TW201107250A - Removal method of causative agent which decrease filtration flux in membrane bioreactor - Google Patents

Abstract

The present invention provides a method to remove a causative agent which decreases filtration flux effectively in a mixture of a membrane bioreactor with a small amount of organic polymer coagulant. A method to remove a causative agent which decreases filtration flux in a membrane bioreactor is characterized such that a remover of the causative agent which decreases filtration flux including a soluble and/or absorbent cationic polymer having a structural unit represented in a predetermined expression as an active component is added to a mixture of membrane bioreactor including the causative agent which decreases filtration flux which is at least one type of humic-like material, a polysaccharide, and an in vitro high-molecular compound of protein, and separated by the membranes.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for removing a substance having a reduced throughput of a separation membrane in a membrane separation activated sludge process. The present application is based on Japanese Patent Application No. 2009-182867, filed on Jan. 5, 2009,,,,,,,,,,,,,,,,, Substance, which is a substance that causes pore clogging in the membrane separation activated sludge method because it blocks the micropores of the membrane: the above substances refer to the multi-audio, protein, humin contained in the influent or produced by microorganisms (humin) ), other water-soluble polymer substances that cause a decrease in the flux of the film. The membrane separation activated sludge method is a method of solid-liquid separation by a separation membrane such as a precision membrane or a super furnace membrane without providing a final sinking tank in the activated sludge method. It is spreading. In addition: In recent years, the need for membrane separation of activated sludge has continued to increase in terms of the need for water reuse.疋 疋 'reality is 'in the 臈 separation of activated sludge method, due to: the material that causes the turbulent flux to decrease. 'There may be pore clogging of the membrane or f 7 in relation to membrane cleaning, replacement, etc. Therefore, it has not been widely promoted. Further, the polysaccharide or protein which is referred to as a substance for reducing the flux-reducing factor 4 201107250 may be contained in the raw water, and may be produced by microorganisms as sometimes shown in the non-patent document. A non-biodegradable component such as humic acid is, for example, a non-patent document 2 and a non-patent document 3, and is a polymer substance contained in waste water, ground water, or the like, which is both hydrophilic and hydrophobic. These filter-reducing substances are dissolved in water due to water solubility, and cannot be separated and removed by flocculation and precipitation. On the other hand, since humic acid and the like are difficult to be degraded by microorganisms, it is difficult to remove them by an activated sludge method or the like, and they can be removed by adsorption treatment using activated carbon or the like, but the cost is extremely high. Therefore, it is difficult to implement a material for reducing the cause of such filtration flux reduction by a known method, and the industry is seeking a countermeasure. "The demand for water in the world is increasing one step at a time, and it is expected to develop a water treatment method of a rate. Nowadays, the necessity of reclaimed water is low and the management is easy and efficient. Therefore, it is a countermeasure against the reduction of membrane transition flux. Various methods are proposed, for example, a method of adding a sub-gas acid to the water to be treated (for example, Patent Document 1), and a method of cleaning the film using a coarse bubble generation device and a g-wind double-diffusion device (for example, Patent Document 2) ), a method of adding an inorganic flocculant to an activated sludge tank (for example, Patent Document 3), a method of adding an organic polymer flocculant (for example, a patent document sentence) Etc. However, it is advisable to take advantage of the complexity of the government, to remove the political rate, and the economical point of view. 忒Special methods are not satisfactory methods. Furthermore, in Patent Document 5, The polyvinylamine of the 1% ionic polymer can be used for the purpose of eliminating the bulking of the use of the squid 2, 2011, 072, pp. Japanese Laid-Open Patent Publication No. 2006-15236 [Patent Document 4] JP-A-2006-3 345 87 [Patent Document 5] Japanese Patent Application No. 2〇〇9_〇〇〇676 No. [Non-Patent Document 1] Naga〇ka η, Ueda S, and Miya A: Effects of bacterial extracellular polymers in membrane-separated activated sludge systems, and... 36 (9) 165-172 (1996) [Non-Patent Document 2] Masaru Ueda and Sakamoto Yoshizawa: Collection and Characterization of Groundwater Rot Plants Using Rigid Adsorption Resins, Research on Atomic Energy Post-treatment vol.12, No.1-2 (2006) [Non-Patent Document 3j The effect of You Zuo 'Nan Youtian Zhizi' Gong Yongzheng Guang·Fully Acid on the activated sludge treatment of domestic wastewater, water and wastewater vol.43, No.12 (2001) L poor content as above, 14 known methods 4 _ Separation activity The method of removing the causative substance by reducing the flux in the sputum is not satisfactory. For example, the method of adding a sub-gas acid to the water to be treated as described in the patent document 不仅 is not only the cost of the chemical liquid. And human X costs, but also reduces the activity of microorganisms Further, in the method of cleaning a film using a coarse bubble generating air diffusing device described in Patent Document 2, there is a problem that the device operating rate is lowered due to frequent cleaning, and the oxygen dissolving efficiency is wasted. Further, as in Patent Document 3 As stated in the article, the method of adding inorganic flocculant 201107250 not only requires a large amount of Dong's addition of Dongcheng, but also the problem of increased pH at the pH value or 5 right; her rabbit; The method of adding the organic, molecular-molecular flocculant described in the literature 4, the method of W, because of the organic polymer flocculation or the destructive resistance of the 轫 handle m 々 double has a lower water job, so the effect Sustainability needs to be improved. Regarding Patent Document 5, the use of polyethyl sinus; + Tian, A 7 Gan, and enamine is limited to the elimination of swelling, and it is not known to remove water-soluble polysaccharides or humins. The object of the present invention is to provide a method for removing the causative substances in the filtration flux-reducing activated sludge tank and removing the low-cause substances in the membrane separation active sludge tank, which is cheaper, simpler and less... "Method phase weight / 5 / Ni amount of production to reduce the concentration, thereby shortening the separation time of the separation membrane ', and extending the cleaning interval. The present invention is related; gu. J,,, > Effectively remove the cause of the excessive enthalpy flux in the membrane separation activated sludge tank #丁口初为方法. Its main purpose is a quantity reduction cause of the material to drop the Fangda Yingtong, method, which is characterized by: Adding the water-soluble and/or water-absorbing cationicity@人彳A as the active ingredient to the filter flux reduction factor, the substance remover is added to the membrane, and the membrane is separated from the active mud mixture, and then 貘&quot ;^7 离., is the preferred method of the monthly method, which can be exemplified by the reduction of the transitional substances in the membrane separation, the humic substances and the polysaccharides contained in the water, Christine, &gt At least one of the female and female proteins Adding 10~2〇〇〇00 mg/L membrane filtration flux to reduce the causative agent removal agent to the activated sludge mixture. Beyun is further preferred as a membrane separation active stain removal method, which is characterized by: The following aspects can be exemplified. The filtration flux of the mud method is reduced. The reason for the removal of the filter material with the following cationic water-soluble polymer as the active ingredient of 201107250 is added to the original material. Membrane separation is carried out in a membrane separation activated sludge mixture containing a material for reducing the cause of alleviation. The cationic water-soluble polymer is characterized by containing a fluorene structural unit represented by the following formula (1) and/or (2): —C- CH2-CR1 - CH2-CR2-4~

C

N (1) ι+η3χ· GH2-CR3~CH2-GR4-)-

LAU) and (2) may also be different; X'Y- is an anion, which may be the same or different, such as the removal method of the transition flux reduction factor described in the above, wherein the 'filter flux reduction factor is At least one species of a lysin-like substance, a plurality of types, and an in vitro polymer compound of a protein. The method for removing the filter flux-reducing factor as described above is a method of adding 10~2()n' 2 υ〇0 mg/L of the filter to reduce the causative substance to the activated sludge mixture. The method for removing a filter flux-reducing factor according to the above, wherein the water-soluble and/or water-absorbing cationic polymer contains a mole % of the formula represented by the above formula (1) and/or (2) Body unit. According to the method of the present invention, compared with the conventional method, the water-soluble and/or water-absorbing cationic polycondensation 8 201107250 of a small amount of organic polymer flocculant can be used at a low cost and with a small amount of sludge production. Membrane separation The concentration of the percolation flux in the activated sludge is reduced. Further, according to the method of the present invention, only the organic polymer flocculant can be added to the activated sludge mixed solution, so that the material for reducing the amount of excessive ruthenium flux can be easily removed without complicating the removal step. [Embodiment] The method of the present invention relates to a method for removing a membrane excess flux causing substance in a membrane separation activated sludge tank by using a flux reduction causative agent. The flux is reduced by the original (10) mass (4), which is a so-called polymer floc (4), which is a water-soluble and/or water-absorbing cationic polymer as a main component. Further, the above polymer may also be a crosslinkable gel. The water/water-absorbing cationic polymer used as a main component of the flux-lowering factor removing agent of the present invention contains a pulse structure unit represented by the following formula (1) and/or (2): ^ CR2| ( 1) 1— C = N -J Ι^ + Η3χ-

G Η 2 - G R3 - G Η 2 — c R

N

C (2) n+h3y- are respectively a hydrogen atom or a methyl group, which may be the same

[In the formulas (1) and (2), I^~R may also be different] or may not be divided, u anion, phase 9 201107250 Water-soluble and/or water-absorbing cationic polymer used in the present invention It is a unit having the fluorene structural unit represented by the above formula U) and/or (2). Further, in the above formulae (1) and (2), specific examples of the anions represented by χ- and γ- are used. Examples include .Cl ' Br_, l/2S〇42_, CH3(CO)CT, and h(c〇)〇. Among them, CP is preferred. The method for producing such a cationic polymer is not particularly limited, and examples thereof include a method of producing an ethylenically unsaturated monomer having a primary amine group or a substituted amine group capable of forming a primary amino group by a conversion reaction, and propylene. A copolymer of a nitrile of nitrile or mercaptoacrylonitrile, and after acid hydrolysis, the cyano group in the above copolymer is reacted with a primary amine group to be deuterated. The ethylenically unsaturated monomer is preferably a compound represented by the formula: CH2 = CRa-NHCORb (wherein, Ra represents a hydrogen atom or a methyl group, and Rb represents an alkyl group having 1 to 4 carbon atoms or a hydrogen atom). In the copolymer of the above ethylenically unsaturated monomer and a nitrile, the substituted amine group derived from the compound can be easily converted into a primary amine group by hydrolysis or alcoholysis. Further, the primary amine group is deuterated by reaction with an adjacent cyano group. The above compound may, for example, be N-vinylformamide (^2^(2)~small vinylacetamide^^^^^^^^). The polymerized molar ratio of the ethylenically unsaturated monomer to the nitrile is usually 2 〇: 80 to 80: 20, and a ratio of the polymerized molar ratio outside the range, such as an ethylenically unsaturated monomer, may be used as needed. Larger aggregate Moer: In general, the more the ratio of the fluorene structural unit in the water-soluble and/or water-absorbing cationic polymer is, the more excellent the performance is when the transition flux is lowered. In addition, the present inventors believe that the ethylene amine structural unit can also be beneficial as 201107250 to contribute to the reduction of the flux as a bypass, which is provided as a filter for the reduction of flux. The polymerization of the above-mentioned ethylenically unsaturated monomer and the guessing substance due to the "difficulty and low cause" of the material depolymerization; = 2: 8 〇 ~ 8: 20, especially good 4 〇: 6 〇 ~ 6 〇:4〇., ear ratio... As an ethylenically unsaturated monomer and guessing the usual free radical polymerization method, it can also be used in the form of blocky... It can be used for block polymerization, aqueous solution polymerization, polymerization, Any one of emulsion polymerization, etc. When the polymerization is carried out in a solvent, it is usually carried out at a raw material monomer concentration of 5 to 8 Gf 4% n, preferably at 20 to 60 %. The polymerization initiator can be used as a general free beauty = The initiator is preferably an azo compound 'more preferably 2,21-azobis(10)-propylpropanate) hydrochloride, etc. Further, the polymerization is usually carried out under a flow of an inert gas / 0 to HHTC. The copolymer obtained can be directly supplied to the deuteration reaction in this state or after dilution. Further, the copolymer can be desolventized and dried by a known method to form a solid as a solid, and dissolved in n times to be supplied to the deuteration reaction. In the deuteration reaction, when the N-ethene-based amine compound represented by the above formula is used In the case of an ethylenically unsaturated monomer, the cationic polymer used in the present invention can be produced by performing the following two-stage reaction, which converts the substituted amine group of the copolymer into a primary amine group, and then Forming a primary amine group to react with an adjacent cyano group to form a ruthenium structure. Further, in the presence of a strong acid, the copolymer may be added to phoenix in water to form a ruthenium structure β in one stage. It is also considered that a primary amine group is first formed as an intermediate structure. As a specific condition of the deuteration reaction, for example, a strong acid of 0.1 to 5.0 equivalents is preferably added in an amount of 0.1 to 5.0 times equivalent to the amine group in the copolymer. 3 〇 times the equivalent of a strong acid, more preferably 〜 7~1.5 times the equivalent of hydrochloric acid, usually at a temperature of 80 to 150 ° C, preferably 90 to 120 ° C, usually heated 〇. 5~20 hours' Thereby, a cationic polymer having a fluorene structural unit is produced. Generally, the larger the equivalent ratio of the strong acid to the substituted amine group is, and the higher the reaction temperature, the higher the reaction temperature is promoted. Supply to reaction The water is usually present in the reaction system in an amount of 10% by mass or more, preferably 2% by mass or more. The water-soluble and/or water-absorbing cationic polymer poison used in the present invention is typically by the following method. To manufacture: according to the above description, the letter N-ethylene carbamide and acrylonitrile copolymerization 'the resulting copolymer is prepared into an aqueous suspension and heated in the presence of hydrochloric acid, thereby being shy by the substituted amine Forming a fluorene structural unit with an adjacent cyano group. Further, by selecting a molar ratio of N-vinylformamide and propylene to the ugly polymerization, and the copolymerization conditions of the copolymer, cations of various compositions can be obtained. The water-soluble and/or water-absorbing cationic polymer thus obtained preferably contains 5 to % of the above formula (1) and/or (7) in the above cationic polymer 1% by mole. The material unit is used as a repeating unit.脒 脒 单 it it it it it it it it it it it it it it it it it it it it it it it it it it it it it it it it it it it it it it it it The amount of 腓 structural unit is higher than that of 去除 去除 去除 腓 腓 腓 腓 腓 腓 腓 腓 腓 腓 腓 腓 腓 腓 腓 腓 腓 腓 腓 腓 腓 腓 腓 腓 腓 腓 腓 腓 腓 腓 腓 腓 腓 腓 腓 腓 腓 腓 腓 腓 腓Above, the content of '冓早兀' is particularly good at 20% or more. The other t is preferably 15 mol%. In addition, the content of the lung structural unit 12 201107250 The upper limit is more preferably 85 mol% or less, and even more preferably 8 mol% or less. Further, if the water-soluble and/or water-absorbing cationic polymer is as described above

In the method of production, the unit represented by the following formulas (3) to (5) may be contained in addition to the above-mentioned unit structure unit. ; L -C-CHa-_CR5_X„ I NHCORe I CN 丄CH^CR3 )__ I N+Hg2 - (3) ~ (5) can also be different. R is the carbon number is anion ♦ (3) . (4) ♦ ( 5) The phase R5, R7 and R8 are each a hydrogen atom or an alkyl group or a hydrogen atom of a methyl group 4. The anion is the same as the anion described above in the above formulas (1) and (2). When the water-soluble and/or water-absorbing cationic polymer contains the above formula (3. (5), it usually contains 0 to 40 moles in the above cationic polymer ι〇〇. The repeating unit represented by the above formula (3), the repeating unit represented by the above formula (4), 〇~7〇莫耳./. The unit of the above formula (1) and/or (2), and the above formula (: composition can be made by the ethylenically unsaturated monomer and guess: Αα molar ratio, or deuteration The conditions of the reaction (temperature or time) are adjusted. 13 201107250 13 of each repeating unit

Further, as a method of producing a water-absorbing cationic polymer, in addition, the "*3C-NMR (13C-nuclear can be exemplified: glyoxal,

A method of reacting a polymer with a polyfunctional substance capable of reacting with a polymer; a method of reacting a water solute to carry out a post-parent; and a method of heating a water-soluble polymer to crosslink it. The filtration flux-reducing factor removing agent in the present invention contains a water-soluble and/or water-absorbing cationic polymer as a main component in an effective component, and may contain other components. As other components, for example, A4, gasification, and the like can be cited. In the present invention, the "amount of active ingredient" means the content of the water-soluble and/or water-absorbing cationic polymer in 100% by mass of the substance-reducing agent according to the flux reduction, and is usually preferably 7 s ^ 〜1〇〇% by mass. When the filtration flux is lowered, the substance removing agent contains other components, and after the cationic polymer is produced, the other components may be added in such a manner as to achieve the desired amount, or may be previously prepared in the raw material of the (co)polymer. Mix other ingredients. When the water-soluble cationic polymer which is the main component of the filter flux-reducing factor removing agent of the present invention is made into a solution of cerium and lanthanum in 1 equivalent of brine, the viscosity at 25 ° C is lower. Preferably, it is 0.01~1〇dL/g, more preferably 11~8 dL/g. If the reduced viscosity does not reach 〇.〇1 dL/g, then there is a difficulty. 201107250 'D ‘Don't reduce the cause of the substance remover, or decrease the filtration flux. Production: The tendency of the function of the substance remover to decrease. On the other hand, if it is folded, it is sticky. When the viscosity exceeds 10 dL/g ’, the viscosity of the aqueous solution of the filter-reducing substance removing agent becomes too high, and thus a problem may occur in the case of addition. Further, the above-mentioned reduced viscosity can be controlled by adjusting water-soluble cationic polymerization: molecular weight, ionic ratio, molecular weight distribution, production method, group 2, and the like. For example, if the molecular weight of the water-soluble cationic poly-polymer is increased, the viscosity tends to increase. The method towel of the present invention reduces the cause of the flux of the above-mentioned materials: the agent is added to reduce the flux containing The membrane separation activity of the causative substance is in the middle of the film, and then the membrane separation is prevented, thereby preventing the membrane flux of the membrane from decreasing by 0. In addition, the material removal agent of the present invention can also be used in the range of effects. In the present invention, the phrase "addition to the membrane separation activated sludge mixture" 1 is added to a membrane separation tank using a precision membrane or a super membrane, And any microorganism in the activated sludge treatment system which is stepped forward of the membrane knife away from the tank, so that it can be contacted with the microorganism in the activated sludge, for example, it can be added to the raw water tank together with the mud and guided to The method in the aeration tank, the method of adding to the membrane type activated sludge tank, the method of directly adding to the anaerobic tank in the equipment for denitrification, etc.; Reduce the causative substance In addition to the effect, will enable the scribe intended to add. Further, it may be added to a flow path such as a side groove or a pipe connecting the respective grooves, and 15 201107250 or a flow regulating groove placed before the respective grooves. (Addition to Activated Sludge) In the method of the present invention, when the filtration flux is reduced in the amount of the substance removing agent to the 'tongue sludge', the filtration flux is lowered to cause the substance to be added, and the amount of addition is high. The amount of the activated sludge mixture is preferably from 1 〇 to mg/L', more preferably from 1 〇 to 1 〇〇〇 mg/L. If the amount of addition is less than 1 〇, it is difficult to obtain the effect of the filter flux reducing factor removing agent. On the other hand, if the amount added exceeds 2 〇〇〇mg/L, it is not only difficult to obtain it sufficiently; the effect of reducing the cause of the substance removing agent is considered, and it is also possible to adversely affect the activity of the microorganism in the active/depleted sludge. . (Addition to the raw water storage tank) When adding the filtration flux reduction factor removing agent to the raw water storage tank, the removal agent may be directly dissolved in the water and directly added to the inflow membrane separation activated sludge. The tank is channeled and guided to the membrane separation activated sludge tank. =&通#Reducing the cause f The amount of the remover used is not limited depending on the transition-concentration, so it is not particularly limited, for example, it is preferably used in the case of the activated sludge mixture. The mg/L excess flux reduces the cause of the substance remover. In addition, the amount of the substance removing agent used in the reduction of the flux may be determined by the following methods: collecting the activated sludge in the processing device, collecting the beaker into the beaker, and the second: removing agent. Evaluation of Total Sugar Concentration of Supernatant (Benzene Sulfate Method) [Examples] 16 201107250 Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to the examples. In the following test examples (Examples and Comparative Examples), the evaluation of the filtration flux-reducing factor removal agent was carried out by measuring the total sugar concentration of the treated water after the sludge treatment and the amount of filter paper filtration. <Measurement of Total Sugar Concentration> The term "total sugar concentration" means the concentration of a polysaccharide which is dissolved in water or is present in a colloidal form in water by using an ultraviolet-visible spectrophotometer (Shimadzu Science Co., Ltd.) The company's uv_3 t 〇〇) measures the absorbance near 490 nm' calculated from a calibration curve obtained using a standard solution. Further, the measurement of the total sugar concentration was carried out in accordance with a conventional method: phenol sulfuric acid method [Hodge, J. E. and Hofreiter, B. T.} Method in Carbohydrate Chemistry, 1, 338 (1962)].

The determination of the removal effect of the over-flux reduction cause substance is performed by calculating the removal rate of the filter flux reduction factor by the following formula. Removal rate (%) = (1 - A^AJxlOO (A,: total sugar concentration of treated wastewater, VIII: filtration flux reduces total sugar concentration after removal of the causative substance) <Measurement of crepe paper & quantity> The so-called filter paper filtration amount refers to a 5c filter paper (manufactured by ADVANTEC) with a diameter of 丨85 mm, which is folded into 16%, placed in a funnel and mounted on a measuring cylinder of % ml. 50 ml of the removed sludge was measured, and the amount of filtration after 5 minutes was measured. 17 201107250 The more the filtration amount after 5 minutes, the more excellent the filtration property is, but the higher the removal effect of the substance due to the reduction of the turbulent flux is. The cationic polymer used in the test examples is summarized in Table 1. 'Bottom [cationic polymer] As the cationic polymer of the present invention, a cationic polymer produced by the following method is used ( Ai, A2, A3). 'Manufacture of cationic polymer A1> Add acrylonitrile and N-vinylformamidine to a four-necked flask equipped with a stirrer, a nitrogen gas introduction tube, and a cooling tube. Mixture of amines (Mohr ratio = 55 · 45) 6 g and 34 g of a mixture of brine. The mixture was heated to 60 ° C while nitrogen was added, and 2,2,-azobis(2-propionylpropane) dihydrochloride aqueous solution was added at a mass ratio of 1% by mass. 〇 12 g, further maintained for 3 hours, to obtain a suspension of the polymer precipitated into water. 20 g of water was added to the suspension, and then 2 equivalents of concentrated hydrochloric acid was added to the methyl thiol group of the polymer, followed by 1 〇 Hold 〇t for 4 hours to obtain a yellow high viscosity liquid. After adding the above high viscosity liquid to a large amount of acetone, the polymer was precipitated. Thereafter, the obtained polymer was chopped and dried under the sail for half a night. The cation is pulverized to obtain a cationic polymer of the powder. (Composition of the ionic polymer A1) The cationic polymer A1 is dissolved in heavy water, and the 13c_nmr spectrum is measured by the method η (manufactured by JEOL Ltd.) The sum of the peaks corresponding to the peaks of each repeating unit in the cable (4) is the composition of the peaks of the respective repeating units. Furthermore, the total amount of the phase of the above-mentioned general formulas (1) and (7) is not determined by the 2011-0750 yuan. In Table 1. In addition, the yang obtained in this way Each unit contained in the ionic polymer A1: R1 to R4 and R5 to R8 in the above formula [(1), (2), (3) to (5)] are hydrogen atoms 'X, γ-, z - is a chloride ion. (Measurement of the reduced viscosity of the cationic polymer A1) A solution of 0.1 g/dL was prepared by dissolving 0.1 g of the cationic polymer A1 in 1 mL of i equivalent of brine. Hua viscometer (〇δ_ΐ(ΐ v_ter) (manufactured by Han〇 Research Co., Ltd.); the viscosity of the cationic polymer A1 of the above solution under hunger. The results are shown in Table i. <Production of cationic polymer A2> 40 g of desalted water and polyethylene glycol 2〇〇〇〇i 2 g were placed in a four-necked flask equipped with a stirrer, a nitrogen gas introduction tube, and a cooling tube. After 2 g of sodium hypophosphite, the temperature was raised to 70 t:, and a mixture of acrylonitrile and N-vinylamine (molar ratio of 50:50) was added dropwise under a nitrogen stream for 2 hours. 120 g. 126 g of an aqueous solution of 2,2,- azobis(2-amidinopropane) dihydrochloride was added in an amount of 5 times by mass. Further, after the mixture was aged for 2 hours, concentrated hydrochloric acid (corresponding to 1% molar % based on sulfhydryl group) was added to raise the temperature to 90 ° C, and left for 3 hours. After the above mixture was added to a large amount of propylene carbonate, the polymer was precipitated, the obtained polymer was chopped, and the polymer was dried at 60 ° C for half an hour, and then pulverized to obtain a powdery cationic polymer. (Composition of cationic polymer A2) The 13C_NMR spectrum of the cationic polymer A2 was measured in the same manner as in the case of the cationic polymer A1, and the composition of each unit was calculated. In addition, 201107250 does not distinguish the structural units of the above formula (1) and (2), and the total amount of the results is shown in

The refractive index of the daughter polymer A2. The results are shown in Table 1. Each unit to R4 and R5 to R8 contained in A2 is <Production of cationic polymer A3> The cationic polymer A3 is subjected to heat treatment of cationic polymer A1 (120. (:, 5 hours)) The cross-linking of the cationic polymer A3 was measured in the same manner as in the above-mentioned cationic polymer A1. The results are shown in Table 1. Further, as a comparative example, a commercially available polymer flocculant was used. B i : Diafloc Κ-405 (containing 55 wt% of dicyandiamide-vaporized ammonium-furfural polycondensate), B2: Diafl〇c K-403B (containing 50 wt% of quaternary polyamine;) 20 201107250 [I&lt;] Remarks AN/NVF=55/45% by mole of polymer hydrochloric acid modified substance AN/NVF=50/50 mol% of polymer hydrochloric acid modified substance 1 1 A1 crosslinked product obtained by 1% aqueous solution Viscosity (cps) 1 1 1 215 Reduced viscosity (V sp/c) ”t CN 〇1 1 1 Composition (mol%) CN rH 22.4 CN 2 inch &lt;N 22.4 〇〇 repeating unit 桊NVF 5 VAM 桊5 VAM桊NVF VAM dicyandiamide-formaldehyde polycondensate dimethylamine-epichlorohydrin polycondensate flocculant polymer&lt;-〇(N 〇qQ ^ ώ 201107250 脎:脒Acid salt unit NVF: N-vinylformamide unit AN: acrylonitrile unit VAM: vinylamine hydrochloride unit AA: acrylic acid unit [Test Example] &lt;Example 1 &gt; Membrane separation active sewage for treating domestic wastewater The activated sludge (pH 6_7, MLSS (mixed liquor suspended solid), 9,000 mg/L) 200 ml was placed in a beaker, and the specified amount was added as an aqueous solution of ι·1 mass%. The filtration flux reduction cause substance removing agent shown in Table 2 was then stirred and mixed for 2 minutes, and allowed to stand overnight. Thereafter, the supernatant was developed by phenol sulfuric acid method, and the absorbance at a wavelength of 49 〇 nm was measured. The measured value is used to calculate the total sugar concentration of the supernatant, thereby determining the removal effect of the substance causing the transition flux reduction. On the other hand, 50 ml of the sludge after removing the filter flux reduction factor is poured into the filter paper installed in the measuring cylinder. The amount of filtered water after 5 minutes was measured. The results are shown in Table 2. &lt;Comparative Example 1 &gt; In addition to the addition of the excessive flux reduction cause substance removing agent, the filtration flux reduction factor substance removal was determined in the same manner as in Example 1. effect The results are shown in Table 2. &lt;Comparative Example 2 &gt; In addition to the use of the polymer flocculants (B1, B2) manufactured by Dia Nitrix Co., Ltd., and examples! Similarly, the filtration flux reduction was determined. 22 201107250 The results are shown in Table 2. Due to material removal effect 23 201107250 Filtration amount (mL) 14.5 00 in 12.5 ^sO inch oq rH rs) 1 ^ 10.5 Removal rate (%) m cn 卜 oo CN to mo U-) (N (N total sugar concentration ( Mg/L) CS 00 &lt; N mmm Addition amount (mg/L) om 〇 2500 2000 o ψ r - H &lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt; m &lt; 1 vH CQ (N PQ Example 1 Comparative Example 1 Comparative Example 2 201107250 [Industrial Applicability] The method of the present invention can use a small amount of a water-soluble and/or water-absorbing cationic polymer as an organic polymer flocculant as compared with the conventional method. The concentration of the substance causing the filtration flux reduction in the membrane separation activated sludge is reduced inexpensively and with a small amount of sludge production. Further, according to the method of the present invention, only the organic polymer flocculant is added to the activated sludge. It is sufficient in the mixed solution, so that the substance for reducing the filtration flux can be easily removed without complicating the removal step. [Simple description of the drawing] No [Main component symbol description] No 25

Claims (1)

201107250 VII. Patent application scope: 1 . A method for removing a causative substance for reducing filtration flux by a membrane separation activated sludge method, characterized in that a filtration flux is reduced by using the following cationic water-soluble polymer as an active ingredient The removing agent is added to the membrane separation activated sludge mixture containing the substance for reducing the filtration flux to perform membrane separation; the cationic water-soluble polymer is characterized by containing the following general formula (1) and/or (2)脒 脒 脒 :: CHz-CR'-CH^CR2-^ IC = N" (1) n+h3x~ —(r CH2-CR3*-CH2 —OR4-4- [In the formulas (1) and (2), R1 to R4 are each a hydrogen atom or a methyl group, and may be the same or different, and X' and γ are anions, respectively, and may be the same or different]. 2. The method for removing a causal agent for reducing the filtration flux according to the first aspect of the patent application, wherein the substance causing the filtration flux reduction is at least one of a humic substance, a polysaccharide, and an in vitro polymer compound of a protein. 3. For the method of removing the cause of filtration flux reduction in the scope of patent application 帛i, add a filter flux reduction factor removing agent of 1 〇 2 〇 (8) to the activated sludge mixture. 4. If you apply for a patent range! The method for removing a causative substance for reducing filtration flux, wherein the water-soluble and/or water-absorbing cationic polymer contains 26 201107250 5 to 90 mol% of the above formula (1) and/or (2) Monomer unit. Eight, schema: (none) 27