KR20010081730A - Fabrication of high permeable reverse osmosis membranes - Google Patents

Abstract

PURPOSE: A manufacturing method of a high-permeability reverse osmosis separation membrane is provided to improve permeation and exclusion efficiency and permeation speed by using a coating solution mixing technique. CONSTITUTION: A non-porous polyamide film is applied on a porous support membrane. The porous support membrane is pretreated by immersing it in a binder solution containing water-soluble aldehyde compound. After immersing the pretreated support in an aqueous solution containing polyamine, it is treated with an organic solution containing acyl halide compound. Then, it is dried to form a polyamide activated film. This film is post-treated by immersing in a solution containing amine, alcohol or acid compounds.

Description

Fabrication method of high permeable reverse osmosis membranes

The present invention relates to a method for manufacturing a highly permeable reverse osmosis membrane, and more particularly, in the preparation of a composite membrane type membrane in which a nonporous polyamide thin film is coated on a porous support membrane, the bonding force between the support and the polyamide thin film. In order to maintain high durability and to maintain high durability, the support is pretreated with a specific binder solution and then immersed in the established coating solution for a predetermined time to form a highly permeable polyamide active layer by surface polymerization to prepare a composite membrane. The composite membrane is treated in an aqueous solution containing amines, alcohols or acids to increase the hydrophilic properties of the membrane, thereby making it possible to effectively perform drinking water production and industrial water separation and purification under low pressure. Preparation of Reverse Osmosis Hollow Fiber Membrane It is about a method.

In general, the separation of a mixture of water and an ionic or low molecular weight nonionic compound is carried out by reverse osmosis membrane separation or low pressure reverse osmosis membrane separation. In general, a widely used polymer is polyvinyl alcohol [ J. Appl. Polym. Sci ., 50 (1993) 1013-1034, polyacrylic acid [ J. Appl. Polym. Sci ., 41 (1990) 2133-2145], cellulose polymers [ J. Membr. Sci. , 106 (1995) 245-257] and amide polymers [ J. Membr. Sci. , 114 (1995) 39-50. These polymers are known to be highly hydrophilic membrane materials because they are polar and have strong hydrogen bonds. Among the above-described polymer materials, cellulose acetate (US Pat. No. 3,494,780, US Pat. No. 3,532,527) and polyamide membrane [US Pat. No. 3,567,632, US Pat. No. 3,948,823, US Pat. No. 4,277,344, US Pat. No. 4,387,024 ] Is the most preferred reverse osmosis membrane.

The structure of the reverse osmosis membrane is divided into asymmetric membrane structure consisting of the most dense structure on the surface of the support layer is made of porous and the pore size decreases toward the surface, and a composite membrane structure coated with a thin nonporous membrane on the porous support membrane. Among them, the composite membrane structure is more commonly used because the membrane formation is relatively easy and the membrane structure can be easily controlled, and a membrane having various performances can be manufactured according to the use. Representative composite membranes are composite membranes (US Pat. No. 3,744,642, US Pat. No. 4,259,183) in which polyamide is coated with a thin film on the polysulfone porous support membrane. Such a composite membrane is prepared by forming a polyamide layer of a crosslinked or uncrosslinked thin film by surface polymerization between a water-soluble monomer of a diamine or a polyamine and a hydrophobic monomer having two or more acyl halide groups on a porous support membrane.

Most reverse osmosis membranes are made of flat membranes and mounted in spiral wound modules for ease of manufacture. In the case of spiral wound modules, the area of the flat membrane that can be mounted in a predetermined space is usually limited to about 300 to 1,000 m 2 / m 3, but in the case of the hollow fiber membrane module, it is 3,600 to 36,000 m 2 / m 3 depending on the diameter of the hollow fiber membrane. Due to the membrane's mounting density, hollow fiber membranes can be mounted in modules of the same size more than 10 times larger than flat membranes.

Although the hollow fiber membrane has the above advantages, it is rarely utilized as a reverse osmosis membrane due to some problems. In general, the shear stress caused by the flow of the feed liquid on the surface of the hollow fiber membrane rather than the flat membrane is very large, the composite membrane requires a strong bonding force between the support and the coating layer. In addition, unlike the flat membrane, since the hollow fiber membrane cannot use a separate mechanical support that can withstand high pressure, an asymmetric membrane made of a material having excellent mechanical properties should be used. A representative membrane is a cellulose acetate membrane. Such cellulose acetate membranes have a low permeation rate, a low salt excretion rate, and a high manufacturing cost, and thus cannot be widely used. In addition, another problem in the preparation of a composite membrane structure in which a thin non-porous membrane is coated on the hollow fiber support membrane is another problem between the hydrophobic support membrane and the reactant aqueous solution when the hollow fiber support membrane is treated with an aqueous solution solution containing a reactant. It's a bitness. If the wettability is not excellent, there is a problem of causing a defect in the active layer formed by surface polymerization when treated with a solution of the organic phase containing other reactants.

In the present invention, in forming a reverse osmosis membrane for separating and refining drinking water and industrial water, the bonding force between the porous support and the polyamide thin film is improved to establish a support pretreatment process for maintaining high durability under high pressure, and the support is used as a reactant. In order to increase the wettability with the solution of the aqueous solution containing, and to formulate the coating solution so that a highly permeable coating active layer can be formed, it has the characteristics of high permeability and salt rejection of strong binding force, and also prepared reverse osmosis pressure Through post-treatment of the separator, the focus is on the development of technology that can further improve the permeability and salt rejection rate of the membrane. Thus, by preparing a reverse osmosis membrane having a high binding force with a support and high permeability and salt rejection ratio, it is intended to solve the problems of the conventional reverse osmosis hollow fiber membrane by maintaining the safety of the membrane even under high shear shear stress and lowering the feed pressure.

Accordingly, an object of the present invention is to provide a method for producing a low pressure reverse osmosis membrane which is effectively applicable to reverse osmosis membrane separation process of an aqueous mixture containing ionic molecules or particles, and particularly useful for separating drinking water and industrial water. .

The present invention provides a method for producing a separator in which a nonporous polyamide thin film is coated on a porous support membrane.

Immersing the porous support in a water-soluble aldehyde compound-containing binder solution to pretreat; Immersing the support pretreated with the binder in a polyamine-containing aqueous solution, and then immersing it in an acyl halide compound-containing organic phase solution, followed by drying at a temperature of 50 to 90 ° C. to form a polyamide active layer; And it is characterized in that the method for producing a reverse osmosis membrane comprising the process of immersing the dried membrane in a post-treatment solution containing an amine, alcohol or acid compound at a temperature of 10 to 50 ℃.

Referring to the present invention in more detail as follows.

The present invention is to prepare a reverse osmosis membrane useful for separation and purification of drinking water and industrial water, to establish a binder system for pretreatment of the support to improve the binding force between the porous support and the polyamide thin film, poly permeability and excellent salt rejection To establish a solution of an aqueous phase containing a reactant capable of forming an amide active layer and a solution of an organic phase comprising another reactant, to establish a coating technique for forming a polyamide active layer on a support, and to improve the permeability of the manufactured composite membrane. It relates to a method for producing a high permeability reverse osmosis membrane according to the establishment of post-treatment technology.

In order to improve the binding force between the support and the polyamide active layer membrane, it is important to select and use a binder that has affinity with the support and is reactive with a part of the reactant contained in the aqueous solution. Thus, in the present invention, a water-soluble aldehyde compound is used as the binder. By pretreatment of the support, the main chain of the aldehyde compound is attached to the coating surface of the support or the adjacent pore wall by physical bonding, and the aldehyde reactor is shared by chemical reaction with the reactant in the aqueous solution to be treated, that is, the amine group or the hydroxyl group. It is connected by a bond, thereby giving a strong bonding force between the polyamide active layer and the support formed by the surface reaction. Due to the strong binding force by the use of this specific binder, even under severe feed solution conditions, the polyamide active layer may not be broken or separated from the support, thereby maintaining durability and securing stability for a long time.

On the other hand, the highly permeable reverse osmosis hollow fiber membrane according to the present invention is prepared by forming a polyamide active layer of a thin film on a porous support by surface polymerization between a water-soluble polyamine having a multifunctional group and a hydrophobic asyl halide having a multifunctional group. In the present invention, two techniques have been developed to manufacture a highly permeable active layer on a support, and the first technique is the development of a coating solution formulation technique for forming a membrane structure capable of exhibiting high permeability characteristics. It is the development of post-treatment technology for the production film to increase the permeability.

As a first technique, the coating solution for forming the polyamide active layer film is composed of two solutions, that is, an aqueous solution containing a monovalent or divalent polyamine, an organic phase solution containing an acyl halide compound, and the like. In order to improve the wettability of the aqueous solution on the support, especially on the surface of the hollow fiber membrane, the aqueous solution contains an emulsifier and a redness enhancer. In order to remove hydrochloric acid generated as a by-product during the surface polymerization between the acyl halide compound and the polyamine, an acid remover such as trivalent amine and sodium hydroxide is included in the aqueous solution.

As a second technique, to improve the permeability of the prepared reverse osmosis membrane by post-treatment of the membrane with a material such as amines, alcohols or acids to increase the hydrophilicity of the active layer to improve the permeation rate of water through the membrane. Particularly, after post-treatment with alcohols or amines and subsequent treatment with aldehydes are more preferable in terms of membrane stability. As a result of the membrane resolution test conducted by the present inventors, the permeability and the salt rejection ratio of the membrane almost changed over time. Rather, it showed slightly improved traits.

The present invention will be described in more detail based on the manufacturing process as follows.

The first process for preparing the reverse osmosis membrane according to the present invention is a process of pretreating the support by immersing the porous support in a water-soluble aldehyde compound-containing binder solution for 1 to 30 minutes, preferably 3 to 10 minutes. At this time, the solution does not enter the support.

The binder used to improve the binding force between the support and the active layer should not change the structure of the support by excessive swelling while having good affinity with the support, and at the same time, it should be reactive with the active layer and connected by covalent bonds by chemical reaction. do. In the present invention, as the binder that satisfies these conditions, a C2-C10 multifunctional water-soluble aldehyde compound is used. Specifically, glutaraldehyde, mugworxaldehyde, adipdialdehyde or phthalaldehyde is used. The above-described aldehyde compound is added to water to prepare a binder solution at a concentration of 1 to 10% by weight, preferably 4 to 8% by weight. In addition, as a reaction catalyst between the binder and the active layer, a small amount of hydrochloric acid may be added at approximately 0.001% to 0.003%.

The second process for preparing the reverse osmosis membrane according to the present invention is a process of forming a polyamide active layer on the pretreated support.

In the present invention, it is advantageous in terms of hydrodynamic or mechanical properties of the membrane that the feed solution to be separated by applying the active layer on the outer surface of the support is supplied from the outside of the support to be permeated into the hollow fiber membrane to allow the permeate to flow inward.

The support pretreated with the binder solution is removed after the surface filtrate is removed and immersed in an aqueous solution containing polyamine or the like for 1 to 10 minutes, preferably 2 to 6 minutes, and then taken out to remove the surface filtrate. Subsequently, it is immersed in an organic phase solution containing an acyl halide compound, treated for 0.1 to 2 minutes, preferably 0.2 to 0.8 minutes, then taken out and completely dried in air, and then heated to 50 to 120 ° C, preferably at a temperature of 50 to 90 ° C. Dry for 30 minutes. As a result, a polyamide active layer is formed on the support to obtain a desired composite membrane.

Aqueous solutions containing polyamines as the table solution are prepared by dissolving ionic emulsifiers, wetting agents, acid removers and the like in addition to polyamines. The polyamine contained in the aqueous solution has two or more monovalent or divalent amine groups, specifically, aliphatic polyamines including ethylenetriamine, triethylenetetraamine, polyethyleneimine, phenylenediamine, and piperazine. Aromatic polyamines, including methylene piperazine, dimethylene piperazine and the like. In order to adjust the physical property of an application | coating active layer, 2 or more types of polyamines may be thrown in and used simultaneously. In particular, in the case of polyethylenimine as a polyamine, it is preferable to use the thing whose molecular weight is 500-20,000 more preferably 1,000-5,000. Examples of the ionic emulsifier include sodium 4-diphenylaminesulfonate, sodium dodecylbenzenesulfonate, sodium lauryl sulfate, polyvinyl alcohol, and the like. Isopropanol, butanol, pentanol, etc. are used as an improvement agent. As the acid remover, inorganic bases such as sodium hydroxide, sodium carbonate, and the like, or trivalent amines including triethylamine, dimethyl piperazine, or the like may be used, or the polyamine may be added as an acid remover. In the aqueous solution described above, the polyamine is contained in an amount of 0.1 to 5% by weight, preferably 0.5 to 2% by weight, the ionic emulsifier is contained in an amount of 0.01 to 1% by weight, preferably 0.05 to 5% by weight, and the redness enhancer is 1 to 30%. The volume% is preferably contained 5 to 20% by volume, the acid remover is contained 0.05 to 5% by weight, preferably 0.3 to 3% by weight.

As another coating solution, an organic phase solution is prepared by dissolving an acyl halide compound in an organic solvent. As the acyl halide compound, a bifunctional aromatic acyl halide compound including terephthaloyl chloride, isophthaloyl chloride, metaphthaloyl chloride and the like, or a trifunctional aromatic acyl halide compound including trimethoyl chloride and the like is used. Preferably, trifunctional trimethoyl chloride alone or a mixture of trimethoyl chloride and another difunctional aromatic acyl chloride compound is used. When the mixture is used, the content of trimethoyl chloride is 50% or more. . In general, in forming a polyamide active layer using a polyamine and an acyl halide compound, the use of the trifunctional compound alone or in combination with the trifunctional compound as the acyl halide compound alone is not used alone. It is known that the excellent but relatively low separation efficiency was a problem. However, in the case of using an aliphatic polyamine having three or more monovalent or divalent amine groups in one molecule as the polyamine contained in the above aqueous solution by the production method according to the present invention, only the difunctional acyl halide compound Even if used, it was possible to prepare an active layer having excellent permeation rate and membrane separation efficiency, which may also be a feature of the present invention. As the organic solvent for dissolving the acyl halide compound, normal hexane, cyclohexane, chlorinated hydrocarbon having 1 to 4 carbons, and the like are used. Preferably, normal hexane can be used. The content of the acyl halide compound in the organic phase solution is 0.01 to 3%, preferably 0.05 to 1%.

Next, as a third process for preparing a reverse osmosis membrane according to the present invention, a post-treatment of the prepared composite membrane is performed.

The aftertreatment solution is prepared by dissolving amines, alcohols or acids in water. Diethylenetriamine, triethylenediamine or triethylenetetraamine may be used as the amine, and ethanol, propanol, butanol, pentanol or triethanolamine may be used as the alcohol, and as acid, acetic acid, citric acid or nitric acid may be used. Use If amine is used, the amine content in the aftertreatment solution is 0.01 to 3%, preferably 0.05 to 1%, and if alcohol is used, the alcohol content is 0.5 to 100%, preferably 5 to 50%, and an acid is used. The acid content in this case is from 0.1 to 10% and preferably from 0.5 to 5%. In particular, when the treatment with an aqueous solution containing alcohols or amines exemplified above, followed by continuous treatment with an aqueous solution containing aldehydes, the stability of the film over time is significantly improved. In this case, the concentration of alcohol or amine is 0.001 to 1%, preferably 0.005 to 0.5%, and the concentration of the aldehyde compound is 0.01 to 1%.

The composite membrane manufactured using the post-processing solution illustrated above is processed for 10 to 90 minutes at the temperature of 10-50 degreeC. The post-treatment method is to immerse the prepared composite membrane in the post-treatment solution at a temperature of 10 to 50 ° C. and atmospheric pressure, or to flow the post-treatment solution to the membrane surface at a temperature of 10 to 50 ° C. and a pressurized condition of 1 to 10 atm. It is. In the case of an aftertreatment solution containing an acid, the former is more effective. In an aftertreatment solution containing an alcohol or an amine, both methods can be used. The effect is almost the same, but the latter is slightly more effective.

After the post-treatment process, the prepared composite membrane is placed in a pure water of 10 ~ 80 ℃ temperature immersed for 30 to 120 minutes to remove the residual material.

In carrying out the above manufacturing process, particular care is required so that the treatment solutions used in each process do not enter the porous support.

On the other hand, the support used in the present invention is an asymmetric structure having a porous and dense surface layer, the diameter of the pores present in the surface layer is preferably 50 nanometer or less, preferably 20 nanometer or less, the material is used for manufacturing a general composite membrane Polymers such as polysulfone, polyetherimide, polyacrylonitrile, cellulose acetate, and polycarbonate used as a support are suitable. The form can use not only a hollow fiber membrane but a flat membrane support.

Although this invention is demonstrated in more detail based on the following Example, this invention is not limited to an Example.

Example 1

Glutalaldehyde and a small amount of hydrochloric acid were dissolved in water to prepare a binder solution having 5% glutaraldehyde and 0.002% hydrochloric acid, and then the polysulfone ultrafiltration hollow fiber membrane support was immersed in the binder solution for 10 minutes to pretreat the support. . At this time, the solution was not allowed to enter the hollow fiber support. The support treated with the binder solution was removed from the surface filtrate and then immersed in an aqueous solution containing 0.7% polyphenylenediamine as polyamine, 0.1% sodium dodecylbenzenesulfonate as emulsifier and 1% as acid remover triethyleneamine. After 3 minutes, the filtrate was removed from the surface. Subsequently, the mixture was immersed in an organic phase solution in which 0.1% of terephthaloyl chloride and 0.3% of trimethoyl chloride were dissolved in normal hexane, taken out after 0.5 minutes, completely dried in air, and dried for 20 minutes at a temperature of 60 ° C. to prepare a composite membrane. The prepared composite membrane was immersed in 20% aqueous solution of triethanolamine for 30 minutes at a temperature of 30 ° C., and then treated. The composite membrane was placed in a pure water at 30 ° C. for 60 minutes to remove residual material to remove the reverse osmosis hollow fiber membrane of the present invention. Prepared.

In addition, the reverse osmosis membrane separation experiment was conducted on the prepared reverse osmosis hollow fiber membranes in which 2000 ppm of salt was dissolved in a continuous feeding process at an operating pressure of 1 MPa and an operating temperature of 25 ° C. The results are shown in Table 1 below.

Examples 2-10

It was prepared in the same manner as in Example 1, except that the composition of the coating solution was changed as shown in Table 1 below. In addition, the prepared reverse osmosis hollow fiber membranes were subjected to the same membrane separation experiment as in Example 1, the results are shown in Table 1 below.

According to Table 1, in the case of the reverse osmosis hollow fiber membranes of Examples 1 to 4 using a mixture of trimethoyl chloride and terephthaloyl chloride as the acyl halide contained in the organic phase solution, a single acyl halide compound was prepared. Compared to the reverse osmosis hollow fiber membranes of Examples 5 to 8 shows a relatively low permeation rate characteristics. The reverse osmosis hollow fiber membranes of Examples 2 to 4 using aliphatic polyamines exhibit somewhat lower permeation rates.

In the reverse osmosis hollow fiber membranes of Examples 6 to 8 using an aliphatic polyamine as the polyamine and a bifunctional terephthaloyl chloride as the alsyl halide alone, the permeation rate was greatly increased and the rejection rate was also increased. The reverse osmosis hollow fiber membrane of Example 1 using a polyamine was observed to decrease the permeation rate rather. Among them, the reverse osmosis hollow fiber membrane of Example 6 prepared using polyethyleneimine has a low permeation rate but an excellent rejection rate, and was prepared using Examples 7 and 8 of diethylenetriamine or triethylenetetraamine. Reverse osmosis hollow fiber membranes have a slightly low rejection rate but have a high permeation rate. Accordingly, the reverse osmosis hollow fiber membranes of Examples 9 and 10 prepared by mixing polyethyleneimine capable of producing a high rejection membrane and diethylenetriamine or triethylenetetraamine capable of producing a high permeability membrane were mixed with each other. It has an even transmission rate and high rejection rate.

Therefore, it is possible to prepare a membrane having high permeability and high exclusion rate by containing an aliphatic polyamine as a polyamine in an aqueous solution and an acyl chloride as an acyl halide in an organic phase solution when preparing the coating solution under the conditions of the above examples. It can be seen that.

Examples 11 and 12

Prepared in the same manner as in Examples 9 and 10, 0.5% of sodium hydroxide was used in place of 1% of the acid remover triethyleneamine. In addition, the prepared reverse osmosis hollow fiber membranes were subjected to the same membrane separation experiment as in Example 1, the results are shown in Table 2 below.

According to Table 2, it can be seen that triethyleneamine is much more effective than sodium hydroxide as an acid remover.

Example 13 and Comparative Example 1

Prepared in the same manner as in Example 10, except that the concentration of glutaraldehyde contained as a binder in the support pretreatment solution was changed as shown in Table 3 below. In addition, for the prepared reverse osmosis hollow fiber membrane was carried out the same membrane separation experiment as in Example 1, the results are shown in Table 3 below.

According to Table 3, the reverse osmosis hollow fiber membrane of Comparative Example 1 prepared without pretreatment of the support with the binder decreased the rejection rate with time, but the membrane was destroyed after 3 hours. In contrast, the reverse osmosis hollow fiber membrane of Example 13 prepared by carrying out a support pretreatment using a binder shows very stable permeation separation characteristics with time.

Examples 14-17 and Comparative Example 2

Prepared in the same manner as in Example 10, except that the prepared composite membrane was immersed in a post-treatment solution as shown in Table 4 for 30 minutes at a temperature of 30 ℃, and then placed in a pure water at a temperature of 30 ℃ Dip for 60 minutes to remove residual material. In addition, for the prepared reverse osmosis hollow fiber membrane was carried out the same membrane separation experiment as in Example 1, the results are shown in Table 4 below.

According to Table 4, the reverse osmosis hollow fiber membrane of Comparative Example 2 prepared without performing the post-treatment process showed a low permeation rate, but was prepared by performing a post-treatment process with an acid, an alcohol, or an amine compound. The reverse osmosis hollow fiber membranes of Examples 14-17 show improved permeation rates. In the reverse osmosis hollow fiber membrane of Example 14 prepared using isopropanol as a post-treatment solution, the permeation rate was increased instead of increasing the permeation rate, but Example 15 prepared using triethyl alcohol amine Reverse osmosis hollow fiber membranes have the effect of improving the permeation rate by about 50% without lowering the rejection rate.

As described above, the reverse osmosis membrane prepared by the manufacturing method according to the present invention has a strong bonding force between the support layer and the polyamide active layer can maintain excellent membrane performance for a long time while maintaining durability even under severe separation process conditions, and also It is possible to manufacture high permeability and high rejection rate membrane by establishing coating solution formulation technology, and it is possible to manufacture membranes having high permeation rate by increasing the permeation rate without lowering rejection rate through post-treatment of the prepared membrane. Large hollow fiber modules can be used to purify water at low pressures, and to achieve a smaller and lower cost for water purifiers, and to extend the scope of application to industrial water recycling and wastewater treatment.

Claims (15)

In the method for producing a separator in which a nonporous polyamide thin film is coated on a porous support membrane, Pretreating the porous support in a water-soluble aldehyde compound-containing binder solution; Immersing the support pretreated with the binder in a polyamine-containing aqueous solution, and then immersing it in an acyl halide compound-containing organic phase solution, followed by drying at a temperature of 50 to 90 ° C. to form a polyamide active layer; And A method of producing a reverse osmosis hollow fiber polyamide composite membrane comprising immersing the dried membrane in a post-treatment solution containing an amine, alcohol, or acid compound and subjecting it to a post-treatment at a temperature of 10 to 50 ° C. The method of claim 1, wherein the support has an asymmetric structure and is a hollow fiber membrane or a flat membrane having a pore diameter of 50 nanometers in the surface layer. The method of claim 1, wherein the water-soluble aldehyde compound is selected from glutaraldehyde, mugwort aldehyde, adipdialdehyde and phthalaldehyde. The method of claim 1 or 3, wherein the content of the aldehyde compound in the binder solution is 4 to 8% by weight. The method of claim 1, wherein the polyamine is an aromatic polyamine selected from aliphatic polyamine, phenylenediamine, piperazine, methylene piperazine and dimethylene piperazine selected from diethylenetriamine, triethylenetetraamine and polyethyleneimine. Method for producing a reverse osmosis membrane. The method of claim 1, wherein the aqueous solution contains 0.5 to 2.0% by weight of polyamine, 0.05 to 5% by weight of ionic emulsifier, 5 to 20% by volume of alcoholic wetting agent, and 0.3 to 3% by weight of acid remover. Method for producing a reverse osmosis membrane. The method of claim 6, wherein the ionic emulsifier is selected from sodium dodecylbenzenesulfonate, sodium lauryl sulfate and polyvinyl alcohol. The method of claim 6, wherein the wetting agent is selected from isopropanol, butanol and pentanol. 7. The method of claim 6, wherein the acid remover is an inorganic base selected from sodium hydroxide and sodium carbonate, a trivalent amine selected from triethylamine and dimethyl piperazine, or an excess polyamine. The method for producing a reverse osmosis hollow fiber polyamide composite membrane according to claim 1, wherein the acyl halide compound contained in the organic phase solution is an aromatic acyl chloride compound having two or three acyl chlorides. The method of claim 10, wherein the aromatic acyl chloride compound is selected from terephthaloyl chloride, isophthaloyl chloride, metaphthaloyl chloride and trimesoyl chloride. The polyfunctional according to claim 1, 5 or 10, wherein an aliphatic polyamine is used as the polyamine, and the acyl halide compound is difunctional selected from terephthaloyl chloride, isophthaloyl chloride and metaphthaloyl chloride. Method for producing a reverse osmosis membrane, characterized in that using an aromatic acyl chloride The method of claim 1, wherein the organic phase solution contains an organic phase solvent in normal hexane and cyclohexane together with an acyl halide compound. The method of claim 1 or 13, wherein the organic phase solution contains an acyl halide compound in an amount of 0.05 to 1% based on the organic phase solvent. The method of claim 1, wherein the amine contained in the aftertreatment solution is selected from diethylenetriamine, triethylenediamine and triethylenetetraamine, the alcohol is selected from ethanol, propanol, butanol, pentanol and triethanolamine, and the acid is Method for producing a reverse osmosis membrane, characterized in that selected from acetic acid, nitric acid and citric acid.