KR102157931B1 - Method for manufacturing water-treatment separation membrane, water-treatment separation membrane manufactured by thereof, and composition for manufacturing water-treatment separation membrane - Google Patents

Abstract

The present invention relates to a composition for interfacial polymerization of a polyamide active layer of a water treatment separation membrane comprising a cyanuric acid compound or a biuret compound, an amine compound, and water.

Description

A method of manufacturing a water treatment separation membrane, a water treatment separation membrane manufactured using the same, and a composition for manufacturing a water treatment separation membrane {METHOD FOR MANUFACTURING WATER-TREATMENT SEPARATION MEMBRANE, WATER-TREATMENT SEPARATION MEMBRANE MANUFACTURED BY THEREOF, AND COMPOSITION FOR MANUFACTURING WATER-TREATMENT SEPARATION}

The present specification relates to a composition for interfacial polymerization of a polyamide active layer of a water treatment separation membrane, a method of manufacturing a water treatment separation membrane, and a water treatment separation membrane manufactured using the same.

The phenomenon that the solvent moves through the separation membrane from the solution with the low solute concentration to the higher solution between the two solutions separated by the semi-permeable membrane is called the osmotic phenomenon.At this time, the pressure acting on the solution side with the high solute concentration due to the movement of the solvent Is called osmotic pressure. However, when an external pressure higher than the osmotic pressure is applied, the solvent moves toward a solution with a low solute concentration, and this phenomenon is called reverse osmosis. Using the reverse osmosis principle, various salts or organic substances can be separated through a semi-permeable membrane using a pressure gradient as a driving force. Water treatment separation membranes using the reverse osmosis phenomenon are used to separate substances at the molecular level and remove salts from salt water or seawater to supply water for households, construction, and industrial use.

A representative example of such a water treatment separation membrane may be a polyamide-based water treatment separation membrane, and the polyamide-based water treatment separation membrane is manufactured by forming a polyamide active layer on a microporous layer support, and more specifically, a polyamide-based water treatment separation membrane. A sulfone layer is formed to form a microporous support, and the microporous support is immersed in an aqueous solution of m-phenylene diamine (mPD) to form an mPD layer, which is again trimesoyl chloride (TriMesoyl Chloride, TMC) It is prepared by immersing in an organic solvent to contact the mPD layer with TMC for interfacial polymerization to form a polyamide layer.

Korean Patent Publication 2014-0005489

In the present specification, a composition for interfacial polymerization of a polyamide active layer of a water treatment separation membrane, a method of manufacturing a water treatment separation membrane, and a water treatment separation membrane manufactured using the same are provided.

An exemplary embodiment of the present specification provides a composition for interfacial polymerization of a polyamide active layer of a water treatment separation membrane comprising a cyanuric acid compound or a biuret compound, an amine compound, and water.

Another exemplary embodiment of the present specification is preparing a porous support;

Coating the composition for interfacial polymerization of the polyamide active layer on the porous support; And

It provides a method for producing a water treatment separation membrane comprising the step of forming a polyamide active layer on the porous support by contacting the composition for interfacial polymerization of the polyamide active layer with an organic solution containing an acyl halide compound to perform interfacial polymerization.

Another exemplary embodiment of the present specification is a porous support; And

It provides a water treatment separation membrane comprising a polyamide active layer including a cyanuric acid compound or a biuret compound provided on the porous support.

Another exemplary embodiment of the present specification provides a water treatment separation membrane manufactured by the method of manufacturing a water treatment separation membrane described above.

Another exemplary embodiment of the present specification provides a water treatment module including the water treatment separation membrane described above.

The water treatment separation membrane according to the exemplary embodiment described in the present specification has an advantage in that the permeate flow rate is increased while maintaining excellent salt removal rate characteristics.

1 shows a water treatment separation membrane according to an exemplary embodiment of the present specification.

Hereinafter, exemplary embodiments of the present specification will be described in more detail.

When a member is referred to herein as being “on” another member, this includes not only the case where a member is in contact with another member, but also the case where another member exists between the two members.

In the present specification, when a part "includes" a certain component, it means that other components may be further included rather than excluding other components unless specifically stated to the contrary.

The composition for interfacial polymerization of the polyamide active layer according to an exemplary embodiment of the present specification may include a cyanuric acid compound or a biuret compound, an amine compound, and water.

In the water treatment separation membrane according to the exemplary embodiments described in the present specification, by adding a cyanuric acid compound or a biuret compound to the aqueous solution when the polyamide active layer is formed, excellent permeation flow rate can be obtained while maintaining the salt removal rate characteristics of the existing water treatment separation membrane.

According to an exemplary embodiment of the present specification, the cyanuric acid compound or the biuret compound is included in the aqueous solution layer, thereby additionally removing by-products generated when the mpD aqueous solution and the TMC organic solution layer are interfacially polymerized, and substances participating in the reaction It is possible to control the reaction rate and reaction while forming a bond with.

According to an exemplary embodiment of the present specification, the content of the cyanuric acid compound or the biuret compound may be 0.01 parts by weight to 5 parts by weight, preferably 0.01 parts by weight to 100 parts by weight of the composition for interfacial polymerization of the polyamide active layer. It may be 2 parts by weight, more preferably 0.01 to 1 part by weight.

According to another exemplary embodiment of the present specification, the content of the cyanuric acid compound may be 0.01 parts by weight to 0.27 parts by weight based on 100 parts by weight of the composition for interfacial polymerization of the polyamide active layer, preferably 0.01 to 0.2 parts by weight. I can.

According to another exemplary embodiment of the present specification, the content of the biuret compound may be 0.1 to 2 parts by weight, and preferably 0.1 to 1 part by weight, based on 100 parts by weight of the composition for interfacial polymerization of the polyamide active layer.

When the cyanuric acid compound and the biuret compound are used in the above range, there is an effect of increasing the permeation flow rate and controlling the reaction.

A method of manufacturing a water treatment separation membrane according to an exemplary embodiment of the present specification includes: preparing a porous support; Coating an aqueous solution containing a cyanuric acid compound or a biuret compound and an amine compound on the porous support; And interfacial polymerization by contacting the composition for interfacial polymerization of the polyamide active layer and an organic solution containing an acyl halide compound to form a polyamide active layer on the porous support.

According to another exemplary embodiment of the present specification, it may further include forming a protective layer on the polyamide active layer.

The step of forming the protective layer may be performed, for example, through a method of immersing the support on which the polyamide active layer is formed in the composition forming the protective layer, or a method of applying a protective layer solution after drying the polyamide active layer. .

According to an exemplary embodiment of the present specification, the aqueous solution and the organic solution may have a coating thickness of 100 to 800 μm, respectively, and may vary depending on the coating concentration or conditions and process conditions, so there is no particular limitation.

According to an exemplary embodiment of the present specification, the thickness of the polyamide active layer may be 0.1 μm to 1 μm, and if it is less than 0.1 μm, the removal rate of the separator decreases, and if it is thicker than 1 μm, the flow rate decreases, thereby deteriorating the function as a separator. I can.

According to an exemplary embodiment of the present specification, the amine compound is not limited as long as it can be used for polymerization of polyamide, but as specific examples, m-phenylenediamine (mPD), p-phenylenediamine (PPD), 1, 3,6-benzenetriamine (TAB), 4-chloro-1,3-phenylenediamine, 6-chloro-1,3-phenylenediamine, 3-chloro-1,4-phenylene diamine, or mixtures thereof Can be preferably used. The content of the amine compound may be 0.1% by weight or more and 20% by weight or less based on 100% by weight of the composition.

According to an exemplary embodiment of the present specification, the step of contacting an aqueous solution containing a cyanuric acid compound or a biuret compound and an amine compound with an organic solution containing an acyl halide compound is known in the art, such as immersion, spray, and coating. Those that are present can be used. When the amine compound and the acyl halide compound are brought into contact, the amine compound and the acyl halide compound react to form polyamide by interfacial polymerization, and are adsorbed on the porous support to form a thin film.

The acyl halide compound is not limited as long as it can be used for polymerization of polyamide, but as a specific example, an aromatic compound having 2 to 3 carboxylic acid halides, trimesoyl chloride, isophthaloyl chloride, and terephthaloyl One or a mixture of two or more selected from the group of compounds consisting of chloride may be preferably used. The content of the acyl halide compound may be 0.05% by weight or more and 1% by weight or less based on 100% by weight of the composition.

The organic solution includes an organic solvent, and the organic solvent includes an aliphatic hydrocarbon solvent such as freon and a hydrophobic liquid that does not mix with water such as hexane, cyclohexane, heptane, and alkanes having 5 to 12 carbon atoms. For example, alkanes having 5 to 12 carbon atoms and mixtures thereof such as IsoPar (Exxon), ISOL-C (SK Chem), ISOL-G (Exxon), etc. may be used, but are not limited thereto.

The aqueous solution containing a cyanuric acid compound or a biuret compound and an amine compound, or an organic solution containing an acyl halide compound may further include a flux improver or a salt removal improver as necessary. As the flux enhancing agent and the salt removal enhancing agent, those known in the art may be used. The content of the flux enhancing agent or the salt removal enhancing agent may be determined according to the type or need, and, for example, 0.01% to 10% by weight may be used based on 100% by weight of the composition.

According to an exemplary embodiment of the present specification, as the porous support, a polymer material coating layer formed on a nonwoven fabric may be used. Examples of the polymer material include polysulfone, polyethersulfone, polycarbonate, polyethylene oxide, polyimide, polyetherimide, polyetheretherketone, polypropylene, polymethylpentene, polymethylchloride and polyvinylidene fluorine. Ride and the like may be used, but are not necessarily limited thereto. Specifically, polysulfone may be used as the polymer material.

According to an exemplary embodiment of the present specification, the thickness of the porous support may be 20 μm to 100 μm, but is not limited thereto and may be adjusted as necessary. In addition, the pore size of the porous support is preferably 1 nm to 500 nm, but is not limited thereto.

An exemplary embodiment of the present specification provides a water treatment separation membrane manufactured by the method of manufacturing a water treatment separation membrane described above.

The water treatment separation membrane according to an exemplary embodiment of the present specification includes a porous support; And a polyamide active layer including a cyanuric acid compound or a biuret compound on the porous support.

1 illustrates the structure of the water treatment separation membrane. According to FIG. 1, the brine 400 passes through the nonwoven fabric 100, the porous support 200 and the polyamide layer 300 of the water treatment separation membrane, so that the concentrated water 600 is removed and the purified water 500 forms the water treatment separation membrane. Obtained through

The water treatment separation membrane may further include an additional layer as needed. For example, the reverse osmosis membrane may further include an antifouling layer provided on the polyamide active layer.

The water treatment separation membrane may be used as a micro filtration membrane, an ultra filtration membrane, a nano filtration membrane, or a reverse osmosis membrane, and specifically, may be used as a reverse osmosis membrane.

According to an exemplary embodiment of the present specification, one or more of the aforementioned water treatment separation membranes may be included in the water treatment module.

The specific type of the water treatment module is not particularly limited, and examples thereof include a plate & frame module, a tubular module, a hollow & fiber module, or a spiral wound module. In addition, as long as the water treatment module includes the water treatment separation membrane according to the exemplary embodiment of the present specification described above, other configurations and manufacturing methods are not particularly limited, and general means known in the art may be employed without limitation. have.

On the other hand, the water treatment module including the water treatment separation membrane manufactured according to the exemplary embodiment of the present specification has excellent salt removal rate and permeation flow rate, and excellent chemical stability, such as household/industrial water purification equipment, sewage treatment equipment, sea desalination equipment, etc. It can be usefully used in water treatment equipment.

Another exemplary embodiment of the present specification provides a composition for interfacial polymerization of a polyamide layer of a water treatment separation membrane that can be used in the manufacturing method according to the above-described exemplary embodiments.

Specifically, the composition for interfacial polymerization of the polyamide layer of the water treatment separation membrane includes a cyanuric acid compound or a biuret compound, an amine compound, and water.

Here, the description of the contents of the cyanuric acid compound or the biuret compound and the amine compound is as described above.

According to another exemplary embodiment of the present specification, the composition for interfacial polymerization of the polyamide layer is water, acetone, dimethyl sulfoxide (DMSO), 1-methyl-2-pyrrolidinone (NMP), hexamethylphosphoamide ( It may further include hexamethylphosphoramide, HMPA), and the like.

Hereinafter, examples will be described in detail to describe the present specification in detail. However, the embodiments according to the present specification may be modified in various forms, and the scope of the present specification is not construed as being limited to the embodiments described below. The embodiments of the present specification are provided to more completely describe the present specification to those of ordinary skill in the art.

Preparation of water treatment separation membrane

Example 1

Based on 100 wt% of the total aqueous solution composition on the polysulfone porous support, 5 wt% of m-phenylene diamine (mPD), 3.6 wt% of TEACSA (Triethylamine) and 10-camposulfonic An aqueous solution containing acid (10-Camphorsulfonic acid) conjugated salt), 0.07 wt% of sodium lauryl sulfate (SLS), 0.1 wt% of cyanuric acid and the rest of distilled water was applied.

Then, based on 100 wt% of the total organic solution composition, an organic solution containing 0.25 wt% of trimesoyl chloride (TMC), 4 wt% of trimethylbenzene (TMB), and the rest of the iso par G organic solution. The solution was coated and subjected to interfacial polymerization to obtain a polyamide layer.

After drying the polyamide layer, a water treatment separation membrane was obtained.

Example 2

A water treatment separation membrane was obtained in the same manner as in Example 1, except that the content of cyanuric acid was adjusted to 0.2 wt%.

Example 3

A water treatment separation membrane was obtained in the same manner as in Example 1, except that cyanuric acid was not added and a burette was added in an amount of 0.3 wt%.

Example 4

A water treatment separation membrane was obtained in the same manner as in Example 3, except that the content of the burette was adjusted to 1.0 wt%.

Comparative Example 1

A water treatment separation membrane was obtained in the same manner as in Example 1, except that cyanuric acid was not added.

After stabilization of the water treatment separation membrane including the obtained polyamide active layer, the salt removal rate (rejection) and the permeation flow rate (flux) were measured and shown in Table 1 below.

The salt removal rate and permeate flow rate were measured after a stabilization time for one day under the conditions of pH 7.5 and a pressure of 225 psi of an aqueous solution containing 2000 ppm NaCl and 100 ppm NaHCO 3, and are shown in Table 1 below.

Salt removal rate (%) Permeate flow rate (GFD) Example 1 99.78 13.19 Example 2 99.79 11.75 Example 3 99.75 13.72 Example 4 99.67 13.43 Comparative Example 1 99.72 11.52

As shown in Table 1, in the case of Examples 1 to 4 including cyanuric acid or biuret in the aqueous solution, compared to Comparative Example 1 not containing cyanuric acid or biuret, it showed an equivalent level of salt removal rate, It can be seen that the permeate flow rate has increased.

100: non-woven
200: porous support
300: polyamide active layer
400: brine
500: purified water
600: concentrated water

Claims (6)

(a) a cyanuric acid compound or a biuret compound; (b) an amine compound; And (c) a composition for interfacial polymerization of a polyamide active layer of a water treatment separation membrane comprising water. The method according to claim 1, wherein (a) the content of the cyanuric acid compound or the biuret compound is 0.01 parts by weight to 5 parts by weight based on 100 parts by weight of the composition for interfacial polymerization of the polyamide active layer. Composition. Preparing a porous support;
Coating the composition for interfacial polymerization of the polyamide active layer of claim 1 or 2 on the porous support; And
Forming a polyamide active layer on the porous support by contacting the composition for interfacial polymerization of the polyamide active layer with an organic solution containing an acyl halide compound to perform interfacial polymerization
A method of manufacturing a water treatment separation membrane comprising a. A water treatment separation membrane manufactured by the method of manufacturing a water treatment separation membrane according to claim 3. Porous support; And
Water treatment separation membrane comprising a polyamide active layer comprising a cyanuric acid compound or a biuret compound provided on the porous support. A water treatment module comprising a water treatment separation membrane according to claim 5.

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