TW200844054A - Water treatment apparatus and method of water treatment - Google Patents

Abstract

A water treatment apparatus involving feeding of raw water to a reverse osmosis membrane treatment unit, wherein the reverse osmosis membrane treatment unit is one for feeding of raw water at a pH value of 7 or below and is fitted with a reverse osmosis membrane treated with a rejection rate enhancing agent composed mainly of a polymer. Further, there is provided a water treatment apparatus involving feeding of raw water to a reverse osmosis membrane treatment unit, wherein the reverse osmosis membrane treatment unit is one for feeding of raw water at a pH value of 7 or below and is fitted on its primary side with rejection rate enhancing agent supply means for supply of a rejection rate enhancing agent composed mainly of a polymer. Still further, there is provided a method of water treatment involving feeding of raw water at a pH value of 7 or below to a reverse osmosis membrane treatment unit, which method comprises the step of either periodically or when the reverse osmosis membrane treatment unit exhibits a drop in rejection rate, treating the reverse osmosis membrane of the reverse osmosis membrane treatment unit with a rejection rate enhancing agent composed mainly of a polymer.

Description

200844054 IX. Description of the Invention [Technical Field] The present invention relates to a water treatment apparatus and a water treatment method using a reverse osmosis membrane. [Prior Art] In order to effectively utilize water resources, the process of recycling, regenerating, and reusing waste water or the process of desalination of seawater is continuously carried out. Therefore, based on such a background, in order to obtain treated water having high water quality, the electrolyte can be removed, and a medium or low molecular nanofiltration membrane or a reverse osmosis membrane can be removed (hereinafter, the reverse osmosis membrane also includes a nanofiltration membrane unless otherwise specified). The use of a reverse osmosis membrane as "RO membrane" is indispensable. On the other hand, due to advances in semiconductor circuit formation technology, circuits having a line width of 65 nm or less can be fabricated. Along with this, the demand for water quality of ultrapure water is also increasing, and it is expected to develop a pure water manufacturing apparatus and a pure water manufacturing method which can reduce the load of the latter stage treatment and can realize pure water production at a higher level. The RO membrane can remove metal ions and the like at a high blocking ratio. Conversely, the metal contained in the feed water is concentrated at a high rate during concentration, so that problems due to scale defects such as calcium, magnesium, potassium, and carbonic acid are generated. Further, iron or aluminum contained in the tap water forms a precipitate in the form of a hydroxide or the like in a neutral to alkali form, and the precipitate significantly degrades the performance of the RO membrane. In order to solve such a problem, a method of adjusting the pH of the feed water of the reverse osmosis treatment apparatus (hereinafter referred to as "RO apparatus") to be acidic has been proposed (for example, Patent Document 1 and Patent Document 2). -4- 200844054 On the other hand, treatment with RO membranes is known to generally increase the blocking rate of ionized substances, and substances which are ionized in response to an increase in pH such as boron, cerium oxide, organic acid or carbonic acid. A method of removing at a high pH has also been proposed (for example, Patent Document 3 and Patent Document 4). Further, in Non-Patent Document 1, it is disclosed that the blocking ratio of NaCl in the RO film varies depending on pH, and the optimum pH range is 6 to 8. Therefore, in order to prevent the scale barrier or the RO membrane performance due to iron oxyhydroxide or aluminum hydroxide from deteriorating, if the reverse osmosis membrane treatment (hereinafter referred to as "RO treatment") is carried out under acidic conditions, boron or oxidation may occur. The blocking rate of hydrazine, organic acid, carbonic acid, and general electrolytes is lowered, causing an increase in the load of the water treatment equipment in the latter stage or an increase in processing equipment. However, the present inventors have previously proposed an RO membrane which has an increase in the blocking ratio of an inorganic electrolyte or a water-soluble organic substance by treatment with an ionic polymer (Patent Document 5). However, in this publication, the RO membrane is treated with an ionic polymer, thereby increasing the blocking rate of a completely dissociated inorganic electrolyte such as NaCl or a water-soluble organic substance such as isopropyl alcohol, but the RO is not used. The RO device of the membrane is supplied to the raw water treatment device and the water treatment method under the conditions of pH 7 or lower. Non-Patent Document 1: Kenichi Ikeda, "Development and Practical Use of Low Pressure Reverse Osmosis Membrane", Membrane Vol. 16, No. 4, 1991, p. 223-232 Patent Document 1: Japanese Patent Laid-Open Publication No. Hei 9-19687 Japanese Unexamined Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. JP-A-2006-110520 SUMMARY OF THE INVENTION An object of the present invention is to provide a water treatment method and water which can solve the above-mentioned conventional problems, and can effectively prevent scale damage when supplying raw water to a treatment. / or the performance of the RO membrane caused by the hydroxide is reduced, and the RO membrane permeating the high-quality water can be prepared to reduce the load of the treatment device, or the water treatment device can be easily By. The water treatment device according to the first aspect is a water treatment feature system including a reverse osmosis membrane treatment device that supplies raw water and membrane-treated water and concentrated water, and the reverse osmosis membrane treatment device has a raw water of pH 7 and has a A reverse osmosis membrane treated with a blocking rate enhancer. The water treatment device according to the second aspect is a water treatment feature system including a reverse osmosis membrane treatment device that supplies raw water and membrane-treated water and concentrated water, and the reverse osmosis membrane treatment device has a raw water of pH 7 and is The primary side has a supply agent for supplying a blocking rate enhancer lifter. The third aspect of the water treatment method is a method for treating a reverse osmosis membrane treated water and a concentrated water by using a reverse osmosis membrane treatment device of pH 7 or less, which is characterized in that the periodicity or the treatment rate of the reverse osmosis membrane is lowered. And a step of treating the reverse osmosis reverse osmosis membrane with a blocking rate enhancer. The treatment device RO device stops the metal and is effective, and the water in the latter stage is composed of a simplified reverse osmosis device, and the reverse osmosis device is supplied below, and the blocking rate water supplied below is supplied to the water treatment device of the water treatment device. - 200844054 According to the present invention, even if the feed water having a pH of 7 or less is supplied to the RO device by treatment with a blocking rate agent, the RO film can be obtained through the water. [Embodiment] Hereinafter, embodiments of the water treatment and treatment method of the present invention will be described in detail with reference to the drawings. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a system diagram showing a water treatment apparatus and a water treatment mode of the present invention. Figs. 2 and 3 are system diagrams showing an example of the RO device blocking rate increasing processing procedure of the present invention. The water treatment device and the water treatment method of the present invention are intended to supply the RO device to the RO device for the purpose of obtaining blockage or fouling of the RO treatment water and the concentrated water to prevent the RO device, preferably provided with the activated carbon column 1 or The filter device 2 is a pretreatment device as the device 2, and a sand filter device, an ultrafiltration device, a precision, a small filter device, or the like can be used. The pretreatment device may be further provided with a pre-set, or may be provided in the front stage of the filter device 2, and the pH adjustment tank 3 may be provided in the front stage of the RO device 4, and the pH of the raw water may be adjusted to 7 or less after the pH adjuster. The raw water below is supplied to the RO unit 4. In the pH adjusting tank 3, the whole pH is 4 to 7, preferably pH = 4.5 to 6.0, and particularly preferably pH = too low, even if it is treated with a blocking rate increasing agent as described later, it is not possible to obtain a sufficiently high water quality. RO treats water and causes problems such as corrosion or deterioration of the RO film itself. In addition, if the pH exceeds: RO membrane, high demineralization rate and water treatment are carried out, and water is p Η 7 . It is better to prevent it as shown in Figure 1. Filter the filter unit and set it again. Therefore, adding ρΗ7 is usually adjusted to 5. pH If the RO membrane is also rotted by the device 7, there will be a 200844354 rust barrier, or a barrier to the precipitation of hydroxides of such polyvalent metals when the feed water contains iron or a polyvalent metal such as Ming. Further, since the pH of the raw water is usually neutral, the pH is usually an acid, but when the pH outside the above range is low, a base can be used. Further, when the pH of the raw water is within the above range, the pH is not required, but the pH is temporarily increased due to the change in the quality of the raw water. Therefore, the pH adjusting mechanism of the pH adjusting tank 3 is preferable. The acid or base to be pH-adjusted can be used as a general user in the pH adjustment, but it is preferred to use hydrochloric acid, sulfuric acid or the like as an acid, and sodium, potassium hydroxide or the like as a base. It is also possible to provide a pH meter in the water supply system such as the pH adjusting tank 3 (not, it is also possible to set the pH to the above range on the concentrated water line of the R〇 device to be described later. For monitoring the RO processing, it is possible to set it up. It is preferable to set the water quality meter 5 in the subsequent stage. The water quality meter 5 is preferably a conductivity meter or a specific resistance meter, and may be a cerium oxide meter or a TOC meter. a plurality of water meters. The pure water is produced by the water treatment device and the water treatment method of the present invention to remove the carbonic acid in the permeated water (RO permeated water) of the RO device, as shown in FIG. 1 to set the membrane degassing after the RO device 4 The apparatus 6 is preferably an acid device. The decarbonation device can be used in the front stage of the RO device and when the degassing device is used in the decarbonation device, the performance of the degassing device is reduced in order to avoid contamination of the degassing film. It is also possible to adjust the shape of the agent to be used in the form of a special agent for the use of the setting agent.) It is simple to adjust the RO, but it can also be set for decarburization as shown in the figure. Good 200844054 again, when this is In the water treatment device and the water treatment method of the invention, when the seawater or the salt water is desalinated, or the wastewater or the circulating cooling water is desalted for recovery, the decarbonation device is preferably disposed in the front stage of the RO device 4. By disposing the decarbonation device in the front stage of the RO device 4 in this way, the RO film can be more effectively prevented from occurring by the RO film, and the recovery rate can be set higher than the present embodiment, and the stripping gas can be used. The apparatus is not limited to a decarbonation apparatus, and a decarbonation tower or a decarbonation apparatus such as bubbling with nitrogen may be used. From the viewpoint of the effect of removing carbonic acid, it is preferred to use a decarbonation column or a stripping gas device as the carbonation device. The RO unit 4 can be used in one stage, and in order to improve the water quality, a plurality of stages of two or more stages can be set. Further, when the RO device 4 is provided in a plurality of stages, the R0 film treated by the blocking rate enhancer described later may be used in all of the RO devices 4, or may be used only in a specific section. Further, when ultrapure water is produced by the water treatment device and the water treatment method of the present invention, an ion exchange resin device, an electric regenerative deionization device, and UV (ultraviolet) oxidation are disposed in the subsequent stage of the membrane degassing device 6 of Fig. 1. The device, the mixed resin (mixed bed type ion exchange resin) device, the ultrafiltration device, etc., are used in the present invention to treat the RO device of the RO device with a blocking rate enhancer (hereinafter, this process is referred to as "blocking rate lifting process" "). The RO device is composed of an R diaphragm module in which an RO membrane element having an RO membrane is attached to a tube. The R 0 film used in the R crucible device of the present invention is a liquid separation membrane in which a pressure higher than the osmotic pressure difference between the solutions is applied to the high concentration side through the membrane to block the solute and the solvent. The film structure of the R 〇 film is, for example, a polymer film such as a composite film or a phase separation film. The material of the RO film to be used in the present invention may, for example, be an aromatic polyamide or an aliphatic polyamine, a polyamine-based material such as a composite material or the like, or a cellulose-based material such as cellulose acetate. Among these, it is particularly preferable to use the aromatic polyamine RO membrane for the blocking rate improvement treatment of the present invention. The form of the RO membrane module is not particularly limited, and for example, a tubular membrane module, a planar membrane module, a spiral membrane module, a hollow membrane module, or the like can be used. The blocking rate-enhancing agent used in the present invention is not particularly limited as long as it can increase the blocking ratio of the water-soluble organic substance or the inorganic electrolyte by applying a blocking rate increasing treatment to the RO film, and is not particularly limited. A compound having a weight average molecular weight of 1,000 or more, particularly an ionic polymer having a weight average molecular weight of 100,000 or more, or a compound having a polyalkylene glycol chain having a weight average molecular weight of 1,000 to 10,000 is used. In the present invention, by using these compounds as a main component of the blocking rate enhancer, the flow rate of the RO membrane can be greatly reduced, the blocking ratio of the RO membrane can be increased, and the low molecular weight which is difficult to remove by conventional RO membranes such as electrolytes. The ionic organic matter, or boron or cerium oxide, can also be effectively removed. In the present invention, the weight average molecular weight is determined by gel permeation chromatography using an aqueous solution of a compound such as a polymer or a polyalkylene glycol, and the obtained chromatogram is converted into a molecular weight of a polyethylene oxide standard. Got it. The weight average molecular weight can be determined by a light scattering method, an ultracentrifugation method or the like in a high molecular weight range which cannot be obtained by a polyethylene oxide standard. -10- 200844054 In the present invention, the weight average molecular weight of the preferred ionic polymer to be used is preferably more than 300,000 and more preferably 1,000,000 or more. When the weight average molecular weight of the ionic polymer is less than 1,000,000, the ionic polymer is stably adsorbed to the permeable membrane, but it is difficult to maintain the state for a long period of time, and the blocking ratio may not be sufficiently improved. The ionic polymer to be used in the blocking rate enhancer of the present invention is not particularly limited, and examples thereof include a cationic polymer, an anionic polymer, and an amphoteric polymer. Among these, a cationic polymer and an anionic polymer are preferably used. The amphoteric polymer preferably has more cationic structural units or anionic structural units than other structural units, and the whole is partial cation or anionic. The cationic polymer used in the present invention may, for example, be a primary amine compound such as polyvinylamine, polyallylamine, polyacrylamide or polyglucosamine, or a secondary amine compound such as polyethylenimine or poly( a tertiary amine compound such as dimethylaminoethyl acrylate or poly(dimethylaminoethyl methacrylate), a quaternary ammonium compound such as a quaternary ammonium group added to a polystyrene, or a polyethylene ruthenium And a compound having a hetero ring such as polyvinylpyridine, polypyrrol or polyvinyldiazole. Further, a copolymerized polymer of these structures or a mixture of a plurality of polymers may be used. Among these, a compound having a hetero ring is preferably used, and a polyethylene diazole is particularly preferably used. The polyethylene diazole is a cationic polymer having a structural unit represented by the formula [1]. In the formula [1], R1 to R4 each independently represent a hydrogen atom or an alkyl group, and the alkyl group of R1 to R4 may, for example, be an alkyl group having 1 to 3 carbon atoms such as a methyl group. -11 - 200844054 [Chemical 1]

R4 / C_ C = N I N

R2

[1] a cationic polymer having a structural unit represented by the formula [1], which may be acrylonitrile or methacrylonitrile, N-vinyl carboxylic acid decylamine, N-isopropenyl carboxylic acid decylamine, N-vinyl carboxylic acid quinone imine or N-isopropenyl ruthenium hydride is copolymerized, and the obtained copolymer is hydrolyzed and deuterated to produce. The polyethylene oxime produced by such a method has a structural unit represented by the general formula [1], and also has a cyano group derived from acrylonitrile or the like, and an aminomethyl thiol group derived from hydrolysis of a cyano group. - the possibility of an amine group or the like formed by hydrolysis of a vinyl carboxylic acid guanamine unit or the like. As a commercially available product of such a cationic polymer, a cationic polymer aggregating agent "Curry Ficks (registered trademark CP111)" manufactured by Delnyd Ricks Co., Ltd. can be used. Polyethylene oxime, since the nitrogen atom of the heterocyclic ring is cationic with the nitrogen atom of the primary amine, has a high cation density and exhibits a high blocking ratio to a cation source in water. In the case of a polymer having another heterocyclic ring, the cationic density can also be increased by imparting a cationic functional group such as a primary amine. A cationic polymer having a weight average molecular weight of 100,000 or more, for example, a polymer having a structure of a -12-200844054 to a tertiary amine or a quaternary ammonium salt in a structural unit such as polyethylene fluorene The adsorption surface can effectively increase the blocking rate of the cation source in the water. The membrane surface of the membrane generally has a negative charge, and the cation molecular weight is large, so that the polymer can be stably adsorbed to the membrane surface, and, because of the high cationicity The high hydrophilicity of the molecule can be greatly reduced. In the anionic polymer to be used in the present invention, a carboxyl group of a polymer having a carboxyl group such as an enoic acid or a polymethacrylic acid or a carboxyl group may be a metal polystyrenesulfonic acid such as sodium or potassium, or a polyglucose sulfate. A polymer such as polyvinyl sulfonic acid or a polymer of a metal salt such as sodium sulfonate or potassium having a polymer of the sulfonic acid group. Further, it is possible to use the polymer or a mixture of a plurality of polymers. Among them, the sulfonic acid group has a sulfonic acid metal salt group, and since it is strongly adsorbed on the surface of the membrane of the permeable membrane to enhance the blocking performance, it is preferable because the flow beam is greatly reduced. On the surface of the membrane permeable to the membrane, there is also a decrease in the blocking ratio with respect to negative, particularly, such as polyamine bond dissociation. Therefore, even if it is an ionic polymer, it has an interaction with the presence of electric charge, and if the weight average molecular weight is more than 1, a more stable bonding state is exhibited, and the effect of improving the negative rate in water can be exhibited. Preferably, the present invention has a polyalkylene glycol chain having an average molecular weight of from 1,000 to 10,000, preferably 200 〇π to the membrane of the permeable membrane. That is, the blocking is promoted by the surface of the sub-polymer, so that the permeate stream, for example, a polymer such as polyacryl or a polymer having the salt, and an acid group having a sulfonic acid group, becomes a copolymer of polystyrene sulfonate. Acid, so it can be stably maintained for a long time, the positive charge film of charge, more significant than the positive surface of the film surface, the compound of the blocking source of the vitamin source, weighing 690, more preferably -13- 200844054 3 0 00~5 0 00. If the weight average molecular weight of the compound having a polyalkylene glycol chain is too small, the blocking rate of the nanofiltration membrane or the reverse osmosis membrane cannot be sufficiently increased, and the immobilization property of the blocking rate improving agent after the treatment is also lowered. . If the weight average molecular weight of the compound having a polyalkylene glycol chain is too large, the permeation flux of the nanofiltration membrane or the reverse osmosis membrane is greatly reduced. The polyalkylene glycol chain has a structure which is presumed to be formed by dehydration polymerization of an alkylene glycol, but can be produced by anionic polymerization of an alkylene oxide base or cationic polymerization by proton. The polyalkylene glycol chain of the compound used in the present invention may, for example, be a polyethylene glycol chain, a polypropylene glycol chain, a poly1,3-propylene glycol chain, or a polytetramethylene glycol chain. These diol chains can be formed, for example, by ring-opening polymerization of ethylene oxide, propylene oxide, oxocyclobutane, tetrahydrofuran or the like. In the present invention, a compound having a polyalkylene glycol chain may be used as a compound in which a polyalkylene glycol chain is introduced into an ionic group. Examples of the ionic group include sulfo-S03H, carboxyl-COOH, amino-indole 2, and quaternary ammonium-N + R3M- (wherein R is a hydrogen atom or a hydrocarbon group, and Μ represents an ion pair such as an alkali metal atom). )Wait. These compounds having a polyalkylene glycol chain may be used singly or in combination of two or more. In the present invention, the RO device is subjected to r〇 treatment under ρΗ7 or less, and in this case, the RO device feed water is rich in anions, so that an ionic group having a compound having a polyalkylene glycol chain is introduced to strongly anionic. The sulfo group is effective. a method for introducing a sulfo group into a polyalkylene glycol chain, for example, adding a solution of glycidol and sodium sulfite in a polyethylene glycol aqueous solution by a reaction under reflux conditions of 7 〇 〜9 〇 ° C, -14- 200844054, The sulfonated polyethylene glycol represented by the following formula [2] or [3] can be synthesized. [Chemical 2]

H(OCHaCH2)i7rrr〇〇tCH*-CHO X Y

Nj ΟII , ν O-S- OCH-CH -(ΟΟΗ,ΟΗ,)πγ 0 x y Q \\ -S-CT ΝίII 〇 [23

oII

-fCH-CHOI i X Y -S —0~ ΝI II ‘100 0 [3] However, in the formula [2], [3], (X, Y) (Η, CH2OH) or (CH2OH, H). However, the sulfonated polyethylene glycol is not limited to the compound represented by the formula [2] or [3], and examples thereof include a compound represented by the following formula [4], a compound represented by the formula [5], and the like. [化3] Ο

II H(OCHaCH2)r^Tr〇〇-S-〇- Na^

II Ο Ο Ο

II II

Na+—Ο—S — (OCHaCH2)5^rn^〇—S—CT Na + -15— (4) 200844054 In the present invention, treatment with an aqueous solution of a compound having a polyalkylene glycol chain having no ionic group introduced therein The RO membrane adsorbs a compound having a polyalkylene glycol chain having no ionic group introduced thereto, thereby increasing the blocking ratio of the nonionic low molecular weight. Further, the RO membrane is treated with an aqueous solution of a compound having a polyalkylene glycol chain having an ionic group introduced thereto, and a compound having a polyalkylene glycol chain having an ionic group introduced thereto is adsorbed on the membrane, whereby the resistance of the ionic solute can be enhanced. Break rate. In the former, although the blocking rate of ionic solutes is increased, the effect of the latter is higher. On the contrary, in the latter, although the blocking rate of nonionic solute is improved, the former blocks the nonionic solute. The rate increase effect is high. Therefore, it is preferable to use both of the objects to be separated and the purpose. According to the present invention, when the blocking ratio of the film of the substrate is high, a higher blocking ratio can be imparted by the bursting rate increasing treatment. In the present invention, the polyalkylene glycol chain is preferably a polyethylene glycol chain. A compound having a polyethylene glycol chain is easy to handle as a blocking rate enhancer because of its high water solubility, and since the affinity of the surface of the composite film is high, the performance over time after the treatment is less reduced. The blocking rate enhancer used in the present invention may contain a blocking rate confirming tracer composed of an inorganic electrolyte or a water-soluble organic compound. By passing the compound as a main component and the water containing the tracer through a nanofiltration membrane or a reverse osmosis membrane, the blocking ratio of the RO membrane can be confirmed over time, and the treatment can be judged to continue or stop. The water treatment time at the time of the blocking rate increase treatment is usually 1 to 50 tracer hours, preferably 2 to 24 hours, and when the tracer concentration through the water reaches a predetermined time. , to determine the RO membrane blocking rate of the established -16 - 200844054 値, and can end the blocking rate improvement process. By using the length of the contact time between the aqueous solution of the lifting agent and the RO membrane, the RO membrane can be immediately started with the blocking rate increasing agent for a plurality of times of blocking rate replacement, and can be efficiently used as a tracer. The inorganic electrolyte sodium salt and the weak electrolyte boric acid are preferably used to use sodium chloride. The tracer may be, for example, a viewpoint of isopropanol or glucose, and when isopropyl alcohol is used as an inorganic strong electrolyte such as sodium chloride, it is preferably 100 to 500 mg/L. When it is another water-soluble organic substance such as isopropyl alcohol, t 5 to 1 000 mg/L is more preferable. The concentration of the blocking rate-enhancing substance (that is, the weight average molecular weight of 1 million and the average molecular weight of 1000-10000) used in the present invention is preferably a solution of about ～1 to 50 mg/L. The compound concentration varies depending on, for example, the above-mentioned weight average molecular polymer is 0.1 to 5 mg/L, the weight average j-polymer is preferably 0.1 to 20 mg/L, and 1 000 to 1 0000 has polyalkylene. Two 0.01 1~lmg/L is preferred. If the concentration is lower than this, the blocking rate can be controlled to the necessary minimum and usually operate. Also, when the non-lifting process is used, the processing of the number of times is not lost. The water-soluble organic compound urea to be used, for example, from the viewpoint of easiness of sodium chloride or nitrate, is preferable from the viewpoint of handling. The concentration of the tracer, preferably 10 to 1 000 mg / L, an inorganic weak electrolyte such as boric acid, 乂 1 to 5000 mg / L is preferred, an aqueous solution of the above-mentioned ionic polymer or a polyalkylene glycol The combination of chains is better. The blocking rate-increasing agent has a cation + sub-amount of 100,000 or more depending on the type of the compound to be used, and an anion of less than 100,000 or more; when it is a compound having a weight average molecular weight alcohol chain, the blocking rate is improved. - 200844054 To be a long time. When the concentration exceeds 50 mg/L, the viscosity of the aqueous solution increases, and the impedance of the RO film increases. Further, when the concentration exceeds 5 Omg/L, an unnecessary thick coating layer (adsorption layer) is formed and the concentration is extremely divided, and conversely, the blocking rate improving effect is weakened. By passing a different blocking rate enhancer through the R〇 device' more than a single blocking rate enhancer, a higher blocking rate can be obtained, and a more stable blocking rate enhancer adsorption state can be obtained. For example, after the cationic polymer is adsorbed on the R ruthenium film, the anionic polymer is adsorbed, whereby the repulsion of ions of the same symbol of each adsorption layer can increase the blocking ratio of the cation and the anion by the cationic polymer and The interaction of the anionic polymer can stabilize the mutual adsorption state. The blocking rate enhancement treatment is carried out by immersing the R0 membrane module in an aqueous solution containing a blocking rate enhancer, preferably by passing water through the primary side of the RO membrane module. The time each time the aqueous solution containing the blocking rate enhancer is passed through water is preferably 2 to 24 hours. If the blocking rate is increased in the aqueous solution to increase the concentration, the water passing time can be shortened, but the reduction in the flow rate can be increased. When the aqueous solution containing the blocking rate increasing agent passes through the water, the "permeable water discharge valve of the RO membrane module can be closed", but by taking out the water while being treated, the treatment can be efficiently performed without stopping the apparatus. The blocking rate enhancer adsorbs to the RO membrane surface efficiently and uniformly. In this case, it is preferable that the operating pressure when the aqueous solution containing the blocking rate increasing agent is supplied to the primary side of the R film module is 0. 3 M Pa or more, and the permeated water amount/blocking rate is made. The supply amount of the aqueous solution of the enhancer is 0.2 or more (for example, 〇·2 to 〇·8). Thereby, the blocking rate can be effectively increased to the RO membrane surface by the -18-200844054 liter agent, and the blocking rate increasing agent can be efficiently and uniformly adsorbed on the RO membrane surface. Next, an embodiment of a method for treating an RO membrane of the present invention will be described in detail with reference to the drawings. 2 and 3 are system diagrams showing the form of an apparatus for carrying out the RO membrane processing method of the present invention. 2, 3, 11 are the treated water tank, 12 is the treated water tank, 13 is the alkaline washing liquid tank, 14 is the acidic washing liquid tank, and 15 is the blocking rate increasing agent aqueous solution A. The tank, 16 is a blocking rate enhancer aqueous solution B tank, 20 is a RO membrane module, Pi is a high pressure pump, P2 is a pump for washing liquid, P3 is a blocking rate lifting agent aqueous solution A pump, P4 is A pump for the blocking rate enhancer aqueous solution B. Vl to V22 are valves. Further, in Figs. 2 and 3, main piping and valves are shown, and other valves, gauges, and pipings are omitted. In Figures 2 and 3, when the treated water RO is treated, the valves V i, V2, V3, V4, V5, and V22 are opened, and the other valves are closed to operate the high pressure pump P!, which will be treated in the water tank 1 1 The treated water is supplied to the R membrane module 20 to separate the RO membrane, and the permeated water is taken out of the system. Further, the concentrated water is discharged to the outside of the system through the valve V3, and a part of the concentrated water is returned to the treated water tank 11 through the valve V4 as needed in order to increase the recovery rate of the treated water. Further, the valves V6 and V@7 are opened as needed, and the permeated water is stored in the treatment tank 12. Further, the valves V18, V19, V2G, and V21 are opened, and the permeated water is supplied to the alkaline cleaning liquid tank 13 and the acidic cleaning liquid tank 14 and the blocking rate increasing agent aqueous solution A tank 1 5 . The blocking rate enhancer aqueous solution B tank 1 6 ' can be used for dilution, adjustment, etc. of the washing liquid or the polymer aqueous solution. By performing the RO treatment, when the permeate stream of the R0 film is lowered and the -19-200844054 drug is washed, the high pressure pump Pi is stopped, the valves v2, v4, 1 are opened, the other valves are closed, and the washing liquid is operated by the pump P2. This is circulated so that the alkaline cleaning liquid in the alkali tank 13 is introduced into one of the RO membrane modules 20 and returned to the inside of the tank 13. At this time, a part of the f-cleaning liquid may be opened and permeable to the outside of the membrane. Alternatively, ϊ, V ! 8, return the permeable membrane cleaning solution to the tank 13 . After the alkali is circulated for a predetermined period of time, the cleaning liquid pump P2 is stopped as the case may be, and after the static liquid is allowed to stand for a certain period of time, the alkaline cleaning liquid is discharged to the outside of the system by a drain pipe (not shown) provided for alkaline washing. Then, V2, V4, V9, and V14 are opened, and the acidic cleaning liquid in the other acidic cleaning liquid tank 14 is turned off and introduced into the RO membrane to be circulated to the primary side, and then returned to the inside of the tank 14 to circulate. At this time, the valve V5 is opened, and a part of the cleaning liquid is transmitted through the membrane, and the V6 and V19 are opened, and the cleaning liquid of the permeable membrane is returned to the tank cleaning liquid for a predetermined period of time, and the cleaning liquid is stopped as the case may be. After the chemical solution is held for a predetermined period of time, the acidic cleaning liquid is discharged to the outside of the system by a drain pipe (not shown) provided in the liquid tank 14. Then, the valves V2, V3, and V7 are opened, and the primary side of the RO membrane module 20, which is treated with the water in the other tanks, is closed and discharged to the outside of the system through the valve V3. Further, the effluent is washed to the cleaning liquid tanks 1 3 and 14 and discharged from the drain pipes provided in the tanks. Washing (rinsing) with the treated water can be carried out between washing with an alkali and washing with an acidic washing solution. In addition, the cleaning of the cleansing liquid and the cleaning with the acidic washing liquid, which is advanced / 8, V 1 3 ' sexual washing liquid secondary side, circle v5, T open V6 cleaning liquid to maintain the liquid Use slot 1 3 valve to make group I 2 0, or snoring or 1 4 . The acid pump P2 is cleaned and acidified for treatment, and the washing can be returned. (The non-inferior washing liquid can be washed by alkaline washing, -20- 200844054 can also be repeated alternately twice or more. Figure 2, when the aqueous solution with a blocking rate enhancer is used to improve the rate of breakthrough, only the blocking rate enhancer aqueous solution is filled with the blocking agent aqueous solution A tank 15 to open V 2, V 4, V i 〇, V ! 5, the closing valve, the washing liquid is operated by the pump p2, so that the blocking rate increasing agent aqueous solution in the blocking rate increasing agent water-dissolving tank 15 is introduced into the side of the R 〇 film module 20, Then, it can be recycled to the inside of the tank 15. In this case, V 5 can also be used to pass a part of the blocking rate enhancer aqueous solution through the membrane to discharge the system, or V6 and V2 can be opened to block the permeable membrane. The rate increasing agent liquid is returned to the tank 15. The blocking rate increasing agent aqueous solution is circulated for a predetermined period of time, and the blocking rate lifting agent liquid is discharged to the outside of the system by a drain pipe (not shown) provided in the tank 15. Next, the valve is opened. V2, V3, V6, V7, then open the valve V20, and other valves to treat the RO membrane mold in the treated water in the water tank 1 2 On the secondary side, one part of the washing discharge liquid is discharged through the valve V3, and the remaining part is discharged to the outside through the tank 15. In Fig. 2, when a different blocking rate ascending agent such as a cationic polymer and an anionic property is used, In the blocking rate increase treatment, for example, the ionic polymer aqueous solution and the cationic polymer aqueous solution respectively block the rate-increasing agent aqueous solution A tank 15 and the blocking rate-enhancing agent aqueous solution 16, and first, open V2, V4, V1Q, V15, the other valve is closed, and the cleaning liquid is operated by the pump P2, so that the blocking rate enhancer aqueous solution A tank 1 5 anionic polymer aqueous solution is introduced into the primary side of the RO membrane module 20 and then returned to the tank 15 for circulation. At this time, the valve V5 can also be opened, and the other resist A can be opened at the same time. After the water is dissolved, the water-soluble closed a 2 〇 external molecules will be filled with the B tank to make it wash, and then the high 21 - 200844054 A part of the molecular aqueous solution is discharged through the membrane, but it is preferred to open v6 and V2G and return the polymer aqueous solution of the permeable membrane to the tank 15. After the anionic polymer aqueous solution is circulated for a predetermined period of time, it is set. The drain pipe (not shown) of the flow rate improver aqueous solution A tank 15 discharges the anionic polymer aqueous solution to the outside of the system. Then, V2, V4, VM, and V16 are opened, and other valves are closed to increase the blocking rate. The aqueous solution of the cationic polymer in the aqueous solution B tank 16 is introduced into the primary side of the RO membrane module 20, and then returned to the inside of the tank 16. The valve V5 can also be opened to open the polymer aqueous solution. A part of the film is discharged through the film, but it is preferable to open V6 and V21 to return the polymer aqueous solution of the permeable film to the cell 16. After the cationic polymer aqueous solution is circulated for a predetermined period of time, the blocking rate is increased. A drain pipe (not shown) of the aqueous solution B tank 16 is discharged to the outside of the system. Then, open the valves V2, v3, v6, and v7, and then open any of the valves V2G or V21, and close the other valves to treat the primary side of the RO membrane module 20 in the water tank 1 2, A portion of the cleaning effluent is discharged to the outside of the system through the valve V3, and the remaining portion is discharged to the outside of the system via either of the grooves 15 or 16. The washing (rinsing) of the treated water is preferably carried out between the treatment with an aqueous solution of an anionic polymer and the treatment with an aqueous solution of a cationic polymer. Further, as described above, the treatment with the anionic polymer aqueous solution and the cationic local molecular solution may be carried out two or more times, but preferably, the anionic polymer is finally used. Treatment of aqueous solution. In Fig. 3, when the blocking rate is increased by the aqueous solution containing one blocking rate increasing agent, only the blocking rate increasing agent aqueous solution is filled with the blocking rate increasing agent aqueous solution A tank 1 5, first When V i 打开 is turned on, the pump P3 is operated, and the blocking rate enhancer aqueous solution of the blocking rate enhancer aqueous solution A tank 15 is introduced into the treated water tank 1 1, and then the high pressure pump P1 is operated to open V i, V2. V4 and V22, the other valves are closed, so that the blocking rate enhancer aqueous solution in the treated water tank 1 1 is introduced into the primary side of the RO membrane module 20, and then returned to the inside of the tank 1 to circulate. At this time, it is preferable to open the valves V3 and V5, and a part of the aqueous solution of the blocking rate enhancer is permeable to the outside of the membrane, and a part of the aqueous solution of the blocking rate enhancer is discharged to the outside of the system. Thereby, the time for stopping the operation of the RO processing apparatus can be shortened. After circulating the blocking rate enhancer aqueous solution for a predetermined period of time, turn off V ! 〇 and stop pump P3 to stop the introduction of the blocking rate enhancer aqueous solution. Next, the valves V2, V3, and V7 are opened, the other valves are closed, the high pressure pump P1 is stopped, and the pump P2 is operated to wash the primary side of the RO membrane module 20 with the treated water in the water tank 12, while The treated water containing the blocking rate increasing agent is discharged to the outside of the system through the valve V3. Also, this operation can be omitted. In FIG. 3, when a blocking rate increase treatment is performed using different blocking ratio increasing agents such as a cationic polymer and an anionic polymer, for example, an anionic polymer aqueous solution and a cationic polymer aqueous solution are respectively filled with a resistor. The rate-up agent aqueous solution A tank 15 and the blocking rate-enhancing agent aqueous solution B-tank 16 first open V! 〇 to operate the pump P3, and block the rate-enhancing agent aqueous solution A in the tank 1 5 anionic polymer The aqueous solution is introduced into the treated water tank 1 1 , and then the high pressure pump Pi is operated to open Vi, V2, V4, and V22, and the other valves are closed to introduce the anionic polymer water-soluble -23-200844054 liquid in the treated water tank 1 1 . After the primary side of the RO membrane module 20, it is circulated back to the inside of the tank 11. At this time, it is preferable to open the valves V3 and V5, and a part of the aqueous polymer solution is permeated through the membrane to be discharged, and a part of the aqueous polymer solution is discharged to the outside of the system. Thereby, the time for stopping the operation of the R0 processing apparatus can be shortened. After circulating the anionic polymer aqueous solution for a predetermined period of time, Vi 关闭 is turned off, and the pump P3 is stopped to stop the introduction of the anionic polymer aqueous solution. Next, V i ! is turned on, the pump P4 is operated, and the cationic polymer aqueous solution in the B-cell 16 of the blocking rate enhancer aqueous solution is introduced into the treated water tank 1 1 , and then the high-pressure pump Pi is operated to open V!, V2. In addition, V4 and V22 are closed to allow the cationic polymer aqueous solution in the treated water tank 1 to be introduced into the primary side of the RO membrane module 20, and then returned to the inside of the tank 1 to circulate. At this time, it is preferable to open the valves V3 and V5, and a part of the aqueous polymer solution is permeated through the membrane to be discharged, and a part of the aqueous polymer solution is discharged to the outside of the system. Thereby, the time for stopping the operation of the RO processing apparatus can be shortened. After circulating the cationic polymer aqueous solution for a predetermined period of time, V η is turned off, and the pump P4 is stopped to stop the introduction of the anionic polymer aqueous solution. Then, the valves V2, V3, and V7 are opened, the other valves are closed, the high pressure pump P i is stopped, and the pump P2 is operated to wash the primary side of the RO membrane module 20 with the treated water in the water tank 12, and will be included. The treated water of the blocking rate increasing agent is discharged to the outside of the system through the valve V3. Washing (rinsing) of the treated water may be carried out between treatment with an anionic polymer aqueous solution and treatment with a cationic polymer aqueous solution. In addition, the flushing may be omitted by stopping the introduction of the aqueous polymer solution, and the RO treatment of the treated water is performed for a predetermined time (about three times the residence time of the treated water tank), and the flushing step can be shortened by -24-200844054. Time and reduce the amount of flushing water. Further, the treatment with the anionic polymer aqueous solution and the cationic polymer aqueous solution may be carried out first or twice, or preferably, the treatment is carried out twice or more. . Further, the above embodiment is an example of the processing procedure of the RO film processing method of the present invention, and the present invention is not limited to the embodiment of the present embodiment, and the processing tanks of Figs. 2 and 3 may be omitted or omitted. The cationic polymer and the anionic polymer are used as a blocking rate enhancer alone. Further, the RO membrane treatment step, the drug washing step, and the blocking rate lifting treatment step may be carried out separately at other places. In other words, the RO membrane element may be taken out of the tube, moved to another location (for example, an RO membrane regeneration factory, etc.) by the place where the RO membrane treatment step is performed, and the medicine preparation may be carried out in a separate preparation tube of the movement destination. The net processing step and/or the blocking rate increase processing step. Further, in the case of Fig. 3, the blocking rate enhancer aqueous solution is supplied to the treated water tank 1 1, but the blocking rate enhancer aqueous solution may be directly injected into the connected treated water tank 〇 and R〇. The piping of the membrane module 20 is provided. Further, in the step of washing the drug, either acid washing or alkali washing may be performed, or the alkali washing may be performed after the acid washing. As the acid agent used for the acid washing, an organic acid such as hydrochloric acid, sulfuric acid or nitric acid, or an organic acid such as citric acid or oxalic acid can be used. As the alkali agent used for the alkali washing, sodium hydroxide, potassium hydroxide, sodium carbonate or the like can be used. Further, as the detergent, an oxidizing agent such as hydrogen peroxide, a reducing agent such as sodium bisulfite, or a surfactant such as sodium alkylbenzenesulfonate may be added. -25- 200844054 EXAMPLES Hereinafter, the present invention will be described in more detail by way of Experimental Examples, Examples and Comparative Examples. [Adjustment example] The 4-inch spiral RO membrane element "RS20-D4" manufactured by Nitto Denko Corporation was placed in a tube, and the blocking rate was raised under the following conditions using the apparatus of Fig. 2 . Further, as a final rinsing step, ultrapure water was passed through at -25 MPa for 0.5 hours to carry out treatment. Blocking rate enhancer: blocking agent with a weight average molecular weight of 4,000 to the RO membrane module. Lifting agent concentration ·· lmg/L Operating pressure: 〇.75MPa Recovery rate: 5 0 % Water running time: 2 0 hours (adjustment example 2) The 4 inch helical RO membrane element "RS20-D4" manufactured by Nitto Denko was stored in a tube, and the following cationic polymer was blocked in the following order using the apparatus of Fig. 2; The rate-increasing treatment is performed by increasing the blocking rate of the anionic polymer. In addition, after the blocking rate increase treatment of the cationic polymer and the blocking rate increase treatment of the anionic polymer, and the blocking treatment of the anionic polymer, the rinsing step is performed as a rinsing step. Pure water was passed through the water at 0.2 5 MPa for 0.5 hour to carry out the treatment. -26- 200844054 <Blocking rate increase treatment with cationic polymer> Blocking rate enhancer: Blocking rate of polyethylene glycol 重量 water supply to RO membrane module with a weight average molecular weight of 4.5 million: 4 mg/ L Operating pressure: 〇.75MPa Recovery rate: 50% Water passing time: 20 hours < Increased blocking rate by anionic polymer> Blocking rate enhancer: Polystyrene with a weight average molecular weight of 1 million Blocking rate of sodium sulfonate to RO membrane module Lifting agent concentration: 16mg/L Operating pressure: 〇.75MPa Recovery rate: 50% Water running time: 20 hours [Experimental example] Used in adjustment examples 1 and 2 The R membrane element and the untreated RO membrane subjected to the blocking rate increase treatment were subjected to RO treatment under the following conditions to measure the blocking ratio of sodium chloride at different feed water pH. The results are shown in Fig. 4 ° Raw water: in ultrapure water to make sodium chloride 400mg/L. Operating pressure: 〇.75MPa Recovery rate: 50% Raw water pH: 5.0~9.0 (with hydrochloric acid and sodium hydroxide) Adjustment) -27- 200844054 In the RO membrane (adjustment examples 1 and 2) subjected to the blocking rate increase treatment, if the pH of the feed water is low, the blocking rate of the RO membrane tends to decrease, but the tendency to decrease is smaller than that of the untreated membrane. In particular, a large difference was observed between the untreated film and the blocking rate-increasing film at p Η = 5 · 0 to 6 · 0. [Example 1] The RO membrane element subjected to the blocking rate increase treatment in the adjustment example 1 was continuously passed through water under the following conditions, and the blocking ratio of sodium chloride and the amount of permeated water & The results are shown in Fig. 5 and Fig. 6. Further, the concentration of inorganic carbonic acid (hereinafter referred to as 1C) of the feed water and the treated water after the passage of water for 12 seconds was measured. The results are shown in Table 1. Raw water: In the case of activated carbon treated tap water to make sodium chloride into the stomach 400mg / L. Operating pressure: 〇.75MPa Recovery rate: 50% Raw water pH: 5.0 Full iron: 50 // g / L (chlorine [Chemical Iron and Pure Chemicals] [Example 2] In Example 1, the same was true except that the raw water P was 6 6.0. The results are shown in Fig. 5, Fig. 6, and Table 1. [Comparative Example 1] In Example 1, the same was true except that the pH of the raw water was 7.5. -28· 200844054 The results are shown in Figure 5, Figure 6, and Table 1. [Comparative Example 2] In the first embodiment, the treatment was carried out except that a 4-inch spiral RO membrane element (untreated film) manufactured by Tosoh Corporation was used for the treatment of the blocking rate increase treatment. The results are not shown in Figure 5, Figure 6, and Table 1. [Comparative Example 3] In Comparative Example 2, the same was true except that the pH of the raw water was 6.0. The results are shown in Fig. 5, Fig. 6, and Table 1. [Comparative Example 4] In Comparative Example 2, the same was true except that the pH of the raw water was 7.5. The results are shown in Fig. 5, Fig. 6, and Table 1. [Example 3] The RO membrane element subjected to the blocking rate increase treatment in the adjustment example 2 was continuously passed through water under the following conditions, and the change in the blocking ratio of sodium chloride and the amount of permeated water was measured. The results are shown in Fig. 7 and Fig. 8. Further, the concentration of 1 C of the feed water and the treated water after the passage of water for 1 hour was measured. The results are shown in Table 1. Raw water: added in ultrapure water so that sodium chloride becomes 400mg/L. Operating pressure: 〇.75MPa Recovery rate: 50% -29- 200844054 Raw water pH: 5.0 Total iron: 50 // g/L (chlorine [Chemical Iron and Pure Chemicals] [Example 4] In Example 3, the same was true except that the pH of the raw water was 6.0. The results are not shown in Figure 7, Figure 8, and Table 1. [Comparative Example 5] In Example 3, the same was true except that the pH of the raw water was 7.5. The results are shown in Table 1.

Blocking rate increase treatment with or without feed water pH 1C concentration: mg/L] inlet outlet example 1 with 5.0 4.0 0.7 Example 2 with 6.0 12.0 1.2 Example 3 with 5.0 4.0 0.7 Example 4 with 6.0 12.0 1.2 Comparative Example 1 There are 7.5 38.0 3.8 Comparative Example 2 Μ J \ ΝΝ 5.0 4.0 1.6 Comparative Example 3 ji ji \\ 6.0 12.0 2.0 Comparative Example 4 Μ J \ 7.5 38.0 4.8 Comparative Example 5 7.5 38.0 3.5 From Figure 5 and Figure 6, or Figure 7 And Examples 1 to 4 of Fig. 8' water supply ρ Η = 5·0 and ρ Η = 6.8, compared with the comparative examples 1 and 4 of the water supply ρ Η = 7.5, not only the rate of decrease of the blocking rate but also the rate of decrease can be suppressed. Suppresses the drop in permeate water -30- 200844054 Low speed. Since it is operated by lowering the pH, it is possible to suppress the rust of Fe. Further, as is clear from Table 1, in Examples 1 and 2 and Examples 3 and 4 in which the R0 film of the blocking rate raising treatment was treated with water supply pH = 5.0 and pH = 6.0, compared with Comparative Examples 1 to 5, The IC concentration in the treated water is reduced, and the decarbonation treatment load is reduced. The present invention has been described with reference to the specific embodiments thereof, and various modifications may be made without departing from the spirit and scope of the invention. Further, the present invention is based on a copending patent application filed on Nov. 16, 2006 (Japanese Patent Application No. 2006-3 1 069 1), the entire disclosure of which is incorporated herein. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a system diagram showing an embodiment of a pure water producing apparatus and a pure water producing unit g of the present invention. Fig. 2 is a system diagram showing an example of the washing and blocking rate increasing processing steps of the RO apparatus of the present invention. Fig. 3 is a system diagram showing another example of the washing and blocking rate increasing processing steps of the RO apparatus of the present invention. Fig. 4' shows a graph showing the relationship between the feed water ρ η and the blocking rate. Figure 5 is a graph showing the change in the blocking rate over time. Figure 6 is a graph showing the change in the amount of water permeated over time. Figure 7 is a graph showing the change in the blocking rate over time. Figure 8 is a graph showing the change in the amount of water permeation over time. -31 - 200844054 [Explanation of main component symbols] 1 : Activated carbon tower 2 : Filter device 3 : pH adjustment tank 4 : RO device 5 : Water quality meter 6 : Membrane degasser 1 1 : Treated water tank 1 2 : Treatment tank 1 3 = Alkaline cleaning solution tank 1 4 : Acid cleaning liquid tank 1 5 : Blocking rate enhancer aqueous solution A tank 1 6 : Blocking rate enhancer aqueous solution B tank 20 : RO membrane module Pi : High pressure pump P2: pump for washing liquid, etc. P3: pumping rate enhancer aqueous solution A pump P4: blocking rate boosting agent aqueous solution B pump: valve-32-

Claims (1)

200844054 X. Patent Application Range: A water treatment device comprising a reverse osmosis membrane treatment device that supplies raw water and a reverse osmosis membrane treated water and concentrated water, characterized in that the reverse osmosis membrane treatment device The raw water is supplied to a supplier below pH 7 and has a reverse osmosis membrane treated with a blocking rate enhancer. 2. The water treatment device of claim 1 wherein the pH of the raw water is 4 to 7. 3. The water treatment device of claim 1, further comprising a decarbonation device in a preceding or a later stage of the reverse osmosis membrane treatment device. 4. The water treatment device according to claim 1, wherein the blocking rate enhancer is an ionic polymer having a weight average molecular weight of more than 100,000 and a polyalkylene oxide having a weight average molecular weight of 1,000 to 10,000. At least one of the compounds of the diol chain. 5. The water treatment device according to claim 4, wherein the ionic polymer is a cationic polymer or an anionic polymer. 6. The water treatment device according to claim 5, wherein the cationic polymer is a primary amine compound, a secondary amine compound, a tertiary amine compound, a quaternary ammonium compound, and a compound having a heterocyclic ring. The water treatment device according to claim 6, wherein the cationic polymer is polyethylene ruthenium. 8. The water treatment device according to claim 5, wherein the anionic polymer is a polymer having a carboxyl group, a molecule having a sulfonic acid group of -33 to 200844054, and any of the alkali metal salts. One. 9. The water treatment device of claim 8, wherein the anionic polymer polystyrene sulfonic acid or an alkali metal salt thereof is 〇10. Water treatment according to claim 4 The device, wherein the compound having a polyalkylene glycol chain is a compound having any one of a polyethylene glycol chain, a polypropylene glycol chain, a poly-1,3 propylene glycol chain, and a polytetramethylene glycol chain. 1 . A water treatment device comprising a reverse osmosis membrane treatment device that supplies raw water and obtains reverse osmosis membrane treated water and concentrated water, wherein the reverse osmosis membrane treatment device uses raw water at pH 7 The following supplier has a blocking rate enhancer supply step for supplying a blocking rate enhancer on the primary side. 1 2 . The water treatment device according to claim 1 , wherein the pH of the raw water is 4 to 7. A water treatment apparatus according to claim 1 which further has a decarbonation apparatus in a preceding stage or a later stage of the reverse osmosis membrane treatment apparatus. 14. The water treatment device according to claim 1 , wherein the blocking rate enhancer is an ionic polymer having a weight average molecular weight of more than 100,000 and a weight average molecular weight of 1000 to 10000. At least one of the compounds of the alcohol chain. The water treatment device according to claim 14, wherein the ionic polymer is a cationic polymer or an anionic polymer. -34-200844054 1 6 The water treatment device of claim 15, wherein the cationic polymer is a primary amine compound, a secondary amine compound, a tertiary amine compound, a quaternary ammonium compound, and Any of the compounds of the heterocyclic ring. The water treatment device according to claim 16 wherein the cationic polymer is polyethylene ruthenium. The water treatment device according to the fifteenth aspect of the invention, wherein the anionic polymer is a polymer having a carboxyl group, a polymer having a sulfonic acid group, and any one of the alkali metal salts. . The water treatment device according to claim 18, wherein the anionic polymer polystyrenesulfonic acid or an alkali metal salt thereof is 〇20. The water treatment device, wherein the compound having a polyalkylene glycol chain has any one of a polyethylene glycol chain, a polypropylene glycol chain, a poly(1,3-propylene glycol chain), and a polytetramethylene glycol chain. Compound. 2 1. A water treatment method for supplying raw water having a pH below 7 to a reverse osmosis membrane treatment device to obtain a water treatment method for reverse osmosis membrane treated water and concentrated water, characterized in that it is periodic or reverse osmosis When the blocking rate of the membrane processing apparatus is lowered, there is a step of treating the reverse osmosis membrane of the reverse osmosis membrane treatment apparatus with a blocking rate increasing agent. 22. The water treatment method according to claim 21, wherein the pH of the raw water is 4 to 7. 2 3 . The water treatment method according to claim 21, wherein -35- 200844054 the blocking rate increasing agent is an ionic polymer having a weight average molecular weight of more than 1 million and a weight average molecular weight of 1 000 〜1 At least one of the compounds having a polyalkylene glycol chain of 0000. 2. The water treatment method according to claim 23, wherein the ionic polymer is a cationic polymer or an anionic polymer. The water treatment method according to claim 24, wherein the cationic polymer is a primary amine compound, a secondary amine compound, a tertiary amine compound, a quaternary ammonium compound, and a compound having a heterocyclic ring. Either. 26. The water treatment method according to claim 25, wherein the cationic polymer is polyethylene hydrazine. The water treatment method according to claim 24, wherein the anionic polymer is a polymer having a carboxyl group, a polymer having a sulfonic acid group, and any of the alkali metal salts. 28. The water treatment method according to claim 27, wherein the anionic polymer is polystyrenesulfonic acid or an alkali metal salt thereof. 29. The water treatment method according to claim 21, wherein the compound having a polyalkylene glycol chain has a polyethylene glycol chain, a polypropylene glycol chain, a poly(1,3-propylene glycol chain), and a polytetraethylene compound. A compound of any of the methylene glycol chains. -36-