1]This application is a patent-pending Korea Korea Patent Application No. 10-2017-0126158 benefit of the filing date of heading No. 10-2016-0136571 filed first year and 09 April 2017, the 28th Korea Intellectual Property Office submitted to the Korea Intellectual Property Office on Oct. 20, 2016 It claims, and all the disclosure of which is incorporated herein by reference.
[2][0011] This application discloses a reverse osmosis membrane method using a composition for forming a reverse osmosis membrane, and this protective layer.
BACKGROUND
[3]
Recently, due to severe water shortages and pollution of the water environment it has emerged as an urgent challenge to develop new water sources. Research on water pollution and has a good life and industrial water, various kinds of domestic sewage and industrial wastewater treatment to the target, there is a heightened interest in water treatment processes using the separator having the advantage of energy conservation. In addition, the strengthening of environmental regulations and is expected to accelerate to accelerate the activation of membrane technology. Traditional water treatment processes are being strengthened to meet the himdeuna regulations, in the case of membrane technology because it guaranteed an excellent treatment efficiency and stable processing are expected to become the dominant technology in the future water treatment applications.
[4]
Liquid separation is classified as microfiltration (Micro Filtration), UF (Ultra Filtration), nanofiltration (Nano Filtration), RO (Reverse Osmosis), couch, the active can send and electrodialysis, etc., depending on the membrane pores. Then in the reverse osmosis method is water permeable, however, be the melting salt to use a semi-permeable membrane showing impermeable to say a process for the desalting operation the high pressure number that for a salt inlet on one side of the semipermeable membrane, the pure salt is removed It is come to the other side to low pressure.
[5]
Specifically, a typical example of such a water treatment membrane is a polyamide-based membrane may be made of water, to form a polysulfonic poncheung over a non-woven fabric to form a microporous support, the microporous support the m- phenylenediamine (m-Phenylene immersing the Diamine, mPD) aqueous solution to form a mPD layer, by dipping or coating it back to trimesoyl chloride (TriMesoylChloride, TMC) an organic solvent by contacting the mPD layer with TMC by interfacial polymerization by the method of forming the polyamide active layer It may have been manufactured. Thus, according to such manufacturing method, since the non-polar solution and the polar solution in contact, the polymerization is up only the interface is formed is a polyamide active layer thickness is very thin.
[6]
On the other hand, there is a condition to be provided in order to be such a polyamide-based water treatment membrane is used commercially, it has a high salt rejection and flux such as excellent performance as a separation membrane. The salt rejection of the membrane is a commercial demand may be at least be not less than 97%, and relatively low pressure in the ability to pass a relatively large amount of water, i.e. high flow characteristics for brackish water.
[7]
On the other hand, in recent years, it has emerged as an important problem to prevent the contamination with the membrane as to improve the performance such as the salt rejection and the flux of the water separation membrane. Membrane contamination is that the suspended solids or dissolved material layer for adsorbing to or adhering to the surface, if contamination occurs, the flux is lowered and is due to a contaminant growth adsorbed microorganisms in membrane surface biofilm (Bio-film) on the separator surface this is liable to secondary pollution formed. In order to obtain permeated water of a constant flow rate, since the contaminated membrane permeability falls, so it is not preferable to be cleaned if the need frequent calibration of the pressure, or severe the membrane contamination.
[8]
Therefore, it is possible to prevent contamination of the film, the more the development of cost-effective method for preparing a reverse osmosis membrane having a salt rejection while superior high flux is demanded.
Detailed Description of the Invention
SUMMARY
[9]
Herein, the reverse osmosis membrane method using a composition for forming a reverse osmosis membrane, and this protective layer is described.
Problem solving means
[10]
The exemplary embodiment of the disclosure is represented by the following general formula (1), there is provided a reverse osmosis membrane for the protective layer forming composition comprising a 500,000 to 700,000 average molecular weight substances.
[11]
Formula 1
[12]
[13]
In the general formula 1, R1 and R2 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Or a substituted or unsubstituted alkyl group, n is from 10,000 to 20,000.
[14]
Another embodiment of the present disclosure to form a polyamide active layer on a porous support; And it provides a reverse osmosis membrane production method including the step of forming the protective layer by using a reverse osmosis membrane for forming a protective layer above the active layer on the polyamide composition.
[15]
Another embodiment of the present disclosure is a porous support; The active layer comprising polyamide on the porous support; And the protective layer, and a protective layer formed on the polyamide active layer provides a reverse osmosis membrane comprising the above-described materials or a crosslinked product.
[16]
Another embodiment of the present disclosure provides a water treatment module including the above-mentioned reverse osmosis membrane for more than one.
[17]
Another embodiment of the present disclosure provides a water treatment apparatus comprising at least one of the foregoing water treatment modules.
Effects of the Invention
[18]
Is manufactured by an exemplary embodiment the composition for protective layer formation according to the reverse osmosis membrane in the reverse osmosis membrane of this specification shows a high cross-linking at least 99.89% higher salt rejection and the boron rejection, by coating a polymer having the viscoelastic to the protective layer.
[19]
In addition, the reverse osmosis membrane prepared by a reverse osmosis membrane, a composition for protective layer formation according to one embodiment of the present disclosure is to increase the mechanical strength due to the cross-linked coating, damage of the reverse osmosis membrane is minimized.
Brief Description of the Drawings
[20]
Figure 1 illustrates a surface of the reverse osmosis membrane in accordance with one embodiment of the present disclosure.
[21]
2 is in the reverse osmosis membrane in accordance with one embodiment of the present disclosure, showing the cross-section of the protective layer.
Best Mode for Carrying Out the Invention
[22]
When that member which is positioned "on" the other element herein, it also includes a case member which is in contact with the other members, as well as if the other member exists between the two members.
[23]
Assuming that any part "includes" a certain component in the present specification, which is not to exclude other components not specifically described are the opposite means that may further contain other components.
[24]
And in more detail described below herein.
[25]
The exemplary embodiment of the disclosure is represented by the following general formula (1), there is provided a reverse osmosis membrane for the protective layer forming composition comprising a 500,000 to 700,000 average molecular weight substances.
[26]
Formula 1
[27]
[28]
In the general formula 1, R1 and R2 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Or a substituted or unsubstituted alkyl group, n is from 10,000 to 20,000.
[29]
According to an exemplary embodiment of the present specification, the R1 and R2 may be the same as or different from each other, and each independently represent a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms.
[30]
According to an exemplary embodiment of the present specification, the R1 and R2 may be hydrogen.
[31]
According to an exemplary embodiment of the present specification, the alkyl group may be linear, branched or cyclic swaeil. Further, according to an exemplary embodiment of the present description, the alkyl groups are methyl, ethyl, n- propyl, iso- propyl, n- butyl, sec- butyl, t- butyl, n- pentyl, iso- the pen may be a group, neo- pentyl, n- hexyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group or a cyclohexyl group. However, the embodiment is not limited thereto.
[32]
According to an exemplary embodiment of the present disclosure, n it may be from 10,000 to 20,000, preferably from 11,000 to 16,000 may be, may be more preferably from 12,000 to 15,000.
[33]
According to an exemplary embodiment of the present disclosure, if the weight average molecular weight of the material 500,000 is less than, if the act as impurities in the protective layer contains the material salt rejection, and the flux a can be reduced, 700,000, greater than excessive molecular weight there is a flux can be reduced by.
[34]
According to an exemplary embodiment of the present disclosure, the amount of the substance may be a 0.3 to 0.5% by weight, based on the total weight of the composition for forming a reverse osmosis membrane, a protective layer, more preferably 0.4 to 0.5% by weight. When the content of the material is less than 0.3% by weight, in the protective layer may be partially formed on the protective layer is a reaction of the material as a whole can not take place film, and can decrease salt rejection and the boron rejection, and the material If the content is greater than 0.5% by weight, the said protective layer is formed excessively on the surface of the polyamide film may decrease the flux.
[35]
According to an exemplary embodiment of the present disclosure, the composition for forming the reverse osmosis membrane, a protective layer may further include one or more of a hydrophilic polymer and a crosslinking agent.
[36]
According to an exemplary embodiment of the present disclosure, the composition for forming the reverse osmosis membrane, a protective layer may further include a hydrophilic polymer.
[37]
According to an exemplary embodiment of the present disclosure, the composition for forming the reverse osmosis membrane, a protective layer may further comprise a crosslinking agent.
[38]
According to an exemplary embodiment of the present disclosure, the composition for forming the reverse osmosis membrane, a protective layer may further include a hydrophilic polymer and a crosslinking agent.
[39]
More specifically, the hydrophilic polymer is a polyvinyl alcohol (Poly Vinyl Alcohol, PVA), and wherein the cross-linking agent may be a glutaraldehyde (Glutaraldehyde, GA). When a reverse osmosis membrane for forming the protective layer composition further comprises one or more of the hydrophilic polymer and a crosslinking agent, a material represented by formula (1) may be crosslinked with at least one of a hydrophilic polymer and a crosslinking agent to form a crosslinked product.
[40]
The polyvinyl alcohol (Poly Vinyl Alcohol), as well as the effect of the flux to improve the hydrophilic groups in the hydrophilic polymer, the film surface is present, have a resistance to contamination.
[41]
The glutaraldehyde (Glutaraldehyde) are able to contribute to the role of cross-linking to the surface of the polyamide layer of the material described later, improved salt rejection with a protective layer which will be described later by being physically adsorbed on the polyamide layer.
[42]
According to an exemplary embodiment of the present disclosure, the composition for forming the reverse osmosis membrane, a protective layer may further contain water in addition to materials of the formula (1).
[43]
According to an exemplary embodiment of the present disclosure, for forming a reverse osmosis membrane, a protective layer composition may further include a hydrophilic polymer in addition to materials of the formula (1), and the other may be water.
[44]
According to an exemplary embodiment of the present disclosure, for forming a reverse osmosis membrane, a protective layer composition may further comprise a cross-linking agent in addition to materials of the formula (1), and the other may be water.
[45]
According to an exemplary embodiment of the present disclosure, for forming a reverse osmosis membrane, a protective layer composition may further comprise a hydrophilic polymer and a crosslinking agent in addition to materials of the formula (1), and the other may be water.
[46]
According to an exemplary embodiment of the present specification, the reverse osmosis membrane, a composition for forming the protective layer may be formed of parts of water substance, a hydrophilic polymer, a crosslinking agent, and the balance of the formula (1).
[47]
According to an exemplary embodiment of the present specification, the content of the hydrophilic polymer may be from 0.1 to 10% by weight, based on the total weight for forming a reverse osmosis membrane, a protective layer composition, may be preferably from 0.1 to 5% by weight, more preferably it may be 1 to 4% by weight.
[48]
According to an exemplary embodiment of the present specification, the content of the crosslinking agent may be a range of 0.01 to 10% by weight, based on the total weight for forming a reverse osmosis membrane, a protective layer composition, may be preferably 0.01 to 5% by weight, more preferably It may be from 0.1 to 2% by weight.
[49]
According to an exemplary embodiment of the present specification, the material represented by Formula 1 as compared with the case of coating with a protective layer only polyvinyl alcohol, polyvinyl alcohol (Poly Vinyl Alcohol) than as with a viscoelastic polymeric (Poly Vinyl Alcohol) 99.89% or more indicates a high salt removal ratio, it is possible to improve boron rejection.
[50]
According to an exemplary embodiment of the present specification, the reverse osmosis membrane comprising a protective layer formed by forming a protective layer including a material represented by the formula (1) composition exhibits at least 99.89% salt rejection, and preferably the removal rate of 99.9% or more salt .
[51]
According to an exemplary embodiment of the present specification, the reverse osmosis membrane comprising a protective layer formed by the protective layer-forming composition comprises a material represented by Formula 1 is the removal rate more than 93% boron, preferably from more preferably more than 93.2%, represents more than 94.3% boron rejection.
[52]
Another embodiment of the present disclosure to form a polyamide active layer on a porous support; And it provides a reverse osmosis membrane production method including the step of forming the protective layer by using the above-described composition onto the polyamide active layer.
[53]
According to an exemplary embodiment of the present disclosure, to the porous support, it may be used on the non-woven fabric having a coating layer of a polymer material. To the polymer material, e.g., polysulfone, polyether sulfone, polycarbonate, polyethylene oxide, polyimide, polyether imide, polyether ether ketone, polypropylene, polymethylpentene, polyvinyl chloride, or polyvinylidene It may be used, such as the fluoride, but are not necessarily limited to these. Specifically, it is possible to use a polysulfone as the polymer material.
[54]
According to an exemplary embodiment of the present disclosure, the polyamide active layer may be formed through an interfacial polymerization of an organic solution containing the aqueous solution and the acyl halide compounds containing an amine compound. More specifically, the method comprising the polyamide active layer is formed and the aqueous layer containing the amine compound to the porous support; And contacting the organic solution containing the acyl halide and an organic solvent in the aqueous layer containing the amine compound may be formed through the step of forming the polyamide active layer.
[55]
Upon contact of the aqueous layer and the organic solution including the amine compound, and with an amine compound and an acyl halide the reaction is coated on the surface of the porous support produce the polyamide by means of interfacial polymerization, it is adsorbed to the microporous support films It is formed. In the contact method, it may be through a method such as dipping, spraying or coating to form a polyamide active layer.
[56]
According to an exemplary embodiment of the present disclosure, a method of forming a solution layer containing an amine compound on the porous support is not particularly limited, if the method capable of forming a solution layer on a support can be used without limitation. Specifically, a method of forming a solution layer containing an amine compound on the porous support may include spraying, coating, dipping, dropping or the like.
[57]
At this time, the aqueous layer may be subjected to additional steps to remove the aqueous solution containing an amine compound of the excess, if necessary. Aqueous layer formed on the porous support when the aqueous solution present on the support is too large, may be unevenly distributed, the aqueous solution if unevenly distributed, the polyamide active layer non-uniformity by the interfacial polymerization of a later be formed have. Therefore, it is desirable to remove the excess aqueous solution after formation of the aqueous layer on the support. Removal of the excess aqueous solution is not specifically limited, for example, can be performed by using a sponge, an air knife, a nitrogen gas blowing, air drying, or compression rolls.
[58]
According to an exemplary embodiment of the present disclosure, the amine compound in the aqueous solution containing the amine compound are amine compounds if used in the manufacture of a water treatment separation membrane, but not limit the types, if there are any specific examples, m- phenylenediamine (mPD ), p- phenylenediamine, 1,2,4-benzene triamine, 4-chloro-1,3-phenylene diamine, preferably 2-chloro-1,4-phenylenediamine or a mixture thereof.
[59]
According to an exemplary embodiment of the present disclosure, the acyl halide compounds, making but are not limited, for example, as an aromatic compound having two or three carboxylic acid halide, trimesoyl chloride (TMC), isophthaloyl as chloride and terephthaloyl chloride may be at least one mixture selected from the compound group consisting of chloride.
[60]
According to an exemplary embodiment of the present disclosure, the organic solvents include aliphatic hydrocarbon solvents such as Freon acids with a carbon number of 5 to 12 as hexane, cyclohexane, heptane, and the hydrophobic liquid that is immiscible with water such as alkanes e. g., it is not the number of carbon atoms is in IsoPar (Exxon) of 5-12 alkanes and mixtures thereof, IsoPar g (Exxon), ISOL-C (SK Chem), ISOL-g (Exxon), but such can be used, thereby limiting.
[61]
Next, forming a protective layer on the polyamide active layer is, for be example, performed by a method of the polyamide active layer is immersed in a formed support to a composition for the above-mentioned reverse osmosis membrane, a protective layer is formed, and the polyamide but may be performed through a method of applying a reverse osmosis membrane for a protective layer-forming composition described above on a substrate an active layer is formed, it is not limited thereto.
[62]
On the other hand, the immersion time can be properly adjusted in view of the thickness of the protective layer to be formed, for example, 0.1 minutes to 10 hours, preferably of about 1 minute to 1 hour. If the immersion time is less than 0.1 minutes, it is not enough to form a protective layer, if the immersion time exceeds 10 hours, the thickness becomes too thick a protective layer has a negative effect to decrease the flux of the reverse osmosis membrane.
[63]
Another embodiment of the present disclosure is a porous support; The active layer comprising polyamide on the porous support; And the protective layer, and a protective layer formed on the polyamide active layer provides a reverse osmosis membrane comprising the above-described materials or a crosslinked product.
[64]
Referring to Figure 1 and showing a cross-sectional view showing the surface of the protection layer 2, it can be seen that the protective layer coating is cross-linked to form a physically adsorbed on the polyamide active layer.
[65]
According to an exemplary embodiment of the present specification, the content of the above-described material may be a 5 to 20% by weight based on the weight of the protective layer, more preferably from 10 to 15% by weight. When the content of the material is less than 5% by weight, the polyamide active layer and the protection away from the crosslinking between the layers, salt removal ratio and boron, and the removal rate may decrease, when the amount of the substance exceeds 20% by weight, an excessive thickness of the protective layer as it may be the flux is reduced.
[66]
According to an exemplary embodiment of the present disclosure, the thickness of the protective layer may be 100nm to 300nm. If the thickness of the protective layer is less than 100nm, and a polyamide active layer can be easily damaged, when more than 300nm can reduce the flux and salt rejection of the reverse osmosis membrane.
[67]
According to an exemplary embodiment of the present specification, the elastic modulus (Young's modulus) of the reverse osmosis membrane may be more than 2GPa, may be specifically 2GPa to 10GPa. Preferably it may be 4.5GPa to about 10GPa, may be more preferably 6GPa to 10GPa.
[68]
And the modulus of elasticity may be a reverse osmosis membrane is easily damaged by the mechanical strength is insufficient if less than 2GPa, if more than 10GPa due to the mechanical strength is lowered, the flexibility of the reverse osmosis membrane can also result in damage to the reverse osmosis membrane.
[69]
The modulus of elasticity is an atomic force microscope; is measured in (Atomic-force microscopy AFM), and to quantify the physical characteristics of the reverse osmosis membrane can be quantified by the following equation.
[70]
[Young's modulus = Tensile Stress (Tensile stress) / strain (Extensional strain)]
[71]
Terms of the present invention, "Atomic force microscopy (atomic force microscopy; AFM)" is a scanning probe microscope (scanning probe microscopy) of high resolution having 1000 times as high as a nanometer level of resolution than typical optical diffraction limit. AFM is to be made to overcome the disadvantages of the scanning tunneling microscope (scanning tunneling microscopy, STM), STM is because it is based on the quantum tunneling (quantum tunneling) concept requires a conductive probe, it can be applied to the conductive or semiconductive sample on the other hand, AFM can be widely to any type of surface, for example, polymers, ceramics, composites, glass and biological specimen used, because use of an atomic force. Generally AFM comprises a probe located in the cantilevered end, to measure the force acting between the sample surface and the ends of the probe. Specifically, it depends on the spring constant of the cantilever probe is located. For example, if the spring constant of the cantilever (about 0.1 to 1 N / m) is smaller than the interaction with the sample surface, the cantilever is bent observed standing refraction (deflection).
[72]
AFM is based on whether the contact between the sample and the AFM probe 1) in contact mode (contact mode), 2) the intermittent mode (or tapping mode, three other of the intermittent mode or tapping mode) and 3) non-contact mode (non-contact mode) the mode is enabled. First, the probe and the sample surface in the contact mode has the distance of less than 0.5 nm, and the van der Waals repulsion forces (Van der Waals repulsive force) acts between them. Allows fast measurements and to fit a rough sample, but the advantage of using the frictional force (friction) analysis, a soft specimen has a disadvantage that may be damaged or deformed. Next, the intermittent mode, the cantilever vibrates at regular intervals 0 people probe is moved in the distance of the sample surface with 0.5 to 2 nm. To analyze the samples combined to weaken the sample or easy to damage the surface at high resolution, and has an advantage suitable for the analysis of biological samples. On the other hand, the slower the scanning speed is difficult and imaging disadvantages in the liquid phase. Finally, the probe in non-contact mode, maintaining the sample surface and from 0.1 to 10 nm, and the distance does not directly contact, the probe and sample surface action between the van der Waals force (attractive Van der Waals force). On the sample Newton pico (10 -12 N) applied to a very small level because the power of a long probe life. However, was compared to the other mode, the low resolution can be analyzed by the inhibition capability contamination layer on the sample surface in order to obtain the best image has the disadvantage that it requires a vacuum in the ultra-high.
[73]
In this specification, as opposed to when not using it in case of using the atomic force microscope to measure the modulus of elasticity of the reverse osmosis membrane, cross-linked coating the material with a viscoelasticity in the protective layer, the elastic modulus of the reverse osmosis membrane over 2Gpa, preferably, it can be seen that the fact that more than, and more preferably, the mechanical strength of the reverse osmosis membrane to increase over 6GPa 4.5GPa.
[74]
Another embodiment of the present disclosure, there is provided a water treatment module including the above-mentioned reverse osmosis membrane for more than one.
[75]
Specific kind of the water treatment module is not particularly limited, and examples thereof include such as a plate (plate & frame) module, a tubular (tubular) module, a hollow fiber (Hollow & Fiber) module or a spiral wound type (spiral wound) module. In addition, the water treatment module which comprises a reverse osmosis membrane described above, or other any other configuration and manufacturing method, etc. are not particularly limited, and can employ the common means known in the art, without limitation.
[76]
Another embodiment of the present disclosure provides a water treatment apparatus comprising at least one of the foregoing water treatment modules. The water treatment apparatus can be effectively used as a water treatment device, such as a domestic / industrial water purification system, sewage system, haedam treatment system according to the application.
Mode for the Invention
[77]
Hereinafter, the embodiment for example, in detail in order to explain the present disclosure will be described in detail. However, embodiments according to the disclosure are can be modified in many different forms, but the scope of the present disclosure be construed as limited to the embodiments set forth herein. The practice of this specification examples are provided to more completely describe the present specification to those skilled in the art.
[78]
< Preparation > Preparation porous support is a polyamide active layer is formed
[79]
DMF (N, N- dimethylformamide) to put the polysulfone solid content of 16% by weight was obtained by dissolving a least 12 hours at 80 uniform liquid. The solution was cast as a 45 ~ 50㎛ thickness on non-woven fabric 95 to the 100㎛ thickness of the polyester material to form a porous polysulfone support.
[80]
Using an aqueous solution containing m-phenylenediamine (mPD) of 4% by weight of a porous polysulfone substrate prepared by the above method to form an aqueous phase.
[81]
By that do the following, trimesoyl chloride (TMC), 1,3,5- trimethylbenzene interfacial polymerization to form the organic layer of the composition coated on the aqueous layer containing the (TMB), and Isopar-G polyamide active layer a formed porous support was prepared.
[82]
< Example 1>
[83]
Polyvinyl alcohol (PVA) 2% by weight of glutaraldehyde (GA) 0.1% by weight and a weight average molecular weight of 600,000 a polyethylene oxide (PEO) for the reverse osmosis membrane a protective layer-forming composition containing 0.3% by weight of the mixture was stirred for 20 min or more. Then, after washing the porous support having a polyamide active layer produced by the production example 1 with distilled water and the high temperature (60 ℃), a reverse osmosis membrane and by coating the composition, and dried at 90 oven 10 minutes to form a protective layer It was prepared.
[84]
< Example 2>
[85]
Example instead of the composition for the reverse osmosis membrane a protective layer formed of the first, polyvinyl alcohol (PVA) 2% by weight of glutaraldehyde (GA) 0.1% by weight and a weight average molecular weight 600,000 for a polyethylene oxide (PEO) protect the reverse osmosis membrane containing 0.5% by weight a reverse osmosis membrane in the same manner as in example 1, except for using the layer-forming composition was prepared.
[86]
< Example 3>
[87]
Embodiment, except Example 1 was used to form the reverse osmosis membrane, a protective layer-forming composition, instead of polyvinyl alcohol (PVA) 2% by weight and a weight average molecular weight of 600,000 a polyethylene oxide (PEO) for the reverse osmosis membrane a protective layer-forming composition containing 0.3% by weight of, subjected to the reverse osmosis membrane was prepared in the same manner as in example 1.
[88]
< Comparative Example 1>
[89]
Example 1 The reverse osmosis membrane in the same manner as in Example 1, except that instead of the composition for a reverse osmosis membrane, a protective layer is formed, polyvinyl alcohol (PVA) for the reverse osmosis membrane, a protective layer-forming composition containing 2% by weight were prepared.
[90]
< Comparative Example 2>
[91]
Example instead of the composition for the reverse osmosis membrane a protective layer formed of the first, polyvinyl alcohol (PVA) 2% by weight of glutaraldehyde (GA) 0.1% by weight and a weight average molecular weight of 200,000 a polyethylene oxide (PEO) reverse osmosis membrane protection containing 0.3% by weight a reverse osmosis membrane in the same manner as in example 1, except for using the layer-forming composition was prepared.
[92]
< Comparative Example 3>
[93]
Example instead of the composition for the reverse osmosis membrane a protective layer formed of the first, polyvinyl alcohol (PVA) 2% by weight of glutaraldehyde (GA) 0.1% by weight and a weight average molecular weight of 200,000 a polyethylene oxide (PEO) reverse osmosis membrane protection comprising from 1% by weight a reverse osmosis membrane in the same manner as in example 1, except for using the layer-forming composition was prepared.
[94]
< Comparative Example 4>
[95]
Example instead of the composition for the reverse osmosis membrane a protective layer formed of the first, polyvinyl alcohol (PVA) 2% by weight of glutaraldehyde (GA) 0.1% by weight and a weight having an average molecular weight of 4,000 Polyethylene glycol (PEG) reverse osmosis membrane protection containing 0.3% by weight a reverse osmosis membrane in the same manner as in example 1, except for using the layer-forming composition was prepared.
[96]
< Comparative Example 5>
[97]
Example instead of the composition for the reverse osmosis membrane a protective layer formed of the first, polyvinyl alcohol (PVA) 2% by weight of glutaraldehyde (GA) 0.1% by weight and a weight having an average molecular weight of 4,000 Polyethylene glycol (PEG) reverse osmosis membrane protection containing 3% by weight a reverse osmosis membrane in the same manner as in example 1, except for using the layer-forming composition was prepared.
[98]
< Comparative Example 6>
[99]
Example instead of the composition for the reverse osmosis membrane a protective layer formed of the first, polyvinyl alcohol (PVA) 2 as in Example 1, except that the weight percent of glutaraldehyde (GA) for the reverse osmosis membrane a protective layer-forming composition containing 0.1% by weight the reverse osmosis membrane was prepared in the same manner.
[100]
[101]
< Experimental Example > Integer Performance
[102]
32,000 ppm NaCl and using the brine containing boron of 5 ppm were evaluated for the Examples 1 to 3 and Comparative Example 1 The performance of the reverse osmosis membrane prepared according to to 6 under 800 psi. By measuring the conductivity difference between the production and the number of the raw water were measured and salt rejection was calculated for a unit time (5 min), the flux by measuring the volume of a number of securing production per membrane unit (Flux). The enemy was adjusted to pH8.
[103]
Young's modulus was calculated through, Stiffness, the Adhesion measurements, and Hertzian model by applying the PinPoint Conductive AFM mode, through the electric contact between the tip and the sample.
[104]
sample size : up to 50mm x 50mm, 20mm thickness
[105]
XY stage : 20mm x 20mm motorized stage
[106]
Z stage : 25mm motorized stage
[107]
[108]
Performance of a reverse osmosis membrane according to the embodiments 1 to 3 and Comparative Examples 1 to 6 measured in this way is shown in Table 1 below.
[109]
TABLE 1
The salt rejection (%) Flux (GFD) Boron removal ratio (%) Young's modulus (GPa)
Example 1 99.92 12.27 95.0 6.37
Example 2 99.93 11.77 94.3 6.40
Example 3 99.89 12.41 93.2 5.94
Comparative Example 1 99.85 15.59 92.2 4.08
Comparative Example 2 99.86 8.84 92.1 4.05
Comparative Example 3 99.87 7.58 92.3 4.20
Comparative Example 4 99.62 8.17 91.5 4.02
Comparative Example 5 99.45 6.91 91.3 3.95
Comparative Example 6 99.65 9.67 91.7 3.92

[110]
GFD of the flux is gallon / ft 2 means the day.
[111]
Comparison containing only according to Table 1, Example 1, a reverse osmosis membrane according to to 3 salt and the removal rate is more than 99.89%, the flux, the boron rejection, and mechanically, while the strength are both excellent, polyvinyl alcohol (PVA) to the protective layer composition a reverse osmosis membrane according to example 1, the flux is a solid, it can be seen that the fact that the salt rejection, the boron rejection, and the mechanical strength is low.
[112]
Further, in comparison to Example 1 and compare to 3 Examples 2 and 3, in contrast with the reverse osmosis membrane, including the weight of the polyethylene oxide-average molecular weight of 200,000 (PEO), containing a polyethylene oxide (PEO) 600,000 weight average molecular weight for the reverse osmosis membrane salt rejection, the boron rejection, and the flux is considerably high, it is confirmed the fact that the mechanical strength is excellent.
[113]
Further, in Example 1 Compared to comparative examples 4 and 5 and to 3, being represented by the formula (1), the weight average for the reverse osmosis membrane having a molecular weight comprises 600,000 a polyethylene oxide (PEO), polyethylene glycol of 4,000 weight average molecular weight ( in contrast to those containing PEG), it can be found the salt rejection, the boron rejection, and the fact that the flux is considerably excellent.
[114]
Example 1 and compared to comparative examples 6 and 2, in contrast to the case of the composition for a reverse osmosis membrane, the protective layer formed contains only the polyvinyl alcohol (PVA) and glutaraldehyde (GA), polyvinyl alcohol (PVA), glutaric when the polyethylene oxide (PEO) represented by the aldehyde (GA) and the formula (1) contained all, it can be confirmed that the salt removal ratio and boron removal ratio is increased.
[115]
Further, when comparing Examples 1 and 2 and Example 3, in contrast to the case where only include polyethylene oxide (PEO) and polyvinyl alcohol (PVA) represented by the general formula (1) in the composition for a reverse osmosis membrane, a protective layer is formed, polyvinyl alcohol (PVA), it can be confirmed that the glue when tar aldehyde (GA), and that include all of the polyethylene oxide (PEO) represented by the general formula (1), salt removal ratio and boron removal ratio is increased.
[116]
Has been described with a preferred embodiment of the present invention over the above, the present invention is not limited to this can be carried out in various modifications in the description of the claims and the invention and are also within the scope of the invention .

Claims

[Claim 1]To for a reverse osmosis membrane protective layer forming composition comprising a 500,000 to 700,000 of material being represented by the formula (1), the weight average molecular weight: [Formula 1] In Chemical Formula 1, R1 and R2 are the same as or different from each other, and each independently hydrogen .; heavy hydrogen; Or a substituted or unsubstituted alkyl group, n is from 10,000 to 20,000.
[Claim 2]
The method according to claim 1, wherein R1 and R2 are hydrogen-forming composition of reverse osmosis membrane protective layer.
[Claim 3]
The method according to claim 1, a hydrophilic polymer, and a reverse osmosis membrane for the protection layer forming composition further comprises at least one cross-linking agent.
[Claim 4]
The method according to claim 1, the amount of the material is 0.3 to 0.5% by weight of the composition for a reverse osmosis membrane, a protective layer is formed, based on the total weight of the composition for forming a reverse osmosis membrane, a protective layer.
[Claim 5]
The method according to claim 3, wherein the hydrophilic polymer is a polyvinyl alcohol (Poly Vinyl Alcohol, PVA), and wherein the crosslinking agent is glutaraldehyde (Glutaraldehyde, GA) is one of a reverse osmosis membrane composition for protective layer formation.
[Claim 6]
The method according to claim 3, wherein the content of the hydrophilic polymer is in the range of 0.1 to 10% by weight of the composition for a reverse osmosis membrane, a protective layer is formed, based on the total weight of the composition for forming a reverse osmosis membrane, a protective layer.
[Claim 7]
The method according to claim 3, the amount of the crosslinking agent is 0.01 to 10% by weight of the composition for a reverse osmosis membrane, a protective layer is formed, based on the total weight of the composition for forming a reverse osmosis membrane, a protective layer.
[Claim 8]
Forming a polyamide active layer on a porous support; And a reverse osmosis membrane method and forming a protective layer using a composition for a reverse osmosis membrane, a protective layer formed according to any one of claims 1 to 7 on the polyamide active layer.
[Claim 9]
A porous support; The active layer comprising polyamide on the porous support; And a reverse osmosis membrane comprising the polyamide comprises a protective layer formed on the active layer, wherein the protective layer is represented by the following general formula (1), 500,000 weight average molecular weight to 700,000 the substance or its crosslinked product: Formula 1 Formula according to 1, R1 and R2 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Or a substituted or unsubstituted alkyl group, n is from 10,000 to 20,000.
[Claim 10]
The method according to claim 9, the amount of the material is 5 to 20% by weight of the reverse osmosis membrane based on the weight of the protective layer.
[Claim 11]
The method according to claim 9, the elastic modulus (Young's modulus) is 2GPa or more reverse osmosis membrane.
[Claim 12]
Water treatment module including a reverse osmosis membrane according to any one of claims 9 to 11, greater than or equal to 1.
[Claim 13]
Water treatment apparatus comprising a treatment module according to claim 12 or 1.