KR101522463B1 - Pressure retarded osmosis membrane aggregates with high flow and pressure retarded osmosis module comprising the same - Google Patents

Abstract

The present invention relates to a high-flow-rate pressure-delayed osmotic membrane assembly, and more particularly, to an osmotic membrane assembly having improved flow rate inside an osmotic membrane, It is possible to promote a uniform flux along the flow path and promote the turbulence along the flow path to increase the flow rate at the osmotic membrane surface to minimize the concentration polarization at the osmotic membrane surface, The present invention relates to a high flow rate pressure delayed osmotic membrane assembly in which the damage of the inner surface of the membrane is minimized and the separation of different bonded osmotic membranes that may occur by forming a separate flow path inside the osmotic membrane is minimized.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a high flow rate pressure delayed osmotic membrane assembly and a pressure delayed osmosis membrane module including the same,

The present invention relates to a high flow rate pressure delayed osmotic membrane assembly, and more particularly, to an osmotic membrane assembly having improved pressure resistance and improved pressure resistance so that osmotic action can be smoothly performed even when the pressure vessel is formed into a spiral form. To a high flow rate pressure delayed osmotic membrane assembly in which damage to the osmotic membrane is minimized by pressure.

If a semi-permeable membrane that transmits water but does not substantially permeate the solute (ions and molecules) dissolved in water is installed between the high concentration solution and the low concentration solution, the solvent of the low concentration solution moves to the high concentration solution to achieve the concentration equilibrium Natural phenomena occur and are called "osmotic" or "osmotic phenomena". The osmotic phenomenon was discovered by German chemist M. Traube in 1867, and the osmotic pressure caused by osmosis was first measured by Pepper in 1877.

Such osmotic phenomena are the core of desalination technology using seawater, which is one of the ways to solve the serious water shortage due to climate change due to global warming, increase in industrial use due to industrialization, and increase in water demand due to population increase.

However, the seawater desalination process up to now is a highly energy-intensive process and still has economic limitations unless it is a water-scarce region like the Middle East.

Methods for removing salts in seawater can be roughly divided into evaporation and reverse osmosis.

The reverse osmosis method has been developed with technology that has been used for the past 30 years, and the development of technologies focused on improving the reverse osmosis membrane capable of obtaining a high recovery rate even at a recent low pressure has been continued.

On the other hand, by continuing the above-mentioned technology development, technologies for recovering the high-pressure energy of brine discharged from the reverse osmosis process have emerged, and as the membrane technology has undergone remarkable development, interest in osmotic power generation Is increasing.

Osmotic power generation means the production of electricity using the osmotic action at the point where two flows with a difference in salinity are produced. The osmotic pressure of 27 bar at the point where sea water having an osmotic pressure of 27 bar meets a river having osmotic pressure near zero Can be used for production.

The power generation uses a reverse osmosis (RO) and other pressure delayed osmosis (PRO) systems. If the pressure is applied to the seawater at a higher pressure than the osmotic pressure by the pressure delay osmotic method, the flux of the water permeating the membrane by the osmotic pressure is reduced, and the osmotic pressure is converted into the hydraulic pressure, .

The above-mentioned power generation using pressure delay osmosis can cope with global warming problem which is an international issue, and it is renewable energy that can replace current fossil fuel energy. Because it uses sea water which is an infinite energy source, It is urgent to develop technology for Zero Inverse. For this purpose, it is necessary to develop various technologies such as development of membrane for pressure delay osmosis, development of osmosis module, and development of pressure delay osmosis power plant.

In the case of double pressure delayed osmosis module, osmotic pressure difference, which is one of the core of osmotic pressure generation, should be generated. To achieve this, the two solutions of varying concentrations need to be kept or flowed as smoothly and as much as possible to the osmotic membrane boundary.

However, in the conventional osmosis pressure-delayed osmosis module, the osmosis membrane is composed of two osmosis membranes in an envelope shape, and water flows into the envelope-shaped osmosis membrane in the porous permeation water outflow pipe of the osmosis module, And there is a problem in that the inflow of water into the envelope-shaped osmosis membrane is difficult in the porous permeate outlet pipe.

In addition, pressure-delayed osmosis does not apply enough pressure to transfer water from the high concentration solution to the low concentration solution, such as reverse osmosis pressure, while minimizing the flux of the water due to osmosis while changing the osmotic pressure to hydraulic pressure to produce a constant pressure Bar There is a problem in that the inflow of water into the envelope-shaped osmosis membrane becomes more difficult in the porous permeated water outlet tube because the pressure is stuck to the envelope-shaped osmotic membrane without causing internal space.

Further, there is a problem that the osmotic membrane is damaged due to the pressure applied from the outside of the osmosis membrane in the form of an envelope having weak pressure resistance, or the osmosis membrane may be damaged due to the spacer provided in the osmosis membrane.

FIG. 1 is a perspective view of a conventional pressure-delayed osmotic membrane assembly. In order to solve the above-mentioned problem, a spacer 2 for forming a flow path is placed in an envelope-shaped osmosis membrane (1, 3) There is still a problem in that the osmotic action is not smooth due to a small amount of flow-in.

Korean Patent Application No. 2012-7007350 discloses a method for producing a quasi-osmosis membrane and a quasi-osmosis membrane, and the said osmosis membrane can also be used for pressure delay osmosis. In one embodiment of the application, the support polymer is coated on one or both sides of the tricot-type mesh support material and the membrane barrier layer is applied to one or both sides of the coated support polymer. . Although the above application describes that the spacer may not be individually contained in the film through the above embodiment, it merely discloses an advantage of not performing the process of manufacturing or providing the spacer separately, There is a problem in that it is difficult to obtain a sufficient flow rate so that the osmotic pressure gradient can be formed well and there is a limit to increase the flow rate.

SUMMARY OF THE INVENTION The present invention has been conceived in order to solve the above-mentioned problems, and an object of the present invention is to improve the flow rate of the osmosis membrane and improve the pressure resistance so that osmosis can be smoothly performed even if the osmosis membrane is formed. And to provide a pressure-sensitive osmotic membrane assembly in which damage to the osmotic membrane is minimized by the pressure exerted outside the osmotic membrane.

A second problem to be solved by the present invention is to provide a pressure-delayed osmosis module having an osmotic effect maximized and a high power density by using a pressure-delayed osmotic membrane assembly formed of a bush.

In order to solve the above first problem, the present invention provides an aggregate comprising a pressure-retarded osmosis membrane having pressure resistance secured under a pressure of 10 kg / cm ² , comprising: a first separator; A second separation membrane; And a plurality of spacers for forming a flow path between the first separation membrane and the second separation membrane.

According to a preferred embodiment of the present invention, at least one of the first separation membrane and the second separation membrane may be a pressure-delayed osmosis membrane.

According to another preferred embodiment of the present invention, the pressure-delayed osmosis membrane comprises a support; A polymeric support layer formed on the support layer; And a polyamide-based active layer formed on the polymer support layer; Lt; RTI ID = 0.0 >

According to another preferred embodiment of the present invention, the support comprises synthetic fibers selected from the group consisting of polyester, polypropylene, nylon and polyethylene; Or a natural fiber including cellulose-based pulp; and a non-woven fabric or a woven fabric.

According to another preferred embodiment of the present invention, the polymer support layer is selected from the group consisting of polysulfone-based polymers, polyamide-based polymers, polyimide-based polymers, polyester-based polymers, olefin-based polymers, halogenated polymers and polyacrylic polymers Lt; / RTI >

According to another preferred embodiment of the present invention, the first separator and the second separator may have a thickness of 70 to 250 탆.

According to another preferred embodiment of the present invention, the first and second separation membranes may be bonded to the remaining three surfaces except for the surface on which the raw water flows.

According to another preferred embodiment of the present invention, the spacer may include at least one of a tricot filter sheet and a mesh sheet.

(5) 18 ≤ p + y ≤ 80 이고, 여기서, 상기 a는 트리코트 여과수로의 개수, b는 메쉬시트의 개수, x는 단일트리코트 여과수로의 두께(밀(mil)), y는 단일 메쉬시트의 두께(밀(mil)), p는 총 트리코트 여과수로의 두께의 합(밀(mil)), p+y는 총 트리코트 여과수로 및 총 메쉬시트 두께의 합(밀(mil))이다.According to another preferred embodiment of the present invention, the spacer satisfies the following condition (1) 2? A + b? 3, where 2? A? 3 and 0? B? 20 (3) 24 ≤ y ≤ 50 (4) When the mesh sheet is not included

(5) 18 ≤ p + y ≤ 80, where a is the number of tricot filtrate, b is the number of mesh sheets, x is the thickness (in mil) of single tricot filtrate, (Mm) of the mesh sheet, p is the total thickness (mil) of the total tricot filtrate, p + y is the sum of the total mesh sheet thickness and total tricot filtrate (mil) )to be.

According to another preferred embodiment of the present invention, the spacer can satisfy the condition (6) 40? P + y? 65.

According to another preferred embodiment of the present invention, the spacer may include a mesh sheet between two different tricot filtrate water.

According to another preferred embodiment of the present invention, the mesh sheet may have a pore size of 6 to 20 mm < 2 >.

In order to solve the second problem, the present invention provides a pressure-delayed osmosis module comprising a plurality of pressure-delayed osmotic membrane assemblies according to the first problem solving means wound in a spiral wound form.

The high flow rate pressure delayed osmotic membrane assembly of the present invention can improve the flow rate inside the osmotic membrane by forming more channels in the osmotic membrane so that the osmotic action can be smoothly performed even if the osmotic membrane assembly is formed as the first or the bellows. The flux can be promoted. Further, as the turbulence is promoted along the flow path, the flow rate at the osmotic membrane surface can be improved to minimize concentration polarization at the osmotic membrane surface. Furthermore, a high salt rejection rate can be achieved.

Secondly, it is possible to minimize the damage of the osmotic membrane due to the pressure applied from the outside of the osmotic membrane due to the improved pressure resistance, and also to minimize the damage to the inside surface of the osmotic membrane which may occur by forming a separate passage in the osmotic membrane have. Furthermore, separation of different bonded osmotic membranes, which may occur by forming a separate flow path in the osmosis membrane, can be minimized.

Third, by using the pressure - delayed osmotic membrane assembly with improved flow rate, it is possible to improve power density by maximizing the effective area of osmotic action and smooth osmotic action.

1 is a perspective view of a conventional pressure-delayed osmotic membrane assembly.
2 is a perspective view of a pressure-sensitive osmotic membrane assembly according to a preferred embodiment of the present invention.
3 is a cross-sectional view of a pressure-delayed osmosis membrane according to a preferred embodiment of the present invention.
FIG. 4 is a perspective view of a case in which a preferred embodiment of the present invention is wound in a spiral form.
5 is an exploded perspective view of a pressure delay osmosis module according to a preferred embodiment of the present invention.
6 is a cross-sectional view of a pressure delay osmosis module according to a preferred embodiment of the present invention.

Hereinafter, the present invention will be described in more detail with reference to the accompanying drawings.

As described above, the conventional bellows type pressure-delayed osmosis module has a problem in that water is difficult to flow into the envelope-shaped osmosis membrane in the porous permeated water outlet tube.

In addition, pressure-delayed osmosis does not apply enough pressure to transfer water from the high concentration solution to the low concentration solution, such as reverse osmosis pressure, while minimizing the flux of the water due to osmosis while changing the osmotic pressure to hydraulic pressure to produce a constant pressure Bar There is a problem in that the infiltration of water into the envelope-shaped osmosis membrane becomes more difficult in the porous permeated water outlet tube because the pressure does not cause an inner space in the envelope-shaped osmotic membrane and sticks to each other.

Further, although a spacer is provided for securing the flow path in the prior art, there is still a problem that the osmotic action is not smooth due to a small flow rate through the spacer.

Furthermore, there has been a problem that the osmosis membrane is damaged by the pressure exerted outside the osmotic membrane, or the inside of the osmotic membrane may be damaged by the pressure exerted by the spacer outside the envelope-shaped osmotic membrane .

Accordingly, the present invention provides an aggregate comprising a pressure-retarded osmosis membrane having pressure resistance secured under a pressure of 10 kg / cm ² , comprising: a first separator; a second separator; And a plurality of spacers for forming a flow path between the first separation membrane and the second separation membrane, thereby solving the above-mentioned problem.

Accordingly, the flow rate inside the osmosis membrane can be improved by forming more flow passages inside the osmosis membrane so that the osmosis action can be smoothly performed even if it is formed into a spiral shape. In addition, by improving the pressure resistance, damage to the osmotic membrane and / or the inner surface of the osmotic membrane due to the pressure exerted outside the osmotic membrane can be minimized.

FIG. 2 is a perspective view of a pressure-sensitive delayed osmotic membrane assembly according to a preferred embodiment of the present invention, and includes a plurality of spacers 51, 52 and 53 between a first membrane 11 and a second membrane 12.

A plurality of spacers 51, 52 and 53 and a first separator are sequentially stacked on the second separator 12 and the first and second separators 11 and 12 and the spacers 51 and 53, The inner spaces in which the spacers 51, 52 and 53 are located by the first and second separation membranes 11 and 12 are separated from the outside of the separation membrane, In order to generate osmotic pressure between the two solutions having different concentrations, the remaining three surfaces except for the surface on which the solution flows from the porous permeated water outlet tube are adhered to each other to have an envelope shape. The first separating membrane 11 and the second separating membrane 12 are sealed through the glue or adhesive along the edges a, c, and d and the portion from which the solution flows from the porous permeated water outlet tube to the pressure delayed osmotic membrane assembly The corresponding portion of FIG. 2B has an unsealed envelope shape. Similarly, the envelope shape acts to fluidly isolate the solution flowing into the pressure-delayed osmotic membrane assembly and the solution flowing out of the pressure-delayed osmotic membrane assembly, whereby the osmotic pressure gradient between the two solutions having different concentrations around the membrane .

First, the separation membranes 11 and 12 will be described.

The separators 11 and 12 included in the preferred embodiment of the present invention may be inserted into Korean Patent Applications No. 2012-0140611 and No. 2012-0140612 by the inventors of the present invention.

Any one or more of the first separation membrane 11 and the second separation membrane 12 of the present invention may be a pressure delayed osmosis membrane.

The first separation membrane 11 and the second separation membrane 12 may be the same or different, and at least one of the first separation membrane and the second separation membrane may be a pressure delayed osmosis membrane, and preferably all of them may be pressure delayed osmosis membranes.

Preferably, the pressure-delayed osmotic membrane comprises a support; a polymeric support layer formed on the support; And a polyamide-based active layer formed on the polymer support layer; And a pressure-sensitive membrane.

3 is a cross-sectional view of a pressure-sensitive delayed osmosis membrane according to a preferred embodiment of the present invention. In the pressure-sensitive osmotic membrane 100, a polymer support layer 102 is formed on a support 103, And the polyamide-based active layer 101 is laminated on the polyamide-based active layer 101.

First, the support 103 can play a role of supporting the membrane, and can give a high hydrophilicity to the support to smooth the flow of water. The support 103 may be in the form of a nonwoven fabric in which the fibers are entangled and have no longitudinal and transverse directionality, or a woven fabric so as to have a longitudinal and transverse directionality. Preferably, the support 103 can be made of synthetic fibers selected from the group consisting of polyester, polypropylene, nylon and polyethylene, or natural fibers including cellulose pulp. However, the material of the support 103 is not limited to the above description.

If the support 103 is a nonwoven fabric layer, the physical properties of the membrane can be controlled according to porosity and hydrophilicity of the material. The non-woven fabric layer may have an average pore size of 1 to 600 μm, and preferably 5 to 300 μm, to improve smooth permeation of water and water permeability required of the pressure delayed osmosis membrane. However, the present invention is not limited to the above description.

If the thickness of the support 103 is less than 80 탆, the strength and support of the entire membrane may be insufficient. If the thickness of the support 103 exceeds 150 탆, the support may be deteriorated.

Next, the polymer support layer 102 formed on the support 103 will be described.

The polymer support layer 102 has a porous structure to secure a high flow rate. The polymer support layer may be formed of any one selected from the group consisting of a polysulfone polymer, a polyamide polymer, a polyimide polymer, a polyester polymer, an olefin polymer, a halogenated polymer, and a polyacrylic polymer, Among the polysulfone-based polymers, polysulfone and polyether sulfone may be used. In olefin-based polymers, polypropylene and polyethylene may be used. Of the halogenated polymers, polybenzimidazole polymers and polyvinylidene difluoride may be used have. However, the present invention is not limited to the above description.

The thickness of the polymer support layer may preferably be 30 to 100 占 퐉. If the thickness is less than 30 占 퐉, maintaining the pressure resistance of the entire membrane may be insufficient. If it exceeds 100 占 퐉, the flow rate may be decreased. However, the present invention is not limited to the above description.

Next, the polyamide-based active layer 101 formed on the polymer supporting layer 102 will be described.

The polyamide-based active layer 101 plays a role in securing a high salt rejection rate that can remove univalent ions that are difficult to remove in a single membrane structure. Furthermore, since the physical properties required for the positive osmosis method are optimized, it is suitable for accommodating a high concentration of seawater in the pressure delay osmosis membrane.

Specifically, the formation of the polyamide-based active layer (101) is carried out in an aqueous solution containing a polyfunctional amine selected from metaphenyldiamine, paraphenyldiamine, orthophenyldiamine, piperazine or alkylated piperidine and an alkylated aliphatic amine , A polyfunctional acyl halide, a polyfunctional sulfonyl halide, or a polyfunctional isocyanate, and then conducting an interfacial polymerization between the compounds.

At least one hydrophilic functional group selected from the group consisting of a hydroxyl group, a sulfonate group, a carbonyl group, a trialkoxysilane group, an anion group and a tertiary amino group is added to an aqueous solution containing the polyfunctional amine- or alkylated aliphatic amine A hydrophilic compound, i.e., a hydrophilic amino compound, may be further added.

More specifically, preferred examples of the hydrophilic compound having a hydroxy group include 1,3-diamino-2-propanol, ethanolamine, diethanolamine, 3-amino-1-propanol, Butanol, 2-amino-1-butanol. The hydrophilic compound having a carbonyl group is selected from the group consisting of aminoacetaldehyde dimethylacetal,? -Aminobutylolactone, 3-aminobenzamide, 4-aminobenzamide and N- (3-aminopropyl) -2-pyrrolidinone .

Further, as the hydrophilic compound containing trialkoxysilane group, (3-aminopropyl) triethoxysilane or (3-aminopropyl) trimethoxysilane may be selectively used.

Further, the hydrophilic compound having an anionic group may be selected from the group consisting of glycine, taurine, 3-amino-1-propylselphenic acid, 4-amino-1-butenesulfonic acid, 2-aminoethylhydrogensulfate, Amino-4-hydroxybenzoylsulfoxide, 3-amino-4-hydroxybenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-aminopropylphosphonic acid, Aminobutyric acid, 4-amino-2-hydroxybutyric acid, 4-aminobutyric acid, and glutamic acid, which may be selected from the group consisting of hydroxybenzoic acid, have.

Further, hydrophilic compounds having one or more tertiary amino groups include 3- (dimethylamino) propylamine, 3- (diethylamino) propylamine, 4- (2-aminoethyl) -Aminoethyl) piperazine, 3,3'-3,3'-diamino-N-methyldipropylamine and 1- (3-aminopropyl) imidazole.

The polyamide-based active layer 101 included in the preferred embodiment of the present invention may be formed as a dense surface layer of the pressure-delayed osmosis membrane to form a structure resistant to pressure resistance, and at the same time, Chemical resistance and high salt rejection rate can be secured.

Accordingly, a preferred embodiment of the present invention ensures stain resistance and chemical resistance. The membrane fouling is a factor which deteriorates the performance of the pressure-delayed osmotic membrane assembly. The osmotic pressure gradient is lowered due to membrane fouling, and the filtration flux through the membrane is reduced. However, There is an advantage that the reduction problem can be minimized.

In addition, although the single membrane structure has a large pore size, it is difficult to remove a small salt such as monovalent ions, but when a polyamide layer is provided, monovalent ions can be removed, thereby achieving a high salt rejection rate, The solute of the derivatizing solution can be prevented from being despread.

The first and second separation membranes 11 and 12 may have a thickness of 70 to 250 탆. If the thickness is less than 70 탆, the strength and supporting ability of the whole membrane is insufficient, and if it exceeds 250 탆, it may cause a decrease in the flow rate. The thicknesses of the first and second separation membranes 11 and 12 may be the same or different from each other.

Next, the spacers 51, 52, and 53 formed between the first and second separation membranes will be described.

The present invention includes a plurality of spacers (51, 52, 53) through which the formation of a flow path in the envelope-like separation membrane formed by the first separation membrane (11) and the second separation membrane (12) can be greatly improved. Tricot filter as a spacer prevents deformation of the membrane during high pressure operation, and the mesh sheet affects the fouling of the module. In detail, the thicker the membrane is, the more smooth the water flow is, and the thicker the mesh sheet, the stronger the module fouling. Fouling of the module means that the crystallized particles or precipitates of the salt compound are accumulated on the surface of the membrane due to a problem caused by the long-term operation of the module, thereby deteriorating the module performance.

In the prior art, since the spacers are included in a single number, the flow path formation in the separation membrane is not smooth and the flow rate into the envelope-like separation membrane can not be increased. However, by including the plurality of spacers 51, 52, 53, It is possible to improve the flow rate to the inside of the separator and to produce a uniform filtration flux along the flow path by increasing the amount of the flow path. Further, as the turbulence is promoted along the flow path, And smoothness was achieved.

On the other hand, the spacer may include at least one of a tricot filtrate and a mesh sheet.

First, the tricot filtered water passages 51 and 53 will be described.

The tricot filtrate is provided in the pressure delayed osmosis membrane to form a flow path and additionally have a function of preventing deformation of the separation membrane. Typically, any tricot can be used as a spacer provided in a pressure-delayed osmotic membrane. Preferably, the tricot can be a polypropylene, a polyethylene, a poly-4-methylpentene, a crystalline copolymer with propylene- Polyamide and polycarbonate, or modified polyester (LMP: Low Melting Polyethylene Terephthalate) in which nylon or polypropylene is copolymerized with polyethylene terephthalate resin, Can be used. However, the present invention is not limited thereto.

Next, the mesh sheet 52 will be described.

The mesh sheet 52 has a function of forming a flow path by being provided in the pressure delay osmosis membrane. In general, any mesh sheet which can be used as a spacer provided in the pressure-delayed osmosis membrane can be used, and it may preferably be a mesh sheet made of polypropylene or polyethylene. However, the present invention is not limited to the above description

Preferably, the mesh sheet 52 may be a mesh sheet having a void of 6 to 20 mm 2 in order to smooth flow path formation. If the air gap is less than 6 mm 2, there is a problem that it may interfere with the flow path formation. If the air gap exceeds 20 mm 2, there is a problem that deformation and fouling of the membrane may be deteriorated under high pressure operation.

Meanwhile, the spacers 51, 52 and 53 included in the preferred embodiment of the present invention can satisfy all of the following conditions (1) to (5).

This can greatly improve the osmotic gradient by greatly increasing the flow rate to the pressure delayed osmotic membrane assembly to offset the reduced effective area in a single pressure delayed osmotic membrane assembly. However, if a thickness range over a certain range including a plurality of spacers is provided, the effective film area may be decreased to affect the module performance degradation. Further, the number of pressure-sensitive delayed osmosis membrane assemblies included in the limited external pressure case (30 in Fig. 4) can be further included so as to obtain the maximum power density. Furthermore, it is possible to solve the problem of defective and osmotic gradient deterioration due to the membrane separation of the pressure-delayed osmotic membrane assembly.

Wherein a is a number of tri-coat filtration water among a plurality of spacers, b is a number of a plurality of spacers among the plurality of spacers, .

The number of the spacers included in the preferred embodiment of the present invention satisfies the above conditions, thereby increasing the flow rate through the flow path improvement and minimizing the effective area reduction of the separation membrane, which may cause osmosis. The durability of the membrane assembly can be maintained. When a large number of spacers exceeding the above range are included to improve the flow path, there may be a problem that the effective area of the separation membrane included in the pressure delay osmosis module to be described below is reduced, There is a problem that the density is reduced.

More specifically, FIG. 4 is an exploded perspective view of a pressure case in which a pressure-retentive osmotic membrane assembly is rolled into a porous permeated water outlet pipe 20 in a pressure case 30, . The reason why the effective area of the separation membrane is reduced as described above is that the amount of the separation membrane included in the inner space of the pressure casing 30 is limited due to the limited space of the pressure casing 30 including the pressure delay osmosis module. Accordingly, by including a large number of spacers, the relatively contained separator can be reduced, and the effective area of the separator can be reduced.

The effective area of the separation membrane for obtaining the maximum power density is determined by the diameter of the porous permeate outlet pipe included in the pressure delay osmosis module, the pressure delay in the direction of the solution flowing into the pressure- The length of the osmotic membrane assembly (the a-plane length in Fig. 2), the number of the pressure-delayed osmotic membrane assemblies contained in the case, and the like. The maximum power density can not be obtained simply by increasing the flow rate and increasing the surface area of the separation membrane. For example, if the length of the pressure-delayed osmotic membrane assembly (a-plane length in FIG. 2) is increased while including more than three spacers, the flow rate can be improved and the surface area of one pressure- The number of pressure delayed osmosis membrane assemblies contained in the case space may be reduced and consequently the surface area of the membrane contained in the case may be reduced.

In addition, when the length of the pressure delayed osmotic membrane assembly (a-plane length in FIG. 2) is made longer, the length of the passage through which the solution flowing into the pressure-delayed osmotic membrane assembly flows from the porous permeable water outlet tube becomes longer, There is a problem that can be deteriorated.

Further, when more than three spacers are included, there is a problem that the first separating membrane and the second separating membrane adhered to each other in a wrapping shape may cause failure of the pressure-sensitive delayed osmotic membrane assembly, There is a problem that the solution flowing inside the case having a different concentration penetrates between the first separating membrane and the second separating membrane which are not adhered and disturb the osmotic action.

Next, a preferred embodiment of the present invention may be a pressure-delayed osmotic membrane assembly satisfying the condition (2) 5? X? 20. X is the thickness (in mil) of the tricot filtrate contained in the spacer. If the thickness of the tricot filtrate (51, 53) is less than 5 mils, there is a problem of reducing the space for securing the flow path to reduce the osmotic gradient. If the thickness exceeds 20 mils, The number of the spacers that can be included in the osmosis membrane aggregate may be reduced, and furthermore, when the spacer having a size of more than 20 mil is applied, the flow of the osmosis membrane may be deteriorated.

When a plurality of tricot filtered water roots are included, the thicknesses of the respective tricot filtered water roots may be the same or different from each other.

Next, a preferred embodiment of the present invention may be a pressure-delayed osmotic membrane assembly satisfying the condition (3) 24? Y? 50. And y is the thickness (in mil) of the mesh sheet contained as a spacer. And preferably a mesh sheet having a thickness of 28 to 46 mil. If the thickness of the mesh sheet is less than 28 mils, sufficient channel can not be secured, fouling may occur in the module, and the performance of the module may be deteriorated. If the mesh sheet is more than 46 mil, It is possible to reduce the effective area per unit volume of the module, which may adversely affect module performance.

Next, a preferred embodiment of the present invention may be a pressure-delayed osmotic membrane aggregate satisfying condition (4) 18 ≤ p when the mesh sheet is not included. Where p is the sum of the thicknesses (in mil) of the total tricot filtrate.

If the above condition is not satisfied, the thickness of the spacer is not sufficient to sufficiently form the passage even when the number of the tricot filtration channels is larger than that of the conventional pressure-delayed osmosis membrane assembly, There is a problem that it is difficult to obtain.

인 것을 만족하는 압력지연 삼투막 집합체일 수 있다. 상기 p+y는 총 트리코트 여과수로 및 총 메쉬시트 두께의 합(밀(mil))이다.Next, a preferred embodiment of the present invention is characterized in that the condition (5)

Lt; RTI ID = 0.0 > osmotic < / RTI > Where p + y is the sum of the total tricot filtrate water and total mesh sheet thickness (mil).

If the above condition is not satisfied, there is a problem that the thickness of the spacer is not sufficient to sufficiently form the flow path, so that it is difficult to obtain a higher flow rate than the conventional pressure-delayed osmotic membrane assembly, or the thickness of the spacer becomes too thick, There may be a problem that the effective area decreases or the osmotic pressure is inhibited as described above because the space between the first separation membrane and the second separation membrane of the pressure-

As described above, a preferred embodiment according to the present invention includes a spacer that satisfies all of the conditions (1) to (5), so that the pressure-delayed osmosis The flow rate to the membrane assembly can be greatly improved. Further, the number of the pressure-sensitive delayed osmosis membrane assemblies included in the limited outer case (30 in Fig. 4) can be included so as to obtain the maximum power density. Further, problems of defective and reduced osmotic pressure due to separation of the membrane of pressure-sensitive osmotic membrane aggregates can be solved.

More preferably, a preferred embodiment of the present invention may satisfy condition (6) 40 ≤ p + y ≤ 65 in addition to the above conditions (1) to (5), whereby a high- It can be generated from the inside to the outside or from outside to inside, and it is possible to maximize the effective area of the separation membrane for the osmosis action by taking into consideration until it is included in the pressure delay osmosis module to be described later. In addition, the increase of the effective area of the separation membrane can improve the osmotic gradient to obtain the maximum power density. Where p + y is the sum of the total tricot filtrate water and the total mesh sheet thickness (in mil).

In a preferred embodiment of the present invention, at least two or more of the spacers may include a tricot filtrate furnace, and more preferably, two mesh tricot filter wafers may include a mesh sheet therebetween.

When the mesh sheet is included in the mesh sheet, the flow rate can be improved, but the entire separation membrane including the mesh sheet is pressed due to the pressure exerted outside the envelope-shaped separation membrane, There is a problem in that it is damaged due to the influence of the heat. Damage to the inner surface of the separation membrane as described above may affect the osmotic action, which may cause a drop in the osmotic pressure gradient.

In order to solve the above problems, the mesh sheet 52 is included between two different tricot filtrate passages 51 and 53 so that the first separation membrane 11 and the second separation membrane 12 are separated from each other by the tricot filtration water The mesh sheet 52 is directly adjacent to the trough coils 51 and 53 and adjacent to the tricot filtrate passages 51 and 52 can minimize damage to the inner surface of the separation membrane that may occur when the mesh sheet is included, The flow rate can be improved and the original osmosis function can be maintained and exerted.

Meanwhile, the present invention includes a pressure-delayed osmosis module including a plurality of pressure-delayed osmotic membrane assemblies according to the present invention wound in a spiral wound form.

More specifically, FIG. 4 is an exploded perspective view of a pressure case in which a preferred embodiment of the present invention is wound in a spiral form. In the pressure delay osmosis module according to a preferred embodiment of the present invention, a plurality of pressure- And may be wound in a spiral shape around the water outlet pipe 20 and positioned inside the pressure case 30. [

The pressure case 30 may be sized and shaped so as to accommodate the pressure-delayed osmosis module disposed therein. Preferably, the plurality of pressure-sensitive delayed osmosis membrane assemblies are wound in a spiral shape, and the shape thereof may be a cylindrical shape . However, the present invention is not limited to the above description. The material of the case can be used without limitation in case of a pressure case material normally used in the pressure delay osmosis system.

FIG. 5 is an exploded perspective view of a pressure-delayed osmosis module according to a preferred embodiment of the present invention. Referring to FIG. 5, a plurality of pressure-sensitive delayed osmotic membrane assemblies 50 are wound in a spiral wound around a porous permeated water outlet pipe 20 do. The cross-sectional diameter of the pressure-delayed osmosis module may vary depending on the diameter of the porous permeate outlet tube, the number and thickness of the pressure-sensitive osmotic membrane aggregate, and the like, and preferably the cross-sectional diameter may be 7.62 to 22.86 cm.

The porous permeated water outlet pipe 20 includes a plurality of holes 21 and a fluid flowing through the porous permeated water outlet pipe 20 passes through the holes 21 to separate the pressure- (11, 12). Specifically, in FIG. 5, the solution A of the two solutions A and B having different concentrations flows into the pressure case 30 and out of the pressure-decompressed osmotic membrane assembly 50, and the solution B is porous And flows into the permeable water outflow pipe 20 through the holes 21 into the separation membranes 11 and 12 of the pressure-reduced osmotic membrane aggregate 50. Through this, two solutions (A, B) having different concentrations are placed inside and outside the separation membranes (11, 12) of the pressure-sensitive delayed osmotic membrane assembly (50), whereby osmotic pressure is generated and operated. However, the two solutions A and B may be injected in the same direction as shown in FIG. 5, but the solutions A and B may be injected in different directions according to the purpose.

The porous permeated water outlet pipe 20 may be used without limitation in the case of an outflow pipe normally used in a pressure-delayed osmosis membrane, and the diameter and length of the porous permeated water outlet pipe 20 may vary depending on the purpose.

The pressure-sensitive delayed osmotic membrane assembly 50 includes a separation membrane 11 and 12 and spacers 51 and 52 and 53. The separation membranes 11 and 12 and the spacers 51 and 52 and 53 are described in detail The same shall apply hereafter.

The pressure-sensitive delayed osmotic membrane assembly 50 is wound around the porous permeated water outlet tube 20 in a spiral wound manner or wound in a spiral shape, The surface area of the membrane can be widened, thereby increasing the effective area of the osmotic action, which is advantageous in that the osmotic pressure gradient is formed well.

Preferably, the mesh sheet 60 may be included between the plurality of pressure-sensitive delayed osmotic membrane assemblies 50. The mesh sheet has an advantage that a fluid flowing between different pressure-delayed osmotic membrane aggregates, for example, a flow path through which the solution A in FIG. 5 can smoothly flow can be formed. 6 is a perspective view of a cross section of a pressure-delayed osmosis module according to a preferred embodiment of the present invention. The mesh sheet 60 may be located between the pressure-sensitive osmotic membrane assemblies 50.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments. It will be understood that various changes and modifications may be made without departing from the scope of the present invention. For example, each component specifically illustrated in the embodiments of the present invention can be modified and implemented. It is to be understood that all changes and modifications that come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.

The present invention will now be described more specifically with reference to the following examples, which should not be construed as limiting the scope of the present invention, but should be construed to facilitate understanding of the present invention.

<Examples>

1. Manufacture of Pressure Delay Osmosis Membrane Assembly

The first and second separators each comprising a nonwoven fabric of PET material having an average pore size of 200 μm as a support layer, a polysulfone mixed polymer support layer and a polyamide active layer were formed to have a total thickness of 0.16 mil, The pressure-delayed osmotic membrane assemblies having a length of 1 m and a length of 1 m, respectively, as shown in FIG. 2 were prepared by varying the number and thickness of the spacers.

2. Manufacture of Pressure Delay Osmosis Module

The prepared pressure-sensitive delayed osmotic membrane assembly was wound into a porous permeable effluent tube in a number of turns as shown in Tables 1 and 2, and a polypropylene (PP) mesh sheet having a pore size of 6.25 mm ² was sandwiched between the respective osmotic membrane assemblies (Outer diameter of double porous permeated water outlet tube of 20 mm, inner diameter of 12 mm) or 20.32 cm (outer diameter of double porous permeated water outlet tube of 38 mm, inner diameter of 28 mm) After the pressure delay osmosis module as shown in Figs. 6 and 7 was manufactured, the module was mounted on an outer case used for a normal pressure delay osmosis as shown in Fig.

<Comparative Example>

The pressure-delayed osmosis membrane module and the pressure-delayed osmosis module were fabricated in the same manner as in Example 1 except that the number and thickness of the spacers were changed according to the conditions shown in Table 2 below. Respectively.

<Experimental Example 1>

The following conditions (1) to (6) of the pressure-relaxed osmotic membrane assemblies prepared in the above-mentioned Examples and Comparative Examples were evaluated, and when satisfied, they were not satisfied. - &gt;&lt; tb &gt;&lt; TABLE &gt;

(Conditions 1 to 6)

(1) 2? A + b? 3, with 2? A? 3 and 0? B? 1.

(2) 5? X? 20

(3) 24? Y? 50

(4) When the mesh sheet is not included

(5)

(6) 40? P + y? 65

Where a is the number of tricot filtrate, b is the number of mesh sheets, x is the thickness (mil) of single tricot filtrate, y is the thickness of a single mesh sheet (mil) (Mil), p + y is the sum of the total tricot filtrate and the total mesh sheet thickness (in mil).

&Lt; Experimental Example 2 > - Measurement of flow rate and power density

In order to evaluate the performance of the pressure-sensitive delayed osmotic membrane assembly prepared in the above-described Examples and Comparative Examples, the active layer of the separation membrane was mounted in the direction of the direction of pressure (direction of pressure) in the pressure-sensitive delayed osmotic membrane assembly, Allow water to migrate from low salinity (raw water, distilled water) to high salinity (inducing solution 35,000 ppm NaCl). At this time, the amount of water movement in the pressure delayed osmosis process was measured by using distilled water and 35,000 ppm of the induction solution at a pressure of 10 kg / cm ² and the flow rate of the pressure delayed osmosis membrane was confirmed by converting the water density into power density.

The performance of the pressure-delayed osmosis process is represented by the power density, and the power density has units of power per unit area (W / m 2). The power density was calculated by the following equation (1) using the flow rate (gfd) and pressure obtained from the performance evaluation of the pressure delay osmosis membrane, and the results are shown in Tables 1 and 2 below.

[Equation 1]

(단, W는 전력밀도, JW는 유량, △P는 압력이다.)

(Where W is the power density, JW is the flow rate, and DELTA P is the pressure).

&Lt; Experimental Example 3 > - Deterioration of membrane surface

In order to investigate the damage of the surface of the separator membrane for the pressure-delayed osmotic membrane assembly performed in Experimental Example 1 for 48 hours, the surface of the membrane was visually inspected to see whether it was pushed by the spacer. When the membrane was not pushed, 0, If present, is changed from 1 to 5 according to the degree, and is shown in Tables 1 and 2 below.

<Experimental Example 4>

In order to confirm whether the separation membrane adhesion failure was confirmed for the pressure-delayed osmotic membrane assemblies performed in Experimental Example 1 for 48 hours, water was injected into the pressure delayed osmotic membrane assembly to check whether water leaked to the outside. 0 &quot; and &quot; 0 &quot;, respectively.

Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Spacer 1 Kinds Tricot Tricot Tricot Tricot Tricot Tricot Tricot thickness
(Mil) 5 16 5 9 16 16 9 Spacer 2 Kinds Tricot Tricot Tricot Tricot Tricot Tricot Mesh sheet thickness
(Mil) 5 16 5 9 16 16 32 Spacer 3 Kinds - - Tricot Tricot Tricot Tricot Tricot thickness
(Mil) - - 5 9 16 16 9 Spacer 4 Kinds - - - - - Tricot - thickness
(Mil) - - - - - 16 - Condition (1) ㅇ ㅇ ㅇ ㅇ ㅇ x ㅇ Condition (2) ㅇ ㅇ ㅇ ㅇ ㅇ ㅇ ㅇ Condition (3) - - - - - - ㅇ Condition (4) x ㅇ x ㅇ ㅇ ㅇ - Condition (5) x ㅇ x ㅇ ㅇ ㅇ ㅇ Condition (6) x x x x ㅇ x ㅇ Pressure Delay Osmosis Module Cross Section Diameter (cm) 10.16 10.16 20.32 10.16 10.16 10.16 10.16 10.16 20.32 Pressure Delay Osmosis Membrane Assembly Number 4 4 12 4 3 3 3 3 12 Pressure level [kg / cm ² ] 10 10 10 10 10 10 10 10 10 Flow rate [gfd] 4.33 4.60 4.70 4.52 5.87 6.40 3.81 6.62 6.89 Power density [W / m ² ] 2.00 2.13 2.17 2.09 2.71 2.96 1.76 3.06 3.19 Membrane surface damage 0 One One One One One One One One Poor adhesion of membrane 0 0 0 One One One 3 One One * Tricot filtration: Epoxy impregnated PET material
* Mesh sheet: pore 6.25mm ² , polypropylene material

Example 8 Example 9 Example 10 Example 11 Comparative Example 1 Comparative Example 2 Comparative Example 3 Spacer 1 Kinds Tricot Tricot Tricot Mesh sheet - Mesh sheet Tricot thickness
(Mil) 9 16 9 28 - 46 20 Spacer 2 Kinds Mesh sheet Mesh sheet Mesh sheet Tricot - - - thickness
(Mil) 55 50 46 16 - - - Spacer 3 Kinds Tricot Tricot Tricot Mesh sheet - - - thickness
(Mil) 16 16 9 28 - - - Spacer 4 Kinds - - - - - - - thickness
(Mil) - - - - - - - Condition (1) ㅇ ㅇ ㅇ ㅇ - x x Condition (2) ㅇ ㅇ ㅇ ㅇ - - ㅇ Condition (3) x ㅇ ㅇ ㅇ - ㅇ - Condition (4) - - - - - - ㅇ Condition (5) ㅇ x ㅇ ㅇ - - - Condition (6) x x ㅇ x - - - Pressure Delay Osmosis Module Cross Section Diameter (cm) 4 4 4 4 4 4 4 Pressure Delay Osmosis Membrane Assembly Number 3 3 3 3 3 5 5 Pressure level [kg / cm ² ] 10 10 10 10 10 10 10 Flow rate [gfd] 1.99 1.75 5.65 4.30 0.80 3.89 4.31 Power density [W / m ² ] 0.92 0.81 2.61 1.99 0.37 1.80 2.09 Membrane surface damage 3 3 2 4 0 5 One Poor adhesion of membrane 2 5 One 3 0 2 0 * Tricot filtration: Epoxy impregnated PET material
* Mesh sheet: pore 6.25mm ² , polypropylene material

Specifically, in Examples 1 to 11 including the spacers in Tables 1 and 2, the flow rate was significantly higher than that in Comparative Example 1. In Examples 1 to 11 including a plurality of spacers, 3, the flow rate and power density were generally high. However, when any one of the conditions 1 to 5 is not satisfied in the embodiment, the amount of the membrane adhesion increases and the flow rate and the power density are lowered (Examples 6, 8, 9 and 11) It can be confirmed that the flow rate or power density obtained without surface damage is reduced (Example 1).

It can also be seen that, in the case of Examples 7 and 10 which satisfy the condition 6, a remarkably excellent flow rate and power density can be obtained even when there is little amount of separation membrane adhesion and surface damage of the separation membrane.

Claims (13)

And a pressure-retarding osmosis membrane having pressure resistance secured under a pressure of 10 kg / cm ² ,
A first separation membrane; A second separation membrane; And a plurality of spacers for forming a flow path between the first separation membrane and the second separation membrane,
Wherein the plurality of spacers comprises at least one of a tricot filtrate furnace and a mesh sheet and satisfies the following conditions (1) to (5):
(1) 2? A + b? 3, with 2? A? 3 and 0? B? 1.
(2) 5? X? 20
(3) 24? Y? 50
(4) When the mesh sheet is not included, 18 ≤ p
(5) 18? P + y? 80
Where a is the number of tricot filtrate, b is the number of mesh sheets, x is the thickness (mill) of single tricot filtrate, y is the thickness (mill) of a single mesh sheet, p Is the sum of the thicknesses (in mil) of the total tricot filtrate and p + y is the sum of the total tricot filtrate and total mesh sheet thickness (in mil). The method according to claim 1,
Wherein at least one of the first separation membrane and the second separation membrane is a pressure-delayed osmosis membrane. 3. The system of claim 2, wherein the pressure-
A support;
A polymeric support layer formed on the support; And
A polyamide-based active layer formed on the polymer support layer; Pressure osmotic membrane assembly. The method of claim 3,
The support being synthetic fibers selected from the group consisting of polyester, polypropylene, nylon and polyethylene; Or natural fibers including cellulose-based pulp. The pressure-sensitive delayed osmotic membrane assembly according to claim 1, The method of claim 3,
Wherein the polymer support layer is at least one selected from the group consisting of a polysulfone polymer, a polyamide polymer, a polyimide polymer, a polyester polymer, an olefin polymer, a halogenated polymer and a polyacrylic polymer. Membrane assembly. The method according to claim 1,
Wherein the first and second separation membranes have a thickness of 70 to 250 占 퐉. The method according to claim 1,
Wherein the first separation membrane and the second separation membrane are bonded to each other at three surfaces except the surface to which the raw water flows. delete delete The method according to claim 1,
Characterized in that the spacer satisfies the following condition (6): &lt; EMI ID =
(6) 40? P + y? 65 The method according to claim 1,
Wherein said spacer comprises a mesh sheet between two different tricot filtrate streams. The method according to claim 1,
Wherein the mesh sheet has a void of 6 to 20 mm &lt; 2 &gt;. 10. A pressure-delayed osmosis module comprising a plurality of pressure-delayed osmotic membrane assemblies according to any one of claims 1 to 7 and 10 to 12 wound in rolls.

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