it gives a polyamide by reaction with the amine. Examples of the polyfunctional acid halide include oxalic acid, malonic acid, maleic acid, fumaric acid, glutaric acid, 1,3,5-cyclohexanetricarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid. 1,3,5-benzenetricarboxylic acid, 1,2,4-benzenetricarboxylic acid, 1,3-benzenedicarboxylic acid, and acid halides of 1,4-benzenedicarboxylic acid can be used. Among acid halides, acid chlorides are preferred, and are acid halides of 1,3,5-benzenetricarboxylic acid, particularly in terms of economy, availability, ease of handling, and ease of reactivity. Trimesic acid chloride is preferred. Although the said polyfunctional acid halide can also be used independently, you may use it as a mixture.

  As the organic solvent that dissolves the polyfunctional acid halide, it is preferable to use an organic solvent that is immiscible with water and does not destroy the porous support membrane. It may be. Typical examples include halogenated hydrocarbons such as liquid hydrocarbons and trichlorotrifluoroethane, but they are substances that do not destroy the ozone layer, are easily available, are easy to handle, In consideration of safety, simple substances such as octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, heptadecane, hexadecane, cyclooctane, ethylcyclohexane, 1-octene, 1-decene or a mixture thereof are preferably used.

  Next, a preferred method for producing a composite semipermeable membrane by forming a polyamide separation functional layer by polycondensation on a microporous support membrane will be described. The polyamide separation functional layer having substantially separation performance in the composite semipermeable membrane is, for example, an aqueous solution containing the aforementioned polyfunctional amine and an aqueous solution containing the aforementioned polyfunctional acid halide and immiscible with water. It forms by making it react on the below-mentioned microporous support membrane using an organic solvent solution. Here, the concentration of the aqueous solution containing the polyfunctional amine is preferably 0.1 to 20% by weight, more preferably 0.5 to 15% by weight.

  In the case of an aqueous solution containing a polyfunctional amine or an organic solvent solution containing a polyfunctional acid halide, an acylation catalyst, a polar solvent, an acid scavenger may be used as long as it does not inhibit the reaction between the two components. In addition, compounds such as surfactants and antioxidants may be contained.

  In the present invention, the microporous support membrane is used to support the polyamide separation functional layer. The configuration of the microporous support membrane is not particularly limited, but preferred examples of the microporous support membrane include a polysulfone support membrane reinforced with a fabric. The pore size and the number of pores of the microporous support membrane are not particularly limited, but there are uniform fine pores or gradually larger fine pores from one side to the other, and the size of the fine pores is It is preferable that the surface of one side is 100 nm or less.

  The microporous support membrane used in the present invention is selected from various commercially available materials such as “Millipore Filter VSWP” (trade name) manufactured by Millipore and “Ultra Filter UK10” (trade name) manufactured by Toyo Roshi Kaisha. “Office of Saleen Water Research and Development Progress Report” No. 359 (1968) can be used.

  The material used for the microporous support membrane is not particularly limited. For example, homopolymers or blend polymers such as polysulfone, cellulose acetate, cellulose nitrate, and polyvinyl chloride can be used, but chemically, mechanically, and thermally. It is preferable to use polysulfone having high stability. A specific production method is illustrated below. An aqueous solution containing 0.5% by weight of sodium dodecyl sulfate and 2% by weight of DMF, wherein a solution of polysulfone in dimethylformamide (hereinafter abbreviated as DMF) is applied on a densely woven polyester fabric or nonwoven fabric to a substantially constant thickness. By wet solidification in the inside, it is possible to produce a microporous support membrane in which fine pores having a diameter of several tens of nm or less are formed on most of the surface.

  When coating the surface of the microporous support membrane with an aqueous solution containing a polyfunctional amine, for example, the aqueous solution can be coated by a known coating method so that the aqueous solution is uniformly and continuously coated on the surface. May be performed by a method of coating the surface of the microporous support membrane, a method of immersing the microporous support membrane in the aqueous solution, or the like. Next, the excessively applied aqueous solution is removed by a liquid draining step. As a method of draining, there is, for example, a method of allowing the film surface to flow naturally while holding the film surface in the vertical direction. After draining, the membrane surface may be dried to remove all or part of the water in the aqueous solution. After that, on the microporous support membrane coated with an aqueous solution containing a polyfunctional amine, the organic solvent solution containing the aforementioned polyfunctional acid halide is applied, and a polyamide separation functional layer is formed by the reaction of both components. Let

  The concentration of the polyfunctional acid halide in the organic solvent solution to be applied is not particularly limited. However, if the amount is too small, the formation of a polyamide separation functional layer as an active layer may be insufficient, which may be a disadvantage. Therefore, the content is preferably about 0.01 to 1.0% by weight in the organic solvent solution. The removal of the organic solvent after the reaction can be performed by an ordinary method, for example, drying by blowing air.

  And in this invention, a composite semipermeable membrane is obtained by the process which the polyamide separation functional layer prepared by the above-mentioned process is made to contact with chlorine dioxide.

  Examples of the method for bringing the polyamide separation functional layer into contact with chlorine dioxide include a method in which chlorine dioxide is directly sprayed on the polyamide separation functional layer and a method in which the polyamide separation functional layer is brought into contact with an aqueous solution containing chlorine dioxide. The polyamide separation functional layer is preferably brought into contact with an aqueous solution containing chlorine dioxide. The method for bringing the polyamide separation functional layer into contact with the solution containing chlorine dioxide is not particularly limited, and the entire composite semipermeable membrane may be immersed in an aqueous solution of chlorine dioxide, or the aqueous solution may be used as at least a part of the polyamide separation functional layer. It may be applied as long as the polyamide separation functional layer and chlorine dioxide are in contact with each other.

  In addition to commercially available products, chlorine dioxide is a known method for generating chlorine dioxide by mixing two or more types of compounds, such as 1) mixing chlorous acid aqueous solution with chlorine gas, 2) chlorous acid aqueous solution and Mixing with an aqueous solution of chlorous acid, 3) mixing of an aqueous solution of chlorous acid with an inorganic acid, 4) mixing of sodium chlorate with an inorganic acid, etc. can also be used. Unlike free chlorine, chlorine dioxide does not generate hypochlorous acid when reacted with water, and does not generate chloramine when reacted with ammonia. In other words, it is a compound that does not have a concern of reacting with amides and amines present in the polyamide molecule to chlorinate nitrogen atoms to further oxidize and promote deterioration of the film. When free chlorine is contained as an impurity in the method for generating chlorine dioxide, it is preferable to add a compound having a nitrogen atom to which a sufficient amount of active hydrogen is bonded to free chlorine. Examples of the compound having a nitrogen atom to which active hydrogen is bonded include ammonia, primary amine, secondary amine, amide compound and the like. Chlorine dioxide decomposes when irradiated with light such as ultraviolet rays to generate free chlorine. In order to avoid this, it is preferable to contact the polyamide separation functional layer and a solution containing chlorine dioxide under light-shielding conditions with an illuminance of 10 or less.

  The solution containing chlorine dioxide is brought into contact with the polyamide separation functional layer at pH 2 or more from the viewpoint of preventing hydrolysis of the polyamide and the stability of the solution. The effect of improving the performance is greatly exhibited in the region where the pH is 6 or more. The effect is preferably in the region where the pH is 13 or less, and more preferably in the region where the pH is 10 or less. Above pH 13, the membrane performance is degraded due to the hydrolysis of the polyamide.

  In addition, in order to increase the effect on membrane modification before contacting with chlorine dioxide, the polyamide separation functional layer may be washed with washing water to remove excess unreacted substances (for example, aromatic monomers) and impurities. is necessary. As a result of intensive studies, it has been found that the effect of membrane modification cannot be obtained if an excessive amount of unreacted substances and impurities are present in a certain amount or more. This is presumably because unreacted substances and impurities generate new compounds by the subsequent reaction with chlorine dioxide and remain in the film. The cleaning liquid used in this cleaning process may be any liquid that contains at least one of water and alcohol for extraction of unreacted substances, but from the viewpoint of non-flammability, a cleaning liquid containing water, that is, cleaning water is used. This washing water may contain alcohol or the like in addition to water.

  In addition, the temperature of the washing water is set to 50 ° C. or higher in order to lower its viscosity and enhance the effect of extracting unreacted substances in the membrane. Preferably it is 60 degreeC or more, More preferably, it is 70 degreeC or more. Although it depends on the type of membrane, it takes about 1 day to extract unreacted materials in the membrane at room temperature (25 ° C), so the temperature of the washing solution should be increased from the viewpoint of shortening the washing time. is necessary.

By this washing treatment, unreacted substances contained in the film are reduced to 0.5 g / m ² or less, preferably 0.2 g / m ² or less. More preferably 0.1 g / ^{m 2} or less, more preferably 0.07 g / ^{m 2,} particularly preferably is reduced to less than 0.05 g / ^{m 2.} The amount of the unreacted substance can be measured by, for example, cutting the composite semipermeable membrane into 10 cm × 10 cm, immersing it in 50 g of ethanol for 8 hours, and performing chromatography and mass spectrometry of components extracted in ethanol.

  By the above washing treatment, for example, the treatment time with a 1% aqueous solution of chlorine dioxide is reduced, and the effect of improving the performance is increased. The reaction time is required to be 1 second or more and 24 hours or less from the viewpoint of the productivity of the composite semipermeable membrane, but the concentration can be appropriately adjusted within the range.

  In addition, when the composite semipermeable membrane subjected to the contact step with chlorine dioxide is not in a wet state, it is preferable to contact with water for a necessary time before the treatment so as to be in a sufficiently wet state. Here, the wet state means that water is contained in the film to be treated, and can be quantitatively expressed by the moisture content (= water content in the film / total weight of the film). The water content of the composite semipermeable membrane during the treatment with the organic compound solution is preferably 5% or more, and more preferably 25% or more.

The composite semipermeable membrane obtained by contact with chlorine dioxide in the method of the present invention was allowed to permeate a sodium chloride aqueous solution having a pH of 6.5 and a concentration of 0.2% by weight at an operating pressure of 0.5 MPa. This is particularly effective for a composite semipermeable membrane having a structure with a salt removal rate of 90% or more, and a significant effect of improving water permeability is obtained. As a result, it is possible to obtain a composite semipermeable membrane having excellent water permeability with an excellent salt removal rate and a permeated water amount of 0.8 m ³ / m ² · day or more.

  The composite semipermeable membrane obtained by performing the treatment specified in the present invention is used as a reverse osmosis membrane for separating a solvent and a solute. For example, by using it as a reverse osmosis membrane at an operating pressure of 0.1 to 3.0 MPa, it is possible to remove harmful substances such as inorganic substances and organic substances and precursors thereof contained in raw water.

As described above, when the reverse osmosis membrane treatment is performed, if the operation pressure is lowered, the capacity of the pump to be used is reduced and the power cost is reduced. On the other hand, the membrane tends to be clogged and the permeated water amount tends to decrease with time. On the other hand, when the operating pressure is increased, the power cost increases for the reasons described above, and the amount of permeated water tends to increase. Moreover, if the amount of permeated water is too high, clogging due to fouling of the membrane surface may occur, and if it is low, the cost will be high. Therefore, in order to perform stable operation with reduced operation cost for brine having an osmotic pressure corresponding to a 0.2% by weight aqueous sodium chloride solution, the operating pressure may be in the range of 0.1 to 3.0 MPa. Preferably, it is in the range of 0.1 to 2.0 MPa, more preferably 0.1 to 1.0 MPa. For the same reason, the permeated water amount is preferably in the range of 0.5 to 5.0 m ³ / m ² · d, more preferably 0.6 to 3.0 m ³ / m ² · d. More preferably, it is in the range of 0.8 to 2.0 m ³ / m ² · d.

  Further, in order to efficiently treat the supplied water and reduce the water production cost, the ratio of the permeated water amount to the raw water supply amount, that is, the recovery rate is preferably 80% or more, more preferably 85% or more, and further 90%. The above is good. However, if it exceeds 99.5%, there is a high possibility of clogging due to fouling of the film surface, so it is preferable not to exceed 99.5%.

  In the present invention, the form of the composite semipermeable membrane is not limited and may be a hollow fiber membrane or a flat membrane. In addition, the modified semipermeable membrane obtained by the modification treatment according to the present invention is used by forming an element or a module by a normal method when used for liquid separation, but its form is particularly limited to a module type, a spiral type, etc. Is not to be done.

In the following examples, the salt removal rate was determined from the following equation by measuring the salt concentration in the feed solution and the salt concentration in the permeate.
Salt removal rate (%) = {1− (salt concentration in permeate) / (salt concentration in feed solution)} × 100
The amount of water permeated was expressed as the amount of permeated water (m ³ / m ² · d) permeating the membrane per unit area (m ² ) per unit time (day).

  The amount of unreacted substances in the membrane was measured by cutting the membrane into 10 cm × 10 cm, immersing it in 50 g of ethanol for 8 hours, and performing chromatography and mass spectrometry of the components extracted in ethanol.

<Reference Examples 1-4>
As the microporous support membrane, a fabric-reinforced polysulfone support membrane (ultrafiltration membrane) produced by the following method was used. That is, it consists of a mixed fiber of polyester fiber having a single yarn fineness of 0.5 dtex and polyester fiber of 1.5 dtex, and has a permeability of 0.7 cm ³ / cm ² · second, an average pore diameter of 7 μm or less, a length of 30 cm, and a width of 20 cm. A wet non-woven fabric is fixed on a glass plate, and a solution (2.5 poise: 20 ° C.) having a polysulfone concentration of 15% by weight with a dimethylformamide (DMF) solvent is cast to a total thickness of 200 μm. Immediately, it was immersed in water to produce a polysulfone microporous support membrane.

Next, this microporous support membrane was immersed in an aqueous solution containing 2.0% by weight of m-phenylenediamine and 2.0% by weight of ε-caprolactam for 2 minutes, and then trimesic acid chloride was added to the decane on the surface. The solution dissolved so as to be 0.1% by weight was applied at a rate of 160 cm ³ / m ² , the excess solution was further removed, and a polyamide separation functional layer was formed by polycondensation on the surface. . At this time, the amount of unreacted substances was 0.56 g / m ² . Therefore, the membrane was washed under the washing conditions shown in Table 1 using distilled water as washing water to reduce the amount of unreacted substances (Reference Examples 2 to 4).

The semipermeable membrane having a polyamide separation functional layer thus obtained was subjected to a reverse osmosis test under conditions of 0.5 MPa and 25 ° C. using a 0.2 wt% sodium chloride aqueous solution adjusted to pH 6.5 as raw water. Went. As a result, the water permeability was 0.75 m ³ / m ² · d, and the salt removal rate of sodium chloride was 93.0%.

<Comparative example 1, Examples 1-3>
The semipermeable membrane having the polyamide separation functional layer obtained in Reference Examples 1 to 4 was brought into contact with a 0.5 wt% chlorine dioxide aqueous solution adjusted to pH 8 at room temperature for 2 minutes. The membrane was then removed from the aqueous solution and immediately washed with water and stored at room temperature. When the performance of the obtained composite semipermeable membrane was tested under the same conditions as in the above Reference Example, the water permeability of this membrane and the salt removal rate of sodium chloride were as shown in Table 2, respectively.

<Example 4>
The semipermeable membrane having the polyamide separation functional layer obtained in Reference Example 3 was brought into contact with a 0.5 wt% chlorine dioxide aqueous solution adjusted to pH 3 at room temperature for 2 minutes. The membrane was then removed from the aqueous solution and immediately washed with water and stored at room temperature. When the performance of the obtained composite semipermeable membrane was tested under the same conditions as in the above Reference Example, the water permeability of this membrane was 0.94 m ³ / m ² · d, and the salt removal rate of sodium chloride was 92.4%. It was.

<Examples 5-7>
The semipermeable membrane having the polyamide separation functional layer obtained in Reference Example 3 was brought into contact with a chlorine dioxide aqueous solution having a pH shown in Table 2. The pH was adjusted using sulfuric acid or sodium hydroxide, and the conditions other than the pH were the same as those in Example 1. The water permeability and sodium chloride removal rate of these membranes were as shown in Table 2, respectively.

From the results of Examples 1 to 7 and Comparative Example 1, according to the method of the present invention, after the step of reducing the amount of unreacted substances in the film to 0.5 g / m ² or less, the step of contacting with chlorine dioxide is performed. It is clear that the membrane water permeability can be greatly improved. Furthermore, the improvement of the membrane performance including the improvement of the salt removal rate is remarkable in the pH 6 to pH 10 region.

<Reference Example 5>
Reference Example 1 except that a microporous support membrane was immersed in a 3.4 wt% aqueous solution of m-phenylenediamine for 2 minutes and then a solution of trimesic acid chloride in decane so as to be 0.15 wt% was used. A composite semipermeable membrane was obtained in the same manner as above. The membrane was washed with distilled water at 60 ° C. for 2 minutes. At this time, the amount of unreacted substances was 0.19 g / m ² . The semipermeable membrane having a polyamide separation functional layer obtained in this manner is an aqueous solution containing 3.5% by weight of sodium chloride adjusted to pH 6.5, and the reverse is performed under conditions of 5.5 MPa and 25 ° C. A penetration test was performed. As a result, the water permeability was 0.73 m ³ / m ² / day, and the salt removal rate was 99.7%.

<Example 8>
The semipermeable membrane having the polyamide separation functional layer obtained in Reference Example 5 was brought into contact with a pH 9 chlorine dioxide aqueous solution. The pH was adjusted using sulfuric acid or sodium hydroxide, and the conditions other than the pH were the same as those in Example 1. When a performance test was performed under the same conditions as in Reference Example 5, the water permeability of this membrane was 1.02 m ³ / m ² · d, and the salt removal rate of sodium chloride was 99.7%.

From the result of Example 8, according to the method of the present invention, after the step of reducing the amount of unreacted substances in the membrane to 0.5 g / m ² or less, the step of bringing into contact with chlorine dioxide greatly increases the membrane water permeability. It is clear that this can be improved.

  The composite semipermeable membrane obtained by the method of the present invention is used as a reverse osmosis membrane for separating a solvent and a solute. For example, it is used in a membrane separation method for removing harmful substances such as inorganic substances and organic substances and precursors thereof contained in raw water.

Claims (2)

A method for producing a composite semipermeable membrane, the step of forming a polyamide separation functional layer by polycondensation reaction of a polyfunctional amine and a polyfunctional acid halide on a microporous support membrane, and then in the composite semipermeable membrane A composite half comprising a step of reducing the amount of unreacted substances to 0.5 g / m ² or less, and then a modification treatment step of contacting the polyamide separation functional layer with chlorine dioxide for 1 second to 24 hours. A method for producing a permeable membrane. 2. The composite semipermeable material according to claim 1, wherein the modification treatment step is to bring the polyamide separation functional layer into contact with a solution containing chlorine dioxide, and the solution containing chlorine dioxide is an aqueous solution having a pH of 6 or more and 10 or less. A method for producing a membrane.