TW201321313A - Methods for improving membrane bioreactor systems - Google Patents

Abstract

A method of conditioning mixed liquor in a membrane bioreactor includes dispersing a treatment additive in the mixed liquor. The treatment additive includes a water soluble block copolymer. Methods for improving flux in a membrane bioreactor and clarifying wastewater are also provided.

Description

Method for improving a thin film bioreactor system

The present invention relates to a method of improving a thin film bioreactor system, and more particularly to a method of treating a microbial mixture and increasing the flux of the thin film bioreactor (MBR) system.

Waste water from municipal and industrial plants can be purified by biologically treating the wastewater in a membrane bioreactor (MBR) system. In MBR, microorganisms consume organic compounds dissolved in wastewater, and the membranes screen suspended solids or biomass from treated wastewater (or mixture) to produce purified water.

The optimum yield of purified water depends on the efficiency of the MBR system and the flux of the membrane. The condition and quality of the microbial organism population in the MBR system will affect the operation of the MBR and the filterability of the mixture. Substances in the mixture (such as extracellular polymeric substances, gelatinous and soluble organic matter) can be deposited on the films, plugging the film and causing increased film resistance and reduced flux.

An inorganic aggregating agent and an inert particulate additive may be added to the MBR system to treat the mixed solution by agglomerating and flocculation of the colloid and other substances, thereby reducing soluble substances in the mixed solution and improving filterability and film throughput . However, such additives may require a specific and narrow pH range, which may increase the sludge concentration, causing the film to wear due to the abrasive nature of the treated additive particles or causing additional film clogging when the process additives themselves are embedded in the film pores. .

The water-soluble cationic polymer can also be used to treat the mixture in the MBR and enhance the flux of the film. However, efficient processing requires a large amount of cationic polymer. Efforts continue to be made to develop and find more improved and cost effective water soluble treatment additives for treating mixtures in MBR systems to enhance membrane throughput and increase MBR efficiency.

In one embodiment, a method of treating a mixture in a thin film bioreactor includes dispersing a treatment additive in the mixture, wherein the treatment additive comprises a water soluble block copolymer.

In another embodiment, a method of increasing flux in a thin film bioreactor includes dissolving a treatment additive in a mixed solution of the treatment mixture and passing the treated mixture through a film, wherein the treatment additive comprises water soluble Sex block copolymer.

In another embodiment, a method of purifying wastewater includes adding wastewater to a membrane bioreactor, and adding a microorganism to the wastewater by adding oxygen in the presence of oxygen to prepare a mixed solution by dispersing the treatment additive therein. The mixture is treated in a mixed liquor, and the treated mixture is filtered using a membrane to produce purified wastewater, the treatment additive comprising a water soluble block copolymer.

Various embodiments increase MBR efficiency by increasing sludge filterability, membrane throughput, reducing membrane cleaning, and reducing the risk from problems associated with peak flow rates. Increased efficiency can be reduced by allowing the MBR to operate with less film, higher film throughput, and reduced film cleaning.

The singular forms "a," "an," End values of all ranges that detail the same characteristics can be independently combined and include the end values. All references are incorporated herein by reference.

The modifier "about" used in connection with the <RTI ID=0.0> </ RTI> </ RTI> includes the stated value and has a definition as indicated by the context (e.g., includes a tolerance range associated with a particular number of measured values).

"As appropriate" or "as appropriate" means that the subsequently described event or circumstance may or may not occur, or that the substance specified subsequently may or may not exist, and that the description includes where the event or circumstance occurs or where the substance The circumstances and conditions in which the event or situation does not occur or the substance does not exist.

"Water soluble" means that a compound (such as a polymer, block copolymer or monomer) described as being water soluble is soluble in water or an aqueous solution. In one embodiment, the term "water soluble" means that the compound, block copolymer or single system is completely miscible in water or an aqueous solution.

"Water insoluble" means that a compound (such as a polymer or monomer) described as being water insoluble is insoluble or slightly soluble in water or an aqueous solution.

In one embodiment, a method of treating a mixture in a thin film bioreactor includes dispersing a treatment additive in the mixture, wherein the treatment additive comprises a water soluble block copolymer.

The mixed liquor or activated sludge may be a mixture of waste water, microorganisms for degrading organic substances in the wastewater, organic matter derived from cell types, cell byproducts or waste products, or cell debris. The mixture may contain colloidal and particulate matter (biomass or biosolids), soluble molecules or biopolymers (such as polysaccharides or proteins).

The MBR system couples biological wastewater treatment and membrane filtration. The MBR can be any type of MBR system. In one embodiment, the MBR system includes a membrane and a bioreactor tank containing microorganisms that biodegrade the organic matter in the wastewater. The bioreactor tank can be an aerobic tank or reactor and can include other types of reactors, such as anaerobic reactors, anoxic reactors, or other aerobic reactors. The influent wastewater can be pumped or gravity fed into the bioreactor tank where it is contacted with microorganisms to form a mixture in the presence of oxygen or aeration. Excess activated sludge can be pumped out of the bioreactor tank and into the sludge holding tank to keep the sludge age in the bioreactor constant. The oxygen source or aeration can be provided by a blower.

In one embodiment, the mixture is filtered through a membrane and the purified water is drained from the system. The mixture can be passed through the membrane under pressure or the mixture can be aspirated via a membrane under vacuum. The membrane module can be immersed in the bioreactor tank or installed in another membrane tank that continuously draws wastewater from the bioreactor tank. The film may be a hollow fiber or flat (in stacked form) microfilter or ultrafilter with an outer microfilter or ultrafilter. Such film materials may include, but are not limited to, chlorinated polyethylene (PVC), polyvinylidene fluoride (PVDF), polyacrylonitrile (PAN), polyfluorene (PSF), polyether oxime (PES), poly Vinyl alcohol (PVA), cellulose acetate (CA), regenerated cellulose (RC), and inorganic materials (such as metals and ceramics).

In one embodiment, the mixture is treated with a dispersion of the treatment additive. The treatment additive increases the film flux by agglutinating and flocculation of the soluble organic compound in the mixture to prevent film contamination. The treatment additive can include a water soluble block copolymer. The water soluble block copolymer may include a water soluble monomer and a water insoluble monomer. The block copolymer may comprise a polymer segment that is attached to a polymer chain obtained from the polymerization of one or more water soluble monomers and obtained from the polymerization of a hydrophobic or water insoluble monomer.

In one embodiment, the block copolymer contains two segments of the formula:

-[E]-[D]-

Wherein E is a polymer segment obtained by polymerization of one or more hydrophobic monomers or water-insoluble monomers, and D is a polymer segment obtained by polymerization of one or more water-soluble monomers.

The hydrophobic polymers are water insoluble and can be prepared by precipitation or emulsion polymerization techniques of one or more hydrophobic monomers. In one embodiment, the hydrophobic monomers include, but are not limited to, alkyl acrylates, alkyl methacrylamides, alkyl acrylamides, alkyl methacrylates, alkyl styrenes, alkenes a higher alkyl ester of an unsaturated carboxylic acid, an alkylaryl ester of an ethylenically unsaturated carboxylic acid, an ethylenically unsaturated decylamine, a vinyl alkylate (wherein the alkyl group has at least 8 carbon atoms, such as Vinyl laurate and vinyl stearate), vinyl alkyl ethers (such as dodecyl vinyl ether and cetyl vinyl ether), N-vinyl decylamine (such as N-vinyl and ethylene) An alkyl ether), and an aralkyl group (such as t-butyl styrene). High carbon number alkyl esters of ethylenically unsaturated carboxylic acids include, but are not limited to, alkyl dodecyl acrylate, dodecyl methacrylate, tridecyl acrylate, tridecyl methacrylate Base ester, octadecyl acrylate, octadecyl methacrylate, ethyl half ester of maleic anhydride, diethyl maleate and alkanols derived from 8 to 20 carbon atoms and olefinic Other alkyl esters of the reaction of saturated carboxylic acids such as acrylic acid, methacrylic acid, maleic anhydride, fumaric acid, itaconic acid and aconitic acid. The alkylaryl esters of ethylenically unsaturated carboxylic acids include, but are not limited to, decyl-α-phenyl acrylate, decyl-α-phenyl methacrylate, dodecyl-α-phenyl acrylate And dodecyl-α-phenyl methacrylate. The ethylenically unsaturated guanamines include, but are not limited to, N-octadecyl acrylamide, N-octadecyl methacrylamide, N,N-dioctyl acrylamide, and the like.

The hydrophobic monomer can be an alkyl acrylate. The alkyl group in the alkyl acrylate has 4 to 16 carbon atoms. The hydrophobic monomer may also be 2-ethylhexyl acrylate. 2-ethylhexyl acrylate can be polymerized by a di-peroxide initiator (2,5-dihydroperoxy-2,5-dimethylhexane) to obtain poly(2-ethylhexyl acrylate) Ester) (PEHA). E can be poly(2-ethylhexyl acrylate) (PEHA).

In one embodiment, D is a polymer segment obtained from the polymerization of one or more water soluble monomers. The water soluble monomers can be nonionic or cationic. D can be obtained by polymerization of a cationic monomer, a nonionic monomer or a combination of a cationic monomer and a nonionic monomer.

In an embodiment, D has the following formula:

-[A] _x -[J] _y -

Wherein A is a nonionic monomer, a J-based cationic polymer, x is 0 or a positive integer and y is 0 or a positive integer. In one embodiment, the molar ratio of x:y is from about 0:100 to about 95:5. In another embodiment, the molar ratio of x:y is from about 10:90 to about 75:25.

In one embodiment, the nonionic monomer can be acrylamide. A can have the following formula:

Wherein R ₁ is hydrogen or C ₁ -C ₃ alkyl. In one embodiment, R ₁ is hydrogen. In another embodiment, R ₁ is methyl.

In an embodiment, J has the following formula:

A salt wherein R ₂ is hydrogen or a C ₁ -C ₃ alkyl group and a G-based ammonium cation. In one embodiment, R ₂ is hydrogen. In another embodiment, R ₂ is methyl.

In an embodiment, the G system

--NHR ₃ N(R ₄ R _5, R ₆ ) ⁺ M ^-

or

--OR ₃ N(R _4, R _5, R ₆ ) ⁺ M ^-

Wherein R ₃ is C ₁ to C ₄ straight or branched alkyl, and R ₄ , R ₅ and R ₆ may be the same or different and are hydrogen, C ₁ to C ₄ straight substituted or branched alkyl a C ₅ to C ₈ cycloalkyl, aromatic or alkyl aromatic group, and an M-line anion such as chloride, bromide or methylsulfate or hydrogen sulfate. R ₄ , R ₅ and R ₆ may be methyl or allyl and R ₃ may be ethyl, propyl or 1-methylethyl. G may also be derived from 2-propenyloxyethyltrimethylammonium chloride (AETAC), 3-methylpropenylpropyltrimethylammonium chloride (MAPTAC), 2-methylpropene chloride Methoxyethyltrimethylammonium (METAC) or diallyldimethylammonium chloride (DADMAC).

In an embodiment, J has the following structure:

These block copolymers can be prepared by water-in-oil emulsion techniques. Such methods are disclosed in U.S. Patent Nos. 3,284,393, Re. 28,474, and Re. 28,576, which are incorporated herein by reference. The resulting copolymer can also be further isolated by precipitation in an organic solvent such as acetone and dried to a powder form. When used, the powder can be readily dissolved in an aqueous medium.

Branching agents such as polyethylene glycol di(meth)acrylate, methylenebis(meth)acrylamide, N-vinyl acrylamide, allyl glycidyl ether, glycidyl acrylate may also be added. And the like, with the proviso that the resulting block copolymer is water-soluble.

In one embodiment, the water soluble block copolymer has a number average molecular weight of from about 100,000 to about 8,000,000. The water soluble block copolymer can have a number average molecular weight of from about 500,000 to about 6,000,000. The molecular weight of the block copolymer is not critical as long as it is soluble in water.

The structure of the block copolymer can be determined by conventional methods, such as by solution viscosity studies or C ¹³ NMR spectroscopy.

In one embodiment, the treatment additive is dispersed in the mixture in any conventional manner and mixed with the mixture prior to contact with the surface of the film. The treatment additive can be added to the mixture upstream of the membrane. The treatment additive may also be added to the area of the bioreactor where it is intensively mixed or allowed to have sufficient time to mix with the mixture (e.g., near the pump station, aeration nozzle or sludge/mixture recovery tube).

The treatment additive is dispersed in any amount suitable for treating the mixture. This amount will vary depending on the particular system to be treated and may be subject to the characteristics of the wastewater (such as turbidity, pH, temperature, flow rate, amount of water, concentration and characteristics of the mixture, suspended solids, floc size, viscosity, and in the system). The influence of the type of pollutants present). The treatment additive can be added in an amount of from about 0.1 ppm by volume based on the volume of the wastewater to about 100 ppm by volume of the living polymer. The treatment additive can also be added in an amount from about 1 ppm by volume to the active polymer to about 80 ppm by volume of the living polymer. The treatment additive can also be added in an amount of from about 10 ppm by volume based on the volume of the spent polymer to about 50 ppm by volume of the living polymer.

In another embodiment, the treatment additive can include other water soluble polymers or inorganic aggregating agents. The other water-soluble polymer or inorganic aggregating agent may be added to the mixed liquid alone or in combination with the water-soluble block copolymer. These other polymers and aggregating agents cooperate with the water soluble block copolymer to treat the mixture and increase the flux in the MBR system. The amount of the treatment additive can be effectively reduced while achieving similar levels of film flux enhancement performance, with the addition of such other polymers or aggregating agents. In another embodiment, the use of the treatment additive can substantially reduce the amount of such other polymers and aggregating agents. Examples of such water-soluble polymers may be tannin-containing polymers, polychlorinated diallyldimethylammonium (polyDADMAC), polychlorinated methacryloxyethyltrimethylammonium (poly) METAC) or a copolymer of N,N-dimethylaminoethyl acrylate methyl chloride (AETAC) and acrylamide (AM).

In one embodiment, the inorganic aggregating agents may be selected from the group of inorganic compounds containing Ca, Mg, Si, Al, Fe, and combinations thereof. The inorganic aggregating agent may be selected from the group consisting of inorganic salts containing Al, Fe, or a combination thereof, or a polymerized type thereof. In another embodiment, a method of increasing flux in a membrane bioreactor includes treating the mixture by dispersing a treatment additive in a mixture and passing the treated mixture through a membrane, wherein the treatment additive comprises Water soluble block copolymer.

In one embodiment, the mixture is treated with a dispersion of a treatment additive. The treatment additive increases the film flux by agglutinating and flocculation of the soluble organic compound in the mixture to prevent film contamination. In one embodiment, the treatment additive comprises a water soluble block copolymer as described above.

In one embodiment, the treatment additive is dispersed in the mixture in any conventional manner and mixed with the mixture prior to contact with the surface of the film. The treatment additive can also be added to the mixture upstream of the film. The treatment additive may also be added to the area of the bioreactor where it is intensively mixed or allowed to have sufficient time to mix with the mixture (e.g., near the pump station, aeration nozzle or sludge/mixture recovery tube).

The treatment additive is dispersed in any amount suitable for treating the mixture. This amount will vary depending on the particular system to be treated and may be subject to the characteristics of the wastewater (such as turbidity, pH, temperature, flow rate, amount of water, concentration and characteristics of the mixture, suspended solids, floc size, viscosity, and in the system). The influence of the type of pollutants present). The treatment additive can be added in an amount of from about 0.1 ppm by volume based on the volume of the wastewater to about 100 ppm by volume of the living polymer. The treatment additive can also be added in an amount from about 1 ppm by volume to the active polymer to about 80 ppm by volume of the living polymer. The treatment additive can also be added in an amount of from about 10 ppm by volume based on the volume of the spent polymer to about 50 ppm by volume of the living polymer.

In another embodiment, the treatment additive can include other water soluble polymers or inorganic aggregating agents as described above.

The membrane bioreactor (MBR) and the mixed liquid are as described above. In one embodiment, the treated mixture is filtered through a membrane and the purified water is drained from the system. The treated mixture can also be passed through the membrane under pressure or the treated mixture can be aspirated through the membrane under vacuum. The membrane module can be immersed in the bioreactor tank or installed in another membrane tank that continuously draws wastewater from the bioreactor tank. The film may be a hollow fiber or flat (in stacked form) microfilter or ultrafilter with an outer microfilter or ultrafilter. Such film materials may include, but are not limited to, chlorinated polyethylene (PVC), polyvinylidene fluoride (PVDF), polyacrylonitrile (PAN), polyfluorene (PSF), polyether oxime (PES), poly Vinyl alcohol (PVA), cellulose acetate (CA), regenerated cellulose (RC), and inorganic materials (such as metals and ceramics).

In another embodiment, a method of purifying wastewater includes adding wastewater to a membrane bioreactor, and preparing a mixture by adding microorganisms to the wastewater in the presence of oxygen, by dispersing the treatment additive in the mixture The mixture is treated in a liquid, and the treated mixture is filtered using a membrane to produce purified wastewater, the treatment additive comprising a water soluble block copolymer.

The wastewater can be from municipal and industrial plants and can contain extracellular polymeric substances and colloidal and soluble organic materials.

In one embodiment, the mixture is treated with a dispersion of a treatment additive. The treatment additive can include a water soluble block copolymer as described above. The treatment additive can be dispersed in the mixture in any conventional manner and mixed with the mixture prior to contact with the surface of the film. The treatment additive can be added to the mixture upstream of the membranes. The treatment additive may also be added to the area of the bioreactor where it is intensively mixed or allowed to have sufficient time to mix with the mixture (e.g., near the pump station, aeration nozzle or sludge/mixture recovery tube).

The treatment additive is dispersed in any amount suitable for treating the mixture. This amount will vary depending on the particular system to be treated and may be subject to the characteristics of the wastewater (such as turbidity, pH, temperature, flow rate, amount of water, concentration and characteristics of the mixture, suspended solids, floc size, viscosity, and in the system). The influence of the type of pollutants present). The treatment additive can be added in an amount of from about 0.1 ppm by volume based on the volume of the wastewater to about 100 ppm by volume of the living polymer. The treatment additive can also be added in an amount from about 1 ppm by volume to the active polymer to about 80 ppm by volume of the living polymer. The treatment additive can also be added in an amount of from about 10 ppm by volume based on the volume of the spent polymer to about 50 ppm by volume of the living polymer.

In another embodiment, the treatment additive can include other water soluble polymers or inorganic aggregating agents as described above.

The treated mixture can be filtered through a membrane to screen suspended solids or biomass and the purified water is discharged from the system. The treated mixture can be passed through the membrane under pressure or the treated mixture can be drawn through the membrane under vacuum. The membrane module can be immersed in the bioreactor tank or installed in another membrane tank that continuously draws wastewater from the bioreactor tank. The film may be a hollow fiber with an outer ultrafilter, or a flat (in stacked form) microfilter or a hollow fiber with an outer microfilter. Such film materials may include, but are not limited to, chlorinated polyethylene (PVC), polyvinylidene fluoride (PVDF), polyacrylonitrile (PAN), polyfluorene (PSF), polyether oxime (PES), poly Vinyl alcohol (PVA), cellulose acetate (CA), regenerated cellulose (RC), and inorganic materials (such as metals and ceramics).

The following examples are provided by way of illustration and not limitation of the invention.

Instance Example 1

Samples of the mixed solutions used in the tests of Examples 1 to 3 were collected from a municipal wastewater treatment plant of the GE China Technology Center. The samples were collected from an activated sludge recovery line in which the MLSS concentration was higher than 10 g/L.

Standard test bottles each test sample and control sample bottle tester (Phipps & Bird ^TM), to ensure proper mixing. Four 500 ml aliquots of the mixture were added to the four vials. The treatment additive (Polymer A or Polymer B) was quickly added to each sample in the amounts shown in Table 1. A control sample was also prepared by adding 500 ml of the mixed solution to the control bottle without adding a treatment additive. All samples were rapidly stirred at 200 rpm for 30 seconds and then stirred for 15 minutes at a slower agitation speed of 50 rpm to thoroughly mix the samples.

The filterability of the mixture of each sample (including the control bottle) was evaluated by a filtration time (TTF) test method. The TTF test method was modified from the standard method (APHA, 1992) Method No. 2710H. A 9 cm filter paper (Whatman GF/C, Cat. No. 1822 090) was placed in a Buchner funnel and allowed to wet to form a good seal. A 200 ml sample from each treated mixture sample and control vial was added to a separate Buchner funnel (prepared as above). A vacuum pressure of 51 kPa (15 inches Hg) was applied using a vacuum pump with a pressure regulator. The time (25%-TTF) required to filter 50 ml of each mixture sample (or 25% of the initial sample volume) was measured and is shown in Table 1.

¹ Polymer A contains about 38% active (by weight) of the AETAC/AM/EHA block copolymer. Its molecular weight is from 4,000,000 to 6,000,000.

² Polymer B contains about 45% active (by weight) of another block copolymer product. The block copolymer is polymerized from a monomer of AETAC/AM/EHA and has a molecular weight of 4,000,000 to 6,000,000. The monomers of these AETAC/AM/EHA are respectively referred to as N,N-dimethylaminoethyl acrylate methyl chloride (AETAC), acrylamide (AM) and 2-ethylhexyl acrylate (EHA). .

This data shows that the additive of the mixture is extremely significantly improved by the addition of the polymer A or the polymer B treatment additive.

Example 2

Standard bottle tested following the test samples and control sample bottle tester (Phipps & Bird ^TM), to ensure proper mixing. Five 500 ml aliquots of the mixture were added to five vials. Treatment additives as shown in Table 2 were added to each sample. A control sample was also prepared by adding 500 ml of the mixed solution to the control bottle without adding a treatment additive. All samples were rapidly stirred at 200 rpm for 30 seconds and then stirred for 15 minutes at a slower agitation speed of 50 rpm to thoroughly mix the samples.

The filterability of the mixture of each sample (including the control bottle) was evaluated by the TTF test method as described in Example 1. A 200 ml sample from each treated mixture sample and control vial was added to a separate Buchner funnel. A vacuum pressure of 51 kPa (15 inches Hg) was applied using a vacuum pump with a pressure regulator. The time (50%-TTF) required to filter 100 ml of each mixture sample (or 50% of the initial sample volume) was measured and is shown in Table 2.

¹ Polymer C contains about 38% active (by weight) of tannin/AETAC block copolymer (wherein AETAC is about 57.5% by weight). The molecular weight is about 75,000.

² Polymer A contains about 38% active (by weight) of the AETAC/AM/EHA block copolymer. Its molecular weight is from 4,000,000 to 6,000,000.

The data shows that treatment additives with tannin containing polymers enhance the filterability of the mixed liquor samples. By means of the block copolymer, the dosage of the tannin containing polymer can be reduced while still providing good filterability. Since these block copolymers exhibit extremely strong flocculation ability, the dose required to achieve the same filter enhancement is much lower.

Example 3

Standard bottle tested following the test samples and control sample bottle tester (Phipps & Bird ^TM), to ensure proper mixing. Six 500 ml aliquots of the mixture were added to 6 vials. Treatment additives as shown in Table 3 were quickly added to each test sample. A control sample was also prepared by adding 500 ml of the mixed solution to the control bottle without adding a treating agent. All samples were rapidly stirred at 200 rpm for 30 seconds and then stirred for 15 minutes at a slower agitation speed of 50 rpm to thoroughly mix the samples.

The filterability of the mixture of each sample (including the control bottle) was evaluated by the TTF test method as described in Example 1. A 200 ml sample from each treated mixture sample and control vial was added to a separate Buchner funnel. A vacuum pressure of 51 kPa (15 inches Hg) was applied using a vacuum pump with a pressure regulator. The time (50%-TTF) required to filter 100 ml of each mixture sample (or 50% of the initial sample volume) was measured and is shown in Table 3.

¹ The polymer and alum aggregating agent or FeCl _{3 were} separately added to the mixed solution.

² The alum agglutinant product is an aqueous product of aluminum chlorohydrate (Al ₂ (OH) ₅ Cl) containing 50% active.

³ A FeCl ₃ solution was prepared directly using anhydrous FeCl ₃ chemical reagent (Sinopharm Chemical Reagent Co., Ltd., China).

The data shows that the block copolymer can be added with an alum or trivalent iron based aggregating agent to enhance the filterability of the mixed liquor samples. By means of the block copolymer, the dosage of the inorganic aggregating agents can be greatly reduced.

Although the exemplary embodiments have been described for purposes of illustration, the above description should not be construed as limiting. Accordingly, various modifications, changes and substitutions may be made by those skilled in the art without departing from the spirit and scope of the disclosure.

Claims (29)

A method of treating a mixed liquid in a thin film bioreactor, comprising dispersing a treatment additive in the mixed solution, wherein the treatment additive comprises a water soluble block copolymer. The method of claim 1, wherein the mixture is passed under pressure through a membrane in the membrane bioreactor. The method of claim 1, wherein the film in the thin film bioreactor is selected from the group consisting of hollow fibers having an outer microfilter or ultrafilter and a flat ultrafilter. The method of claim 3, wherein the film material is selected from the group consisting of chlorinated polyethylene, polyvinylidene fluoride, polyacrylonitrile, polyfluorene, polyether oxime, polyvinyl alcohol, cellulose acetate, and regenerated cellulose. . The method of claim 1, wherein the water-soluble block copolymer comprises a water-soluble monomer and a water-insoluble monomer. The method of claim 5, wherein the water-soluble block copolymer comprises a polymerization obtained by polymerization of a hydrophobic or water-insoluble monomer attached to a polymer chain obtained by polymerization of one or more water-soluble monomers. Chain segment. The method of claim 6, wherein the water-insoluble single system is selected from the group consisting of alkyl acrylates, alkyl methacrylamides, alkyl acrylamides, alkyl methacrylates, alkyl styrenes, ethylenically unsaturated carboxylic acids. High alkyl number of acid, alkylaryl ester of ethylenically unsaturated carboxylic acid, ethylenically unsaturated decylamine, vinyl alkylate, vinyl alkyl ether, N-vinyl decylamine and aralkyl a group of people. The method of claim 1, wherein the water-soluble block copolymer contains two segments represented by the formula: -[E]-[D]- wherein E is a polymerization of a hydrophobic monomer or a water-insoluble monomer The polymer segment obtained by the reaction and D is the polymer segment obtained from the polymerization of one or more water-soluble monomers. The method of claim 8, wherein in one embodiment, the water soluble monomers are nonionic or cationic. The method of claim 8, wherein E is poly(2-ethylhexyl acrylate). The method of claim 8, wherein D has the formula: -[A] _x -[J] _y - wherein A is a nonionic monomer, a J-based cationic polymer, x is 0 or a positive integer and y is 0 Or a positive integer. The method of claim 11, wherein the molar percentage of x:y is from about 0:100 to about 95:5. The method of claim 11, wherein the nonionic mono-system guanamine. The method of claim 11, wherein A has the following formula: Wherein R ₁ is hydrogen or C ₁ -C ₃ alkyl, and in one embodiment, R ₁ is hydrogen. The method of claim 11, wherein J has the following formula: A salt wherein R ₂ is hydrogen or a C ₁ -C ₃ alkyl group and a G-based ammonium cation. The method according to item 15 of the request, wherein G has the _{formula: - NHR 3 N (R 4} R 5, R 6) + M - or _{--OR 3 N (R 4, R} 5, R 6) + M - wherein R ₃ is a C ₁ to C ₄ linear or branched alkyl group, and R ₄ , R ₅ and R ₆ may be the same or different and are selected from hydrogen, C ₁ to C ₄ straight or branched alkyl, a group of C ₅ to C ₈ cycloalkyl, aromatic or alkyl aromatic groups, and an M ^- -based anion such as chloride, bromide or methylsulfate or hydrogen sulfate. The method of claim 15, wherein the G system is derived from 2-propenyloxyethyltrimethylammonium chloride, 3-methylpropenylpropyltrimethylammonium chloride, and 2-methylpropene chloride. a group consisting of methoxyethyltrimethylammonium and diallyldimethylammonium chloride. The method of claim 15, wherein J has the following structure: The method of claim 1, wherein the water soluble block copolymer has a number average molecular weight in the range of from about 100,000 to about 8,000,000. The method of claim 1, wherein the treatment additive is added to the mixture upstream of the membranes. The method of claim 1, wherein the treatment additive is added to the mixture at a location selected from the group consisting of a pump station, an aeration nozzle, and a sludge or a mixture recovery tube. The method of claim 1, wherein the treatment additive is added in an amount of from about 0.1 ppm by volume based on the volume of the mixture to the active polymer to about 100 ppm by volume of the living polymer. The method of claim 1, wherein the treatment additive additionally comprises a water soluble polymer or an inorganic aggregating agent. The method of claim 23, wherein the additional water-soluble polymer is blended or separately added to the water-soluble block copolymer. The method of claim 23, wherein the inorganic aggregating agent is blended with the water-soluble block copolymer or separately added to the mixed solution. The method of claim 23, wherein the additional water-soluble polymer is selected from the group consisting of a tannin-containing polymer, polychlorinated diallyldimethylammonium, polychloromethacrylic acid oxiranylethyl A group consisting of methylammonium, a copolymer of N,N-dimethylaminoethyl acrylate methyl chloride and acrylamide. The method of claim 26, wherein the inorganic aggregating agent is selected from the group consisting of inorganic compounds containing Ca, Mg, Si, Al, Fe, and combinations thereof. A method of increasing flux in a thin film bioreactor comprising dispersing a treatment additive in a mixture and passing the mixture through a film, wherein the treatment additive comprises a water soluble block copolymer. A method for purifying wastewater, comprising adding wastewater to a membrane bioreactor, adding microorganisms to the wastewater to prepare a mixed solution, treating the mixed solution with a treatment additive, and filtering the mixed solution with a membrane to produce purified water; The treatment additive comprises a water soluble block copolymer.