KR20110079141A - Manufacturing method of polyamide composite membrane and composite membrane thereby - Google Patents

Abstract

PURPOSE: A producing method of a polyamide system composite film, and the polyamide system composite film are provided to secure the high flux at the low driving pressure. CONSTITUTION: A producing method of a polyamide system composite film comprises the following steps: preparing an aqueous solution obtained by mixing polyamine, class 3 polyamine salt, and polar solvents, and coating the solution on a porous supporter; and contacting the porous supporter with an organic solution containing a poly-functional acid halide compound and a non-ionizing solvent for obtaining a polyamid layer.

Description

Manufacturing Method of Polyamide Composite Membrane and Composite Membrane Thereby {MANUFACTURING METHOD OF POLYAMIDE COMPOSITE MEMBRANE AND COMPOSITE MEMBRANE THEREBY}

The present invention relates to a method for preparing a polyamide-based composite membrane and to a composite membrane, and more particularly, applying an aqueous solution including a polyamine, a tertiary polyamine salt, and a polar solvent to a surface of a porous support; And forming a polyamide layer by interfacial polymerization by contacting the porous support coated with the aqueous solution with an organic solution containing a polyfunctional acid halogen compound and a non-polar solvent, and a composite membrane therefrom. It is about.

As the conventional water treatment membranes, reverse osmosis membranes, nano separation membranes, ultrafiltration membranes, microfiltration membranes, etc. may be mentioned. Recently, nano separation membranes and forward osmosis membranes are emerging as a new field of interest due to the superior performance compared to required energy. Nano-membrane is derived from the concept of nano filtration, and the main separation object of nano-membrane is divalent ion having solute size of nanometer (nm), or various kinds of monosaccharides and low molecular weight organic materials. This can be called.

The nano separation membrane is a membrane whose filtration range is present at the boundary between the reverse osmosis membrane and the ultrafiltration membrane, and may be particularly applied to remove minerals from water with low pollution, separation of antibiotic substances, ultrapure water production, or heavy metal washing. Of course, reverse osmosis membranes can also separate these materials, but because the selective separation ability of the nanometer-specific solutes is lower than that of the nanomembrane and the operating pressure must be higher than that of the nanomembrane, the energy consumption is much higher than that of the nanomembrane process. have. Therefore, it is a natural phenomenon that the nano-membrane that can separate a larger amount of material at a relatively low pressure has recently been in the spotlight.

In addition, interest in the concept and process development of the forward osmosis membrane using the osmotic pressure is increasing. The forward osmosis membrane induces the flow of water by the difference in concentration between the two ends of the membrane, and it is known that the concentration polarization phenomenon must be minimized in order to improve the permeate flow rate. To this end, it is necessary to control the membrane thickness and improve the permeation characteristics of the active layer. It can be said to contribute to this.

There are a number of methods for producing a polyamide composite membrane, and among them, Cadette has disclosed a method for preparing a composite membrane by reacting piperazine with TMC / IPC in US Pat. No. 4,259,183. There are a number of known patents that improve the physical properties through additives and post-treatment. For example, US Pat. Nos. 4,765,897, 4,812,270, and 4,824,574 are post-treated with inorganic strong acids and rejection enhancers, and US Pat. No. 6,280,853 uses an oxide material to post-treat the membrane. A method of treatment coating is introduced.

In addition, U.S. Patent Nos. 4,769,148 and 4,859,384 disclose a technique for inducing a flow rate increase by adding a cationic wetting agent to the piperazine layer during membrane preparation.

In addition, US Pat. Nos. 4,619,767 and 4,737,325 disclose a method for preparing a composite membrane by interfacial reaction between PVA / amino compound and TMC, not interfacial reaction between MPD and TMC.

US Patent No. 4,950,404 discloses a method for producing a highly permeable membrane by increasing the flexibility of the support layer by including a polar aprotic solvent in an aqueous solution.

In addition, US Pat. No. 6,113,794 discloses a manufacturing method for coating a hydrophilic polymer using polyacrylonitrile as a supporting layer.

Some techniques for obtaining good salt rejection and sufficient flow rates of composite membranes, for example, studies of changing the structure of monomers added to polyamide reactions (US Pat. Nos. 4,761,234, 4,634,829, 5,019,264, 5,160,619) , 5,271,843, 5,336,409, etc., a method of increasing the flow rate through post-treatment (US Pat. Nos. 4,938,872, 927,540), and researches for developing substances to be added during preparation (US Pat. Nos. 5,234,598, 5,258,203) In addition, there are techniques for increasing the inherent performance of the separator by adding various additives to the aqueous solution layer.

 As a technology for preparing an osmosis membrane using osmotic pressure, US Pat. No. 7,445,712 discloses a method of preparing a membrane in the form of an asymmetrical single membrane using cellulose acetate and cellulose triacetate used in the preparation of reverse osmosis membrane. Since the polyamide composite membrane is excellent in the salt excretion property, forward osmosis membrane development using the same has been in progress.

However, the composite membranes designed or manufactured by the aforementioned patents have a reduction in salt excretion rate when the flow rate is improved, and thus, there is a need for improvement in terms of process efficiency or energy due to the flow rate improvement.

An object of the present invention is to provide a method for producing a polyamide-based composite membrane that can permeate a high flow rate while maintaining a salt excretion rate when applied to water treatment.

Another object of the present invention is to provide a polyamide-based composite membrane produced by the above method.

Method for producing a composite membrane of the present invention for achieving the above object comprises the steps of applying an aqueous solution containing a polyamine, a tertiary polyamine salt and a polar solvent on the surface of the porous support; And forming a polyamide layer by interfacial polymerization by contacting the porous support coated with the aqueous solution with an organic solution including a polyfunctional acid halogen compound and a non-polar solvent.

The porous support is preferably cast one component selected from the group consisting of polysulfone, polyethersulfone, polyimide, polypropylene and polyvinylidene fluoride on the polyester nonwoven fabric.

The polyamine is preferably one or more selected from the group consisting of phenylenediamine, cyclohexanediamine, piperazine and derivatives thereof in an amount of 0.1 to 10% by weight based on the total weight of the aqueous solution.

The tertiary polyamine salts include 1,4-diazabicyclo [2,2,2] octane (DABCO), 1,8-diazabicyclo [5,4,0] undec-7-ene (DBU), 1, 5-diazabicyclo [4,3,0] non-5-ene (DBN), 1,4-dimethylpiperazine, 4- [2- (dimethylamino) ethyl] morpholine, N, N, N ', N'-tetramethylethylenediamine, N, N, N ', N'-tetramethyl-1,3-butanediamine, N, N, N', N'-tetramethyl-1,4-butanediamine (TMBD) , N, N, N ', N'-tetramethyl-1,3-propanediamine, N, N, N', N'-tetramethyl-1,6-hexanediamine (TMHD), 1,1,3, A salt formed by reaction of a strong acid with at least one selected from the group consisting of 3-tetramethylguanidine (TMGU) and N, N, N ', N', N "-pentamethyldiethylenetriamine, It is preferably contained 0.01 to 2% by weight relative to the.

The polar solvent is at least one selected from the group consisting of ethylene glycol derivatives, propylene glycol derivatives, 1,3-propanediol derivatives, sulfoxide derivatives, sulfone derivatives, nitrile derivatives, ketone derivatives and urea derivatives based on the total weight of the aqueous solution 0.01 It is preferable that 1 weight% is contained.

The polyfunctional acid halogen compound is preferably one or more selected from the group consisting of isophthaloyl chloride, trimesoyl chloride and terephthaloyl chloride in an amount of 0.01 to 1% by weight based on the total weight of the organic solution.

The nonpolar solvent is dihydrofuran, dihydropyrane, toluene, hexane, diphenyl ether, octyl ether, dimethylformaldehyde, tetrahydrofuran, 1-octadecene, tetradecane and derivatives thereof. It is preferable that one or more selected from the group consisting of 0.5 to 5% by weight based on the total weight of the organic solution.

The organic solvent constituting the organic solution is 5 to 12 carbon atoms, it is preferable that the saturated, unsaturated hydrocarbons are linear, branched or cyclic, or a mixture of hydrocarbons in this range.

The composite membrane of the present invention is a porous support; And a polyamide layer formed by interfacial polymerization by contacting an aqueous solution including a polyamine, a tertiary polyamine salt, and a polar solvent on the surface of the porous support, and an organic solution including a polyfunctional acid halogen compound and a nonpolar solvent.

The polyamide-based composite membrane of the present invention contains a tertiary polyamine salt and a polar solvent in an aqueous solution during interfacial polymerization, and further contains a nonpolar solvent in addition to the acid halide compound in the organic solution to interfacially polymerize to form a polyamide layer. The salt rejection rate can be maintained while improving the performance, so that the high flow rate can be transmitted under a relatively low driving pressure.

Polyamide-based composite membrane production method of the present invention for achieving the above object comprises the steps of applying an aqueous solution containing a polyamine, a tertiary polyamine salt and a polar solvent on the surface of the porous support; And forming a polyamide layer by interfacial polymerization by contacting the porous support coated with the aqueous solution with an organic solution including a polyfunctional acid halogen compound and a non-polar solvent.

The first step in the method for producing a polyamide-based composite membrane of the present invention is to apply an aqueous solution containing a polyamine, a salt of a tertiary polyamine, and a polar solvent to the surface of the porous support. In this case, the porous support serves to support the polyamide membrane formed by interfacial polymerization. In the present invention, a functional group-containing polymer is bonded to the surface of the porous support in the form of a nonwoven fabric as a support. The material of the nonwoven fabric is not particularly limited, and any of natural fibers and synthetic fibers may be used. In terms of economy, artificial fibers are commonly used, and nonwoven fabrics using fibers such as polypropylene, polyethylene, nylon, polyester, and polyurethane as synthetic fiber nonwoven fabrics for a support are common. Glass fibers or the like may be used as necessary, and these may be used alone or in combination of several species.

As the functional group-containing polymer bonded to the surface of the nonwoven fabric, one or more components selected from the group consisting of polysulfone, polyethersulfone, polyimide, polypropylene and polyvinylidene fluoride are preferably cast. These polymers can be used as a support because they are easy to manufacture porous and have chemical resistance. Typically, the nonwoven fabric is prepared by knife casting a solution containing 15 to 20% by weight of a functional group-containing polymer.

On the other hand, the porous support used in the composite membrane production method of the present invention preferably has a pore size of 1 ~ 500nm of the support layer. The pore size of more than 500 nm may be manifested as a defect of the final composite film due to depression during thin film formation.

The polyamine is one component that is interfacially polymerized to form a polyamide layer. In general, a polyamide-based composite membrane is formed by interfacial polymerization between a polyamine and a polyfunctional acid halide, wherein the polyamine refers to a polyfunctional primary or secondary amine having 2-3 amine functional groups per monomer. Examples of the primary or secondary polyamines include aromatic primary diamines which are metaphenylenediamine, paraphenylenediamine and derivatives thereof; Aliphatic primary diamines such as ethylenediamine; Cycloaliphatic primary diamines such as cyclohexanediamine; Cycloaliphatic secondary amines such as piperazine; Aromatic secondary amines such as N, N'-dimethyl-1,3-phenylenediamine and the like can be used.

These may be used alone or in combination of two or more thereof, and are used in an amount of 0.1 to 10% by weight, preferably 0.5 to 2% by weight based on the total weight of the aqueous solution. If the content is less than 0.1% by weight, polyamide layer formation is not stable. If the content is more than 10% by weight, the polyamide layer is thick and the permeate flow rate of the finally formed composite membrane is reduced.

When the tertiary polyamine salt forms a membrane composed of a polyamide layer by interfacial polymerization of a polyamine and a polyfunctional acid halide, the third polyamine salt serves to form pores in the membrane to improve flow rate. In addition, it serves to promote the interfacial reaction by performing the acid acceptor action of the acid generated during the interfacial polymerization reaction. Salts of tertiary polyamines for this purpose include 1,4-diazabicyclo [2,2,2] octane (DABCO), 1,8-diazabicyclo [5,4,0] undec-7-ene (DBU). ), 1,5-diazabicyclo [4,3,0] non-5-ene (DBN), 1,4-dimethylpiperazine, 4- [2- (dimethylamino) ethyl] morpholine, N, N , N ', N'-tetramethylethylenediamine, N, N, N', N'-tetramethyl-1,3-butanediamine, N, N, N ', N'-tetramethyl-1,4-butane Diamine (TMBD), N, N, N ', N'-tetramethyl-1,3-propanediamine, N, N, N', N'-tetramethyl-1,6-hexanediamine (TMHD), 1, At least one selected from the group consisting of 1,3,3-tetramethylguanidine (TMGU) and N, N, N ', N', N "-pentamethyldiethylenetriamine is preferably a salt produced by reaction with a strong acid Do.

The tertiary polyamine salt used in the present invention is a reaction product between a strong acid and a tertiary polyamine. A reaction product prepared by reacting a tertiary polyamine having a strong acid with n amine groups in a molar ratio of 1: n (n is 0.5 to 2). to be. At this time, it is preferable to use aliphatic sulfonic acid, aromatic sulfonic acid, cyclo-aliphatic sulfonic acid, trifluoroacetic acid, nitric acid, hydrochloric acid, sulfuric acid, or a mixture thereof.

The tertiary polyamine salts may be used alone or in combination of two or more thereof, and the amount of the tertiary polyamine salt is preferably contained in an amount of 0.01 to 2% by weight based on the total weight of the aqueous solution. If the content of the tertiary polyamine salt is less than 0.01% by weight, it is not preferable to form an appropriate membrane pore, and when the content of the tertiary polyamine salt exceeds 2% by weight, the removal performance is not increased due to a rapid flow rate increase.

In the polyamide-based composite membrane production method of the present invention, the aqueous solution applied to the porous support includes a polar solvent as an additional component. Polar solvents function by activating the interfacial polymerization by affecting the interfacial tension between aqueous and organic solutions. The polar solvent is preferably at least one selected from the group consisting of ethylene glycol derivatives, propylene glycol derivatives, 1,3-propanediol derivatives, sulfoxide derivatives, sulfone derivatives, nitrile derivatives, ketone derivatives and urea derivatives. The amount of use is preferably 0.01 to 1% by weight, more preferably 0.05 to 0.5% by weight based on the total weight of the aqueous solution. If the content of the polar solvent is less than 0.01% by weight, the surface activity is weak, which is not preferable. If the content of the polar solvent exceeds 1% by weight, the removal performance of the ionic material is lowered.

Examples of the ethylene glycol derivatives include 2-methoxyethanol, 2-ethoxyethanol, 2-propoxyethanol, 2-butoxyethanol, di (ethylene glycol) -t-butylmethyl ether and di (ethylene glycol). Hexyl ether, (2-methoxyethyl) ether, (2-ethoxyethyl) ether and the like.

Examples of the 1,3-propanediol derivatives include 1,3-heptanediol, 2-ethyl-1,1-hexanediol, 1,3-hexanediol, 1,3-pentanediol, and the like.

Examples of the sulfoxide derivatives include dimethyl sulfoxide, tetramethylene sulfoxide, butyl sulfoxide and methylphenyl sulfoxide.

 Examples of the sulfone derivatives include dimethyl sulfone, tetramethylene sulfone and butyl sulfone.

Examples of the nitrile derivatives include acetonitrile, propionitrile and the like.

Examples of the urea derivatives include 1,3-dimethyl-2-imidazolidinone and the like, and examples of the ketone derivatives include acetone, 2-butanone, 2-hexanone, 3-hexanone, and 3; -Pentanone, cyclohexanone, cyclopentanone and the like.

It is preferable to adjust the pH of the 2nd polyfunctional amine aqueous solution of this invention to the range of 7-10. Below pH 7, the permeate flow rate decreases, and above pH 10, the removal rate is reduced by hydrolysis. At this time, pH is adjusted by putting a basic substance. However, it is not necessary to add a basic substance when the aqueous solution contains a salt of an amine in which one or more amine groups can act as an acid acceptor.

In the first step of the present invention, there is no particular limitation on the method in which the aqueous solution containing the composition is applied to the porous support. For example, various coating methods such as dipping, spray coating, roll brush coating, gravure coating, knife coating and the like may be appropriately selected. On the other hand, when the aqueous solution is excessively applied to the support in excess of the required amount may be added a process in which the excess solution can be removed by a suitable method. For example, the excess solution may be removed by pressing with a rubber plate or the like or passing the nip roller.

On the other hand, the second step in the composite membrane production method of the present invention is to form a polyamide layer by interfacial polymerization by contacting the porous support coated with the aqueous solution described above in contact with the organic solution containing a polyfunctional acid halogen compound and a non-polar solvent It includes a step.

In the above, first, the organic solvent constituting the organic solution including another raw material of interfacial polymerization is a saturated or unsaturated hydrocarbon having 5 to 12 carbon atoms, and is a chain, branched or cyclic, or a mixture of hydrocarbons belonging to this range. Do. Representatives are, for example, hexane and heptane. Commercially available isopar solvent (Isopar Series, manufactured by ExxonMobil). The isopha solvent is a mixture of 8 to 12 carbon atoms, and a material having a low boiling point may cause a fire. Thus, the isopha solvent is preferably used for the purpose of avoiding this.

The polyfunctional acid halogen compound is another reactant of interfacial polymerization which forms a polyamide layer by contacting and polymerizing at the interface with the polyamine described above. In the production method of the present invention, it is preferable to use at least one selected from the group consisting of isophthaloyl chloride, trimesoyl chloride and terephthaloyl chloride. The amount of the polyfunctional acid halogen compound is preferably contained in an amount of 0.01 to 1% by weight based on the total weight of the organic solution.

On the other hand, the non-polar solvent contained in the organic solution induces stable polymerization during interfacial polymerization and serves to reduce the defect of the support. The nonpolar solvent is selected from the group consisting of, for example, dihydrofuran, dihydropyran, toluene, hexane, diphenyl ether, octyl ether, dimethylformaldehyde, tetrahydrofuran, 1-octadecine, tetradecane and derivatives thereof. It is preferred that one or two or more mixtures be used. As the dihydrofuran derivative, for example, the nonpolar solvent is 2,3-dihydrofuran, 2,5-dihydrofuran, 2,3-dihydro-5-methylfuran, 2,5-dimethoxy-2, 5-dihydrofuran; Examples of the dihydropyran derivatives include 3,4-dihydro-2-ethoxy-2H-pyran, 3,4-dihydro-2H-pyran, 2,3-dihydropyran and the like.

The nonpolar solvent is preferably contained in 0.5 to 5% by weight based on the total weight of the organic solution. At this time, if the content of the nonpolar solvent is less than 1% by weight, it does not affect the formation of the interfacial polymerization. Therefore, the flow rate is not improved. There is a difficulty in lowering the removal performance because of the defect.

Polyamide-based composite membrane of the present invention prepared by the above method is a porous support; And a polyamide layer formed by interfacial polymerization by contacting an aqueous solution including a polyamine, a tertiary polyamine salt, and a polar solvent on the surface of the porous support, and an organic solution including a polyfunctional acid halogen compound and a non-polar solvent.

      The polyamide layer has a thickness of 100 to 300 nm and forms a pore size of 1 to 100 mm 3.

Hereinafter, the present invention will be described in detail by Examples and Experimental Examples. The following Examples and Experimental Examples are only illustrative of the present invention, and the scope of the present invention is not limited to the following Examples and Experimental Examples.

< Example  1>

On the polyester nonwoven fabric, 18 wt% of polysulfone containing solution was cast to 50 ± 10 μm thick in dimethylformamide as a solvent, and immediately immersed in a distilled water bath at 25 ° C. to solidify. The support was prepared. Thereafter, the nonwoven fabric-reinforced polysulfone microporous support was sufficiently washed with water to replace the solvent and water in the substrate, and then dried at room temperature and stored in pure water. The polysulfone microporous support thus obtained was obtained with 0.9% by weight of meta-phenylenediamine (MPD), 1.1% by weight of N, N, N ', N'-tetramethyl-1,6-hexadiamine (TMHD), 0.99% by weight. The water layer on the surface was removed by immersion compression for 20 seconds in an aqueous polyfunctional amine solution containing% toluenesulfonic acid (TSA) and 0.19% by weight of 2-ethyl-1,3-hexanediol (EHD) as a polar solvent.

The support was immersed in an organic solution in which 0.1% by weight of trimezoyl chloride (TMC) and 1% by weight of 2,3-dihydrofuran (DHF) was dissolved in an isopar solvent for 1 minute, followed by excess organic The solution was removed and dried in air for 1 minute to form a polyamide separator. The membrane obtained by the above method was immersed in 0.2 wt% sodium carbonate-containing base aqueous solution at room temperature for 2 hours, and then washed with distilled water to prepare a composite membrane. The performance of the obtained composite membrane was measured at 25 ℃, 75psi aqueous sodium chloride (NaCl) solution of 2,000ppm, the result was 95.08% salt rejection, 19.92 gfd permeation rate.

< Example  2>

A composite membrane was prepared in the same manner as in Example 1, except that 2,3-dihydrofuran (DHF) was changed in Example 1 as shown in Table 1 above.

< Example 3 ~ 4>

A composite membrane was prepared in the same manner as in Example 1, except that in Example 1, the concentration of the aqueous solution layer and 2,3-dihydrofuran were added to the organic solution layer.

< Comparative example  1 ~ 2>

The composite was carried out in the same manner as in Example 1, except that a polyfunctional aqueous amine solution prepared according to the composition and its content shown in Table 1 below was used and only trimezoyl chloride (TMC) was used for the organic solution layer. The membrane was prepared.

< Experimental Example  1>

For the composite membranes prepared in Examples 1 to 4 and Comparative Examples 1 and 2, using a 2,000 ppm sodium chloride (NaCl) aqueous solution, the performance evaluation of the membrane, such as permeation flux and salt excretion rate at 25 ℃, 75 psi conditions It measured and the result is shown in following Table 1.

Table 1

division Aqueous solution layer (wt%) Organic solution layer (wt%) Permeate Flow Rate
(gfd)
Salt removal rate
(%) MPD TSA TMHD EHD TMC DHF Example 1 0.9 0.99 1.1 0.19 0.1 One 19.92 95.08 Example 2 0.9 0.99 1.1 0.19 0.1 3 21.68 95.06 Comparative Example 1 0.9 0.99 1.1 0.19 0.1 0 18.76 95.06 Example 3 1.47 1.47 1.33 0.2 0.1 3 16.31 96.24 Example 4 1.47 1.47 1.33 0.2 0.1 5 16.06 95.28 Comparative Example 2 1.47 1.47 1.33 0.2 0.1 0 13.05 95.96

As shown in Table 1, by containing the DHF in the appropriate concentration range in the organic solution layer of the present invention, it was confirmed that the permeation flux improved effectively without loss of salt removal rate.

Therefore, when the composite membrane prepared by the present invention is applied to water treatment and seawater desalination processes, the same flow rate or higher flow rate can be obtained at a relatively lower pressure than conventional products, resulting in energy saving effect, process efficiency improvement, and treatment cost. Can bring about savings.

While the invention has been shown and described with reference to certain exemplary embodiments thereof, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention as defined by the appended claims.

Polyamide-based composite membrane prepared according to the present invention can be applied to industrial water, drinking water, food manufacturing process fields to which the conventional nano separation membrane and reverse osmosis membrane is applied, operating the forward osmosis process using osmotic pressure using high salt excretion characteristics In addition, it can be applied to a wide range of applications such as wastewater treatment, seawater desalination pretreatment, food manufacturing process, and concentration process.

Claims (14)

Applying an aqueous solution comprising a polyamine, a tertiary polyamine salt, and a polar solvent to the surface of the porous support; And A method of manufacturing a polyamide-based composite membrane comprising forming a polyamide layer by interfacial polymerization by contacting the porous support coated with the aqueous solution with an organic solution containing a polyfunctional acid halogen compound and a non-polar solvent. The method of claim 1, wherein the porous support is a synthetic fiber nonwoven fabric A method for producing the polyamide-based composite membrane, characterized in that one component selected from the group consisting of polysulfone, polyethersulfone, polyimide, polypropylene and polyvinylidene fluoride is cast on it. The method of claim 1, wherein the polyamine is at least one selected from the group consisting of phenylenediamine, cyclohexanediamine, piperazine, and derivatives thereof. The method of claim 3, wherein the content of the polyamine in the aqueous solution is 0.1 to 10% by weight. The salt of claim 1 wherein the salt of the tertiary polyamine is 1,4-diazabicyclo [2,2,2] octane (DABCO), 1,8-diazabicyclo [5,4,0] undec-7- En (DBU), 1,5-diazabicyclo [4,3,0] non-5-ene (DBN), 1,4-dimethylpiperazine, 4- [2- (dimethylamino) ethyl] morpholine, N, N, N ', N'-tetramethylethylenediamine, N, N, N', N'-tetramethyl-1,3-butanediamine, N, N, N ', N'-tetramethyl-1, 4-butanediamine (TMBD), N, N, N ', N'-tetramethyl-1,3-propanediamine, N, N, N', N'-tetramethyl-1,6-hexanediamine (TMHD) At least one selected from the group consisting of 1,1,3,3-tetramethylguanidine (TMGU) and N, N, N ', N', N "-pentamethyldiethylenetriamine is a salt formed by reaction with a strong acid Method for producing the polyamide-based composite membrane, characterized in that. The method of claim 1, wherein the tertiary polyamine salt is contained in an amount of 0.01 to 2% by weight based on the total weight of the aqueous solution. According to claim 1, wherein the polar solvent is one or more selected from the group consisting of ethylene glycol derivatives, propylene glycol derivatives, 1,3-propanediol derivatives, sulfoxide derivatives, sulfone derivatives, nitrile derivatives, ketone derivatives and urea derivatives Method for producing the polyamide-based composite membrane, characterized in that. The method of claim 1, wherein the polar solvent is contained in an amount of 0.01 to 1% by weight based on the total weight of the aqueous solution. The method of claim 1, wherein the polyfunctional acid halogen compound is at least one selected from the group consisting of isophthaloyl chloride, trimezoyl chloride and terephthaloyl chloride. The method according to claim 1, wherein the polyfunctional acid halogen compound is contained in an amount of 0.01 to 1% by weight based on the total weight of the organic solution. The group of claim 1, wherein the nonpolar solvent is dihydrofuran, dihydropyran, toluene, hexane, diphenyl ether, octyl ether, dimethylformaldehyde, tetrahydrofuran, 1-octadecene, tetradecane and derivatives thereof. Method for producing the polyamide-based composite membrane, characterized in that at least one selected from. The method according to claim 1, wherein the nonpolar solvent is contained in an amount of 0.5 to 5% by weight based on the total weight of the organic solution. The polyamide-based composite according to claim 1, wherein the organic solvent constituting the organic solution has 5 to 12 carbon atoms, and is a saturated, unsaturated hydrocarbon which is linear, branched or cyclic, or a mixture of hydrocarbons in this range. Method of Making Membranes. Porous support; And A polyamide type comprising a polyamide layer formed by interfacial polymerization by contacting an aqueous solution containing a polyamine, a tertiary polyamine salt, and a polar solvent on the surface of the porous support, and an organic solution containing a polyfunctional acid halogen compound and a nonpolar solvent. Composite membrane.