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WO2021132304A1 - Procédé et dispositif de traitement des eaux résiduaires - Google Patents

Procédé et dispositif de traitement des eaux résiduaires Download PDF

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Publication number
WO2021132304A1
WO2021132304A1 PCT/JP2020/048101 JP2020048101W WO2021132304A1 WO 2021132304 A1 WO2021132304 A1 WO 2021132304A1 JP 2020048101 W JP2020048101 W JP 2020048101W WO 2021132304 A1 WO2021132304 A1 WO 2021132304A1
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Prior art keywords
wastewater treatment
culture solution
surfactant
wastewater
culture
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Japanese (ja)
Inventor
涼介 鈴木
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Sanyo Chemical Industries Ltd
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Sanyo Chemical Industries Ltd
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F3/02—Aerobic processes
    • C02F3/12—Activated sludge processes
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12M—APPARATUS FOR ENZYMOLOGY OR MICROBIOLOGY; APPARATUS FOR CULTURING MICROORGANISMS FOR PRODUCING BIOMASS, FOR GROWING CELLS OR FOR OBTAINING FERMENTATION OR METABOLIC PRODUCTS, i.e. BIOREACTORS OR FERMENTERS
    • C12M1/00—Apparatus for enzymology or microbiology
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/10—Biological treatment of water, waste water, or sewage

Definitions

  • the present invention relates to a wastewater treatment method and a wastewater treatment apparatus.
  • an activated sludge treatment method is known in which wastewater containing organic matter is introduced into a biological treatment tank and treated with activated sludge to remove organic matter and the like. Further, following this active sludge treatment, a membrane module having a separation membrane such as a back-penetration membrane, an ultrafiltration membrane, a microfiltration membrane, and a hollow yarn membrane is passed through, and the load of organic substances is high, which is sufficient.
  • MLR Membrane Bio-Reactor
  • the sludge used for such activated sludge treatment is mainly composed of microorganisms in the biological treatment tank, and is an agglomeration of microorganisms grown using organic matter in wastewater as a nutrient source. Therefore, while the activated sludge treatment purifies the organic matter in the wastewater, the microorganisms proliferate accordingly and the amount of sludge generated increases. In addition, it is not a closed system treatment in which microorganisms existing in the biological treatment tank are not mixed with microorganisms from the outside world at all, but microorganisms universally present in the natural world are always mixed. Therefore, the microorganisms involved in biological treatment are diverse and have various characteristics and functions. Therefore, the microorganisms that predominate in the biological treatment tank differ depending on the wastewater to be treated.
  • a method of improving the efficiency of wastewater treatment and the ability to prevent the formation of bulking by using a method of dominated Bacillus which has a high growth rate among microorganisms in the wastewater treatment environment and produces a large amount of enzymes that decompose organic matter.
  • a method of adding Bacillus subtilis to a biological treatment tank containing sludge used for activated sludge treatment can be considered, but Bacillus subtilis added to microorganisms already predominantly present in the biological treatment tank. Is preyed on, and it may be difficult to predominate the Bacillus subtilis added later in the biological treatment tank.
  • Patent Documents 1 and 2 In order to occupy and maintain Bacillus, chemicals containing silicon compounds and minerals may be added, but the cost of the chemicals and the clogging of the separation membrane due to the generation of scale by the chemicals and the cleaning cost thereof are high. It becomes a problem (Patent Documents 1 and 2).
  • a small amount of culture solution is used by supplying a culture solution of fat-degrading bacteria that has been cultivated and grown in advance to the wastewater containing fat and oil and further growing the fat-degrading bacteria in the process of biological treatment. Therefore, a method is also disclosed in which the fats and oils in the fats and oils-containing wastewater can be treated in a state where they can be drained in a state suitable for environmental protection, and the generation of sludge can be significantly reduced.
  • the degrading bacteria will be preyed on by the microorganisms that predominantly exist in the biological treatment tank, and the water treatment efficiency will decrease (Patent Document 3).
  • a protein that contributes to the decomposition of an organic substance is efficiently produced by a microorganism, a culture solution for wastewater treatment containing the protein is prepared, and the culture solution for wastewater treatment is used to promote the decomposition of the organic substance. It is an object of the present invention to provide a wastewater treatment method capable of increasing wastewater treatment efficiency and a wastewater treatment device that can be used in the wastewater treatment method.
  • the present invention comprises culturing in a culture tank a microorganism that secretes and produces protein (A) that contributes to the decomposition of organic substances in wastewater in a culture medium containing a surfactant (B).
  • a process for preparing a culture solution for wastewater treatment which comprises causing the microorganism to secrete and produce the protein (A) to prepare a culture solution for wastewater treatment containing the microorganism, the protein (A), and the surfactant (B).
  • Wastewater treatment method containing: A culture solution for wastewater treatment containing a microorganism that secretes and produces a protein (A) that contributes to the decomposition of organic substances in wastewater, the above protein (A), and a surfactant (B).
  • a protein that contributes to the decomposition of an organic substance is efficiently produced by a microorganism, a culture solution for wastewater treatment containing the protein is prepared, and the culture solution for wastewater treatment is used to produce an organic substance. It has the effect of promoting decomposition and increasing wastewater treatment efficiency. In addition, the load in wastewater treatment can be reduced to suppress bulking formation, and wastewater treatment efficiency can be improved.
  • FIG. 1 is a schematic view schematically showing an example of the wastewater treatment apparatus of the present invention.
  • FIG. 2 is a schematic view schematically showing an example of the wastewater treatment apparatus of the present invention using the MBR membrane.
  • the present invention is described above by culturing a microorganism that secretes and produces a protein (A) that contributes to the decomposition of organic substances in wastewater in a culture medium containing a surfactant (B) in a culture tank.
  • It includes a culture solution addition step of adding the culture solution for wastewater treatment to the wastewater from the culture tank, and a wastewater treatment step of performing active sludge treatment of the wastewater in the presence of the culture solution for wastewater treatment in the biological treatment tank. It is a wastewater treatment method.
  • the activated sludge treatment of wastewater involves a microorganism that secretes and produces a protein (A) that contributes to the decomposition of organic matter in the wastewater, a protein (A), and a surfactant (in a biological treatment tank). It is carried out in the presence of a culture solution for wastewater treatment containing B) and.
  • the organic matter contained in the wastewater is fragmented by the protein (A). Fragmented organic matter is easily decomposed by microorganisms existing in the biological treatment tank. Therefore, the wastewater treatment efficiency can be improved.
  • the microorganism that decomposes organic matter in the biological treatment tank may be a microorganism that secretes and produces protein (A), or may be another microorganism.
  • the microorganism existing in the biological treatment tank may be one kind or two or more kinds.
  • microorganisms secreting and producing protein (A) are cultured in a surfactant-containing culture solution containing a surfactant (B).
  • a surfactant-containing culture solution containing a surfactant (B) To secrete and produce protein (A).
  • a culture solution for wastewater treatment containing a microorganism, a protein (A), and a surfactant (B) is prepared.
  • the protein (A) can be efficiently produced in large quantities.
  • the microorganisms are less likely to be affected by external factors when secreting and producing the protein (A).
  • the surfactant-containing culture solution may contain microorganisms in advance. That is, the surfactant-containing culture solution may contain microorganisms as a constituent component. Further, the surfactant-containing culture solution does not have to contain microorganisms in advance. When the surfactant-containing culture solution does not contain microorganisms, the process of preparing the culture solution for wastewater treatment may be performed after adding the microorganisms to the surfactant-containing culture solution. In addition, the culture solution for wastewater treatment contains microorganisms as a constituent component.
  • the protein (A) secreted and produced by microorganisms can be continuously supplied to wastewater.
  • protein (A) can be continuously produced by culturing microorganisms in a culture tank.
  • the cost of purchasing the protein (A) is high, so that the cost of treating the wastewater is high.
  • the microorganism that secretes and produces the protein (A) plays a role in producing the protein (A) in the process of preparing the culture solution for wastewater treatment.
  • the produced protein (A) plays a role of fragmenting organic substances in the wastewater treatment step. Therefore, in the wastewater treatment step, even if the microorganism secreting and producing the protein (A) does not predominantly exist in the biological treatment tank, a sufficient amount of the protein (A) can be supplied to the biological treatment tank. .. Therefore, the wastewater can be sufficiently treated even if the microorganism that secretes and produces the protein (A) is not predominantly present in the biological treatment tank.
  • microorganisms that secrete and produce protein (A) may be predominantly present in the biological treatment tank in the wastewater treatment step.
  • a microorganism secreting and producing protein (A) is directly added to a biological treatment tank as in a conventional wastewater treatment method, the microorganism secreting and producing protein (A) sufficiently secretes and produces protein (A).
  • the protein (A) is sufficiently supplied to the biological treatment tank because it is preyed on by the microorganisms existing in the biological treatment tank. As a result, the organic matter in the wastewater is less likely to be fragmented by the protein (A), and the wastewater treatment efficiency is not sufficiently improved.
  • the surfactant (B) exerts a function of promoting the secretory production of the protein (A). Therefore, the concentration of the protein (A) in the culture solution for wastewater treatment can be increased by using the surfactant (B).
  • the microorganism is further cultured in the culture solution containing no surfactant (B) in the culture tank before the step of preparing the culture solution for wastewater treatment.
  • the above-mentioned surfactant (B) is added to the above-mentioned surfactant-free culture solution.
  • the culture time in the wastewater treatment culture solution preparation step is the total time of the culture time in the surfactant-free culture solution preparation step and the culture time in the wastewater treatment culture solution preparation step. It is preferably 10% or more, preferably 10 to 90%, and even more preferably 60 to 80% based on the above. If the amount of the surfactant is large relative to the amount of the microorganism, the growth of the microorganism is suppressed, and the microorganism may be killed or the growth is inhibited.
  • the surfactant-free culture solution preparation step When the surfactant-free culture solution preparation step is performed, the surfactant is added after culturing a certain amount of microorganisms, so that the growth of the microorganisms is less likely to be suppressed and the microorganisms can grow sufficiently. Therefore, the protein (A) can be suitably secreted and produced.
  • the microorganisms In the preparation of the culture solution containing no surfactant, the microorganisms may be cultured in a culture solution containing microorganisms in advance, or the microorganisms may be added to the culture solution containing no microorganisms to culture the microorganisms.
  • the obtained surfactant-free culture solution contains microorganisms as a constituent component.
  • the total time of the culture time in the culture solution preparation step containing no surfactant and the culture time in the culture solution preparation step for wastewater treatment refers to the culture tank in the culture solution preparation step containing no surfactant.
  • the time from the start of culturing to the end of culturing in the culture tank in the process of preparing the culture solution for wastewater treatment is shown.
  • the time when the culture starts in the culture tank in the process for preparing the culture solution containing no surfactant is the time when the microorganism is added to the culture tank, and the time when the culture ends in the culture tank in the process for preparing the culture solution for wastewater treatment is obtained by culturing.
  • the degree of progress of the culture can be confirmed by measuring the turbidity (also referred to as OD) of the culture solution.
  • the turbidity (OD) of this culture solution relatively represents the number of microorganisms in the culture solution.
  • the turbidity (OD) of the culture solution is calculated by the following measuring method and calculation formula.
  • ⁇ Measurement method of turbidity (OD) of culture solution Using a surfactant-free culture solution containing sampled microorganisms and a culture solution for wastewater treatment, using a turbidity meter [for example, UV-1700 manufactured by Shimadzu Corporation], and using a quartz cell having an optical path length of 1 cm. And measure the turbidity.
  • the surfactant-free culture solution and the wastewater treatment culture solution are centrifuged at 1500 rpm for 5 minutes at 4 ° C., and the supernatant is discarded.
  • the surfactant (B) used in the wastewater treatment method of the present invention is composed of a nonionic surfactant (B1), an anionic surfactant (B2), an amphoteric surfactant (B3) and a cationic surfactant (B4). It is preferably at least one surfactant selected from the above group, and more preferably a nonionic surfactant (B1).
  • Preferred nonionic surfactants (B1) are alcohol alkylene oxide (hereinafter, alkylene oxide may be abbreviated as AO) adduct (B1a), alkylphenol AO adduct (B1b), and fatty acid AO adduct (B1a).
  • AO alcohol alkylene oxide
  • B1a alkylphenol AO adduct
  • B1b alkylphenol AO adduct
  • B1a fatty acid AO adduct
  • B1c polyhydric alcohol type nonionic surfactant
  • B1d polyhydric alcohol type nonionic surfactant
  • HLB is known as a measure of hydrophilicity and hydrophobicity of nonionic surfactant (B1). The higher the HLB value, the higher the hydrophilicity.
  • the HLB of the nonionic surfactant (B1) is preferably 0.1 to 16 from the viewpoint of wastewater treatment efficiency, and more preferably 1 to 16.
  • the number average molecular weight of the nonionic surfactant (B1) is preferably 100 to 20,000, more preferably 200 to 20,000, from the viewpoint of wastewater treatment efficiency.
  • Examples of the alcohol AO adduct (B1a) include polyoxyethylene alkyl ether, polyoxyalkylene alkyl ether and polyalkylene glycol.
  • the alcohol AO adduct (B1a) ethylene oxide of a higher alcohol having 8 to 24 carbon atoms (decyl alcohol, dodecyl alcohol, coconut oil alkyl alcohol, octadecyl alcohol, oleyl alcohol, etc.) (hereinafter, ethylene oxide is referred to as EO).
  • propylene oxide may be abbreviated as PO) 1 to 20 mol adduct (including block adduct and / or random adduct) . And so on).
  • Examples of the EO 0 to 20 mol and / or PO 1 to 20 mol adduct of the higher alcohol having 8 to 24 carbon atoms include the EO adduct of decyl alcohol. Also included are EO8 mol / PO7 mol block adducts of decyl alcohol.
  • alkylphenol AO adduct (B1b) examples include an alkylphenol AO adduct having an alkyl group having 6 to 24 carbon atoms.
  • Specific examples of the alkylphenol AO adduct (B1b) include EO1 to 20 mol and / or PO1 to 20 mol adduct of octylphenol, and EO1 to 20 mol and / or PO1 to 20 mol adduct of nonylphenol.
  • fatty acid AO adduct (B1c), EO1 to 20 mol and / or PO1 of fatty acids having 8 to 24 carbon atoms (decanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, coconut oil fatty acid, etc.) Included are ⁇ 20 mol additions.
  • fatty acid AO adduct B1c
  • polyhydric alcohol type nonionic surfactant (B1d) As the polyhydric alcohol type nonionic surfactant (B1d), EO and / or PO addition of 2 to 8 valent polyhydric alcohols (glycerin, trimethylolpropane, pentaerythritol, sorbit, sorbitan, etc.) having 3 to 36 carbon atoms.
  • nonionic surfactants (B1) the alcohol AO adduct (B1a) and the polyhydric alcohol-type nonionic surfactant (B1d) are preferable. More preferred are the decyl alcohol EO adduct of the alcohol AO adduct (B1a), the EO and / or PO block adduct (B1d) of the coconut oil fatty acid diethanolamide.
  • anionic surfactant (B2) examples include ether carboxylic acid (B2a) and its salt, sulfate ester (B2b) and its salt, ether sulfate ester (B2c) and its salt, sulfonate (B2d), and sulfosuccinate (B2d).
  • Examples of the ether carboxylic acid (B2a) and a salt thereof include an ether carboxylic acid having a hydrocarbon group (8 to 24 carbon atoms) and a salt thereof.
  • an ether carboxylic acid having a hydrocarbon group (8 to 24 carbon atoms) and a salt thereof examples include sodium lauryl glycol acetate.
  • Examples of the sulfate ester (B2b) and a salt thereof include a sulfate ester having a hydrocarbon group (8 to 24 carbon atoms) and a salt thereof.
  • Specific examples of the sulfate ester (B2b) and its salt include sodium lauryl sulfate and triethanolamine lauryl sulfate.
  • ether sulfate ester (B2c) and a salt thereof examples include an ether sulfate ester having a hydrocarbon group (8 to 24 carbon atoms) and a salt thereof.
  • Specific examples of the ether sulfate ester (B2c) and a salt thereof include polyoxyethylene lauryl ether sulfate sodium salt and polyoxyethylene lauryl ether sulfate triethanolamine salt.
  • Examples of the sulfonate (B2d) include dodecyldiphenyl ether disulfonic acid sodium salt, dodecylbenzenesulfonic acid sodium salt, naphthalene sulfonic acid sodium salt and the like.
  • sulfosuccinate (B2e) examples include polyoxyethylene lauryl sulfosuccinate disodium salt, sulfosuccinate lauryl disodium salt, sulfosuccinate polyoxyethylene lauroylethanolamide disodium salt and the like.
  • Examples of the phosphoric acid ester (B2f) include disodium octyl phosphate and disodium lauryl phosphate.
  • ether phosphate ester (B2g) examples include polyoxyethylene octyl ether phosphate disodium salt and polyoxyethylene lauryl ether phosphate disodium salt.
  • fatty acid salt (B2h) examples include sodium octylate salt, sodium laurylate salt, sodium stearate salt and the like.
  • ether carboxylic acid (B2a) and sulfonate (B2d) are preferable. More preferred are a sodium polyoxyethylene lauryl ether acetate salt of ether carboxylic acid (B2a) and a sodium dodecyldiphenyl ether disulfonic acid salt of sulfonate (B2d).
  • the pKa of the anionic group of the anionic surfactant (B2) in water (25 ° C.) is preferably 1 to 5, more preferably 1 to 4, and particularly preferably 1 to 3.6. is there.
  • Specific examples of anionic groups having a pKa of 1 to 5 include a carboxyl group (-COOH), a sulfate group (-OSO 3 H), a sulfo group (-SO 3 H), a sulfino group (-SO 2 H), and a sulfeno.
  • the anionic surfactant (B2) has two or more anionic groups, any one of the pKas may be in the above range, and the pKas of all the anionic groups are in the above range. preferable.
  • amphoteric tenside agent (B3) examples include a carboxylate-type amphoteric tenside agent (B3a), a sulfate-type amphoteric tenside agent (B3b), a sulfonate-type amphoteric tenside agent (B3c), and a phosphate ester salt.
  • B3d type amphoteric tenside agent and the like are included.
  • Examples of the carboxylate-type amphoteric tenside agent (B3a) include an amino acid-type amphoteric tenside agent (B3a1), a betaine-type amphoteric tenside agent (B3a2), and an imidazoline-type amphoteric tenside agent (B3a3).
  • amino acid type amphoteric surfactant (B3a1) amphoteric surfactants having an amino group and a carboxyl group in the molecule, and examples thereof include compounds represented by the following general formula (1).
  • R is a monovalent hydrocarbon group having 1 to 20 carbon atoms.
  • n is an integer of 1 or more.
  • m is an integer of 1 or more.
  • M is a monovalent or divalent cation such as proton, alkali metal, alkaline earth metal, ammonium (including cations derived from amines and alkanolamines) and quaternary ammonium.
  • alkylaminopropionic acid type amphoteric surfactants sodium cocaminopropionate, sodium stearylaminopropionate, sodium laurylaminopropionate and dodecyl- ⁇ -aminopropionic acid
  • alkylaminoacetic acid type amphoteric surfactants sodium laurylaminoacetate, etc.
  • N-lauroyl-N'-carboxymethyl-N'-hydroxyethylethylenediamine sodium examples thereof include alkylaminoacetic acid type amphoteric surfactants (sodium laurylaminoacetate, etc.) and N-lauroyl-N'-carboxymethyl-N'-hydroxyethylethylenediamine sodium.
  • the betaine-type amphoteric tenside (B3a2) is an amphoteric tenside having a quaternary ammonium salt-type cation moiety and a carboxylic acid-type anion moiety in the molecule.
  • Examples of the betaine-type amphoteric surfactant (B3a2) include compounds represented by the following general formula (2).
  • R is a monovalent hydrocarbon group having 1 to 20 carbon atoms.
  • betaine-type amphoteric surfactant examples include alkyldimethylbetaine (betaine stearyldimethylaminoacetate and betaine lauryldimethylaminoacetate, etc.) and amide betaine (coconut oil fatty acid amidepropyl betaine, etc. (palm oil fatty acid amidepropyldimethyl).
  • Aminoacetate betaine and the like) and laurate amide propyl betaine and the like) alkyldihydroxyalkyl betaine (lauryl dihydroxyethyl betaine and the like) and cured coconut oil fatty acid amide propyl dimethylaminoacetate betaine can be mentioned.
  • imidazoline-type amphoteric surfactant (B3a3) examples include 2-alkyl-N-carboxymethyl-N-hydroxyethyl imidazolinium betaine.
  • amphoteric surfactants include glycine-type amphoteric surfactants such as sodium lauroylglycine, sodium lauryldiaminoethylglycine, lauryldiaminoethylglycine hydrochloride and dioctyldiaminoethylglycine hydrochloride; sulfobetaine-type such as pentadecylsulfotaurine.
  • Amphoteric surfactants colamidopropyldimethylammoniopropanesulfonic acid (CHAPS), colamidopropyldimethylammonio 2-hydroxypropanesulfonic acid (CHASPO) and sodium 2- (dodecylamino) ethanesulfonate; lauryldimethylamine oxide, etc.
  • Alkylamine oxide type amphoteric surfactant and the like are included.
  • Examples of the phosphate ester salt-type amphoteric tenside agent (B3d) include miltefosine.
  • amphoteric tenside agents preferred are carboxylate-type amphoteric surfactants (B3a) and phosphate ester salt-type amphoteric surfactants (B3d). More preferred are betaine lauryldimethylaminoacetate and sodium propionate cocaminopropionate, which are carboxylate-type amphoteric surfactants (B3a).
  • the pKa of the anionic group of the amphoteric tenside (B3) in water (25 ° C.) is preferably 1 to 5, more preferably 1 to 4, and particularly preferably 1 to 3.6.
  • the pKa of the amphoteric surfactant (B3) due to the cationic group is preferably 8 to 14, more preferably 9 to 14, and particularly preferably 9.2 to 14.
  • the anionic group having a pKa of 1 to 5 is the same as that of the anionic group exemplified in the anionic surfactant (B2).
  • Examples of the cationic group having a pKa of 8 to 14 include a quaternary ammonio group, a primary to tertiary amino group and the like, and a salt group thereof.
  • the amphoteric tenside (B3) has two or more anionic groups, any one of the pKas may be in the above range, and the pKas of all the anionic groups are in the above range. preferable.
  • any one of the pKas may be in the above range, and it is more preferable that the pKas of all the cationic groups are in the above range.
  • the cationic surfactant (B4) includes an amine salt-type cationic surfactant (B4a), a quaternary ammonium salt-type cationic surfactant (B4b), and the like.
  • the primary to tertiary amines are inorganic acids (hydrochloric acid, nitric acid, sulfuric acid, hydrogen iodide, etc.) or organic acids (acetic acid, formic acid, oxalic acid, lactic acid, gluconic acid, adipine). Acids, alkylphosphoric acid, etc.) neutralized.
  • inorganic or organic acid salts of aliphatic higher amines higher amines such as lauryl amine, stearyl amine, cetyl amine, hardened beef amine and rosin amine
  • higher grade of lower amines higher grade of lower amines.
  • Examples include fatty acid (stearic acid, oleic acid, etc.) salts.
  • Examples of the secondary amine salt type include inorganic acid salts or organic acid salts such as ethylene oxide adducts of aliphatic amines.
  • Examples of the tertiary amine salt type include aliphatic amines (triethylamine, ethyldimethylamine and N, N, N', N'-tetramethylethylenediamine, etc.) and ethylene oxide of aliphatic amines (2 mol).
  • alicyclic amines N-methylpyrrolidin, N-methylpiperidin, N-methylhexamethyleneimine, N-methylmorpholin and 1,8-diazabicyclo (5,4,0) -7-undecene, etc.
  • Inorganic or organic acid salts of nitrogen-containing heterocyclic aromatic amines (4-dimethylaminopyridine, N-methylimidazole and 4,4'-dipyridyl, etc.); triethanolamine monostearate, stearamide ethyl diethylmethylethanol Examples thereof include inorganic acid salts and organic acid salts of tertiary amines such as amines.
  • Examples of the quaternary ammonium salt-type cationic surfactant (B4b) include tertiary amines and quaternary agents (alkylating agents such as methyl chloride, methyl bromide, ethyl chloride, benzyl chloride and dimethyl sulfate; ethylene oxide and the like). What is obtained by the reaction with.
  • lauryltrimethylammonium chloride didecyldimethylammonium chloride, dioctyldimethylammonium bromide, stearyltrimethylammonium bromide, lauryldimethylbenzylammonium chloride (benzalkonium chloride), cetylpyridinium chloride, polyoxyethylenetrimethylammonium chloride and stearamide ethyldiethyl.
  • examples thereof include methylammonium metosulfate.
  • cationic surfactants (B4) a quaternary ammonium salt-type cationic surfactant (B4b) is preferable, and lauryltrimethylammonium chloride is more preferable.
  • the pKa due to the cationic group of the cationic surfactant (B4) is preferably 8 to 14, more preferably 9 to 14, and particularly preferably 9.2 to 14.
  • the cationic group having a pKa of 8 to 14 include a quaternary ammonio group, a primary to tertiary amino group and the like, and a salt group thereof.
  • the cationic surfactant (B4) has two or more cationic groups, any one of the pKas may be in the above range, and the pKas of all the cationic groups should be in the above range. preferable.
  • the surfactant (B) may be used as it is, or may be mixed with water and used as an aqueous diluent (aqueous solution or aqueous dispersion) if necessary. ..
  • the total concentration of the surfactant (B) in the aqueous diluent is appropriately selected depending on the type of microorganism, the type of protein (A) and the type of extraction method, but from the viewpoint of wastewater treatment efficiency and handleability, it is aqueous. Based on the weight of the diluent, 0.1 to 99% by weight is preferable, and 1 to 50% by weight is more preferable.
  • the amount (% by weight) of the surfactant (B) used in the culture solution used in the wastewater treatment method of the present invention is appropriately selected depending on the type of microorganism, the type of protein (A), and the type of extraction method.
  • the content (% by weight) of the surfactant (B) in the surfactant-containing culture solution is based on the weight of the surfactant-containing culture solution, and has cell toxicity, wastewater treatment efficiency, and resistance to protein denaturation. From the viewpoint, 0.001 to 10% by weight is preferable, more preferably 0.01 to 8% by weight, then further preferably 0.05 to 5% by weight, and particularly preferably 0.1 to 2. 5% by weight.
  • the medium contained in the surfactant-free culture medium and the surfactant-containing culture medium used in the wastewater treatment method of the present invention is not particularly limited as long as it is a cell culture medium generally used in the art. It can be either a natural medium or a synthetic medium containing a carbon source, a nitrogen source or other essential nutrients.
  • Examples of the carbon source include carbohydrates such as glucose, fructose, sucrose and starch, organic acids such as acetic acid and propionic acid, and alcohols such as ethanol and propanol.
  • nitrogen source examples include ammonium salts of inorganic or organic acids such as ammonia, ammonium chloride, ammonium sulfate, ammonium acetate and ammonium phosphate, or other nitrogen-containing compounds, as well as peptone, meat extract and corn steep liquor.
  • ammonium salts of inorganic or organic acids such as ammonia, ammonium chloride, ammonium sulfate, ammonium acetate and ammonium phosphate, or other nitrogen-containing compounds, as well as peptone, meat extract and corn steep liquor.
  • inorganic salts include primary potassium phosphate, dipotassium phosphate, magnesium phosphate, magnesium sulfate, sodium chloride, ferrous sulfate, manganese sulfate and copper sulfate. , Calcium carbonate and the like are used.
  • the microorganism that secretes and produces the protein (A) used in the wastewater treatment method of the present invention includes, but is not limited to, examples below.
  • Examples of microorganisms that secrete and produce protein (A) include prokaryotes and eukaryotes having a cell wall containing a polysaccharide in the outermost layer.
  • the outermost layer is a layer located outside the cell membrane and is in direct contact with the external environment on the outermost surface of the cell.
  • the polysaccharide is a compound in which a monosaccharide takes a multimer by glycosidic bond and does not contain lipopolysaccharide.
  • Bacteria that are prokaryotes include eubacteria and archaea. Ectobacteria include Gram-negative and Gram-positive bacteria.
  • eukaryotes having a cell wall containing a polysaccharide in the outermost layer include fungi and algae.
  • Gram-negative bacteria include Escherichia, Thermus, Rhizobium, Pseudomonas, Pseudomonas, Shewanella, Vibrio, Salmonella, Acetobacter, Synechocystis, Xanthomonas, Gluconobacter, etc. And Xanthomonas sp. And so on.
  • Gram-positive bacteria examples include Bacillus, Streptmyces, Corynebacterium, Brevibacillus, Bifidobacterium, Lactococcus, Enterococcus, Pediococcus, Leuconostoc, and the like.
  • fungi examples include Basidiomycota, Ascomycota, Chytridomycota, Neocalimastigomycota, Blastocladiomycota, Blastocladiomycota, Blastocladiomycota, Blastocladiomycota, Blastocladiomycota, Blastocladiomycota, Blastocladiomycota Gate (Gromeromycota), Mucoromycotina, Basidiomycotina, Chytridiomycotina, Kickxellomycotina, etc.
  • the Ascomycota (Ascomycota), Ambrosiozyma, Arxula, Babjevia, Blastobotrys, Candida, Citeromyces, Clavispora, Debaryomyces, Dekkera, Dipodascus, Galactomyces, Geotrichum, Hanseniaspora, Hansenula, Kazachstania, Kloeckera, Kluyveromyces, Lipomyces, Aspergillus, Lodderomyces, Metschnikowia , Myxozyma, Nadsonia, Ogataea, Minuta, Pachysolen, Pichia, Saccharomyces, Saccharomycopsis, Saitoella, Saprochaete, Saturnispora, Schizoblastosporion, Schizosaccharomyces, Sporopachydermia, Starmerella, Stephanoascus, Symbiotaphrina, Sympodiomyces, Tetrapisispora
  • algae examples include cyanobacteria (cyanobacteria), which are eubacteria, and unicellular organisms (diatoms, yellow-green algae, dinoflagellates, etc.), which are eukaryotes.
  • cyanobacteria cyanobacteria
  • unicellular organisms diatoms, yellow-green algae, dinoflagellates, etc.
  • the microorganism in the present invention is preferably at least one selected from the group consisting of eubacteria, archaea and fungi. More preferably, they are Gram-positive bacteria and / or fungi, and most preferably Bacillus and Corynebacterium, Aspergillus, Saccharomyces, Pichia, Candida, Schizosaccharomyces, Yarrowia, Hansenula, Oga. is there. One type of microorganism may be used, or two or more types may be used in combination. Further, in the present invention, when the microorganism is a Gram-positive bacterium and / or a fungus, the surfactant (B) is preferably a nonionic surfactant (B1).
  • the protein (A) that contributes to the decomposition of organic substances in wastewater in the present invention is not particularly limited, but includes enzymes, peptides, and the like.
  • Examples of the protein (A) include enzymes ⁇ oxidoreductases (cholesterol oxidase, glucose oxidase, ascorbic acid oxidase, peroxidase, etc.), hydrolyzing enzymes (lysoteam, protease, aldehyde dehydrogenase, serine protease, amylase, lipase, cellulase, glucoamylase, etc.).
  • enzymes ⁇ oxidoreductases cholesterol oxidase, glucose oxidase, ascorbic acid oxidase, peroxidase, etc.
  • hydrolyzing enzymes lysoteam, protease, aldehyde dehydrogenase, serine protease, amylase, lipase, cellulase, glucoamylase, etc.
  • Iisomerase glucose isomerase, etc.
  • transfer enzyme acyl transferase, sulfotransferase, etc.
  • synthase fatty acid synthase, phosphate synthase, citrate synthase, etc.
  • elimination enzyme pectin lyase, etc.
  • lipase, amylase, cellulase, protease, and aldehyde dehydrogenase are particularly preferable from the viewpoint of ease of protein production and wastewater treatment efficiency.
  • microorganisms that produce lipase include Yarrowia and Pseudomonas.
  • microorganisms that produce amylase include Pseudomonas and the like.
  • microorganisms that produce cellulase include Bacillus and the like.
  • microorganisms that produce protease include Escherichia and the like.
  • microorganisms that produce aldehyde dehydrogenase include Pseudomonas and the like.
  • a surfactant (B) and a medium are mixed, and then a microorganism secreting and producing protein (A) is added to culture containing the surfactant. It may be a liquid.
  • Mixing of the surfactant (B) and the medium can be performed by adding the surfactant (B) to the medium at 4 ° C. to 99 ° C. and stirring with an aeration facility, a stirring blade, a stirrer or the like. Further, the surfactant (B) may be added while stirring the medium with a stirring blade or the like.
  • Pre-culture Microorganisms that secrete and produce protein (A) are pre-cultured. Preculture can be performed on agar medium at 15-43 ° C. for 3-72 hours.
  • Process for preparing a culture medium containing no surfactant The medium is sterilized by autoclave at 121 ° C. for 20 minutes, and a microorganism that secretes and produces the protein (A) precultured on an agar medium using a platinum loop is added and cultured. , Prepare a culture medium containing no surfactant.
  • the culture temperature is preferably 15 to 43 ° C.
  • Surfactant addition step The surfactant-free culture solution prepared in the surfactant-free culture solution preparation step is added to prepare a surfactant-containing culture solution.
  • Wastewater treatment culture solution preparation step Microorganisms that secrete and produce protein (A) are cultured in a surfactant-containing culture solution containing a surfactant (B) to prepare a wastewater treatment culture solution.
  • the culture temperature is preferably 15 to 43 ° C.
  • the culture time of the microorganism that secretes and produces the protein (A) in the surfactant-free culture solution preparation step and the wastewater treatment culture solution preparation step is 12 to 72 hours based on the amount of the protein (A) produced. Is preferable.
  • the wastewater treatment method of the present invention includes a culture solution addition step of adding the wastewater treatment culture solution to the wastewater from the culture tank, and an activated sludge treatment of the wastewater in the presence of the wastewater treatment culture solution in the biological treatment tank. Includes a wastewater treatment step.
  • the biological treatment tank may be provided with a separation membrane.
  • the wastewater may be supplied to the biological treatment tank through steps such as a solid-liquid separation step and a flow rate adjustment step, and may be treated with activated sludge in the presence of a culture solution for wastewater treatment.
  • the solid-liquid separation step can be performed in a solid-liquid separation tank having a function of solid-liquid separation of wastewater
  • the flow rate adjusting step can be performed in a flow rate adjusting tank having a function of adjusting the flow rate of wastewater. It is preferable that steps such as a solid-liquid separation step and a flow rate adjusting step are appropriately provided depending on the type of wastewater and the scale of the plant.
  • the time when the culture solution for wastewater treatment is added to the wastewater is not particularly limited, but from the viewpoint of wastewater treatment efficiency, it is preferable that the wastewater is before being supplied to the biological treatment tank, and more preferably, the wastewater is solid-liquid separated. Therefore, it is preferable that the wastewater is added while being supplied to the biological treatment tank.
  • a method of adding the culture solution for wastewater treatment to a solid-liquid separation tank containing wastewater or a flow rate adjusting tank can be mentioned.
  • the protein (A) is an enzyme
  • the protein contained in the wastewater treatment culture solution is contained between the wastewater treatment culture solution preparation step and the culture solution addition step.
  • the enzyme activity of protein (A) can be measured using a commercially available kit or the like.
  • a fluorescent proteolytic enzyme assay kit manufactured by Thermo Fisher Scientific Co., Ltd.
  • This kit contains a reagent whose fluorescence intensity is increased by the enzymatic activity of a proteolytic enzyme.
  • the reagent can be added and allowed to stand at room temperature for 5 to 60 minutes, then the fluorescence intensity can be measured, and the protease activity in the sample water can be calculated from a calibration curve or the like prepared in advance.
  • ⁇ mol / min (Unit)
  • ⁇ mol / min (Unit)
  • the amount of a predetermined decomposition product produced when the reference protein is decomposed under predetermined conditions per hour can be used. ..
  • the amount of the wastewater treatment culture solution added per day is, for example, 10 mL / day and 1,000 to 10,000 U / day when the enzyme activity per weight of the wastewater treatment culture solution is 10,000 to 100,000 U / g. It is preferable to control the amount to 100 mL / day in the case of g and 1,000 mL / day in the case of 100 to 1,000 U / g.
  • the enzyme activity and the amount of the culture solution for wastewater treatment added per day can be adjusted and optimized according to the type of organic matter contained in the wastewater, the type of enzyme, the treatment scale, and the like.
  • the wastewater treatment apparatus of the present invention uses a culture solution for wastewater treatment containing a microorganism that secretes and produces a protein (A) that contributes to the decomposition of organic substances in the wastewater, the protein (A), and a surfactant (B).
  • This is a wastewater treatment apparatus used for treating wastewater with active sludge, and the microorganism is cultured in a surfactant-containing culture solution containing the surfactant (B) to obtain the wastewater treatment culture solution.
  • a culture tank for this purpose and a supply means for adding the culture solution for wastewater treatment from the culture tank to the wastewater are provided.
  • the wastewater treatment apparatus of the present invention is added by the measuring means for measuring the enzyme activity value of the protein (A) in the wastewater treatment culture solution and the supply means.
  • the amount of the wastewater treatment culture solution to be added is determined based on the measured enzyme activity value, and the amount of the wastewater treatment culture added by the supply means based on the determined addition amount. It is preferable to further provide a control means for controlling the amount of the liquid added. Further, it is more preferable that the addition amount determining means determines the addition amount of the culture solution for wastewater treatment per day.
  • An example of a device for controlling the amount of the culture solution for wastewater treatment added per day is a flow rate control device.
  • the enzyme activity and the amount of the culture solution for wastewater treatment per day can be adjusted and optimized according to the type of organic matter contained in the wastewater, the type of enzyme, the treatment scale, and the like.
  • FIG. 1 is a schematic view schematically showing an example of the wastewater treatment apparatus of the present invention.
  • the wastewater treatment device 1 shown in FIG. 1 is a living organism that serves as a place for treating wastewater from a raw water tank 10, a flow rate adjusting tank 20 in which wastewater is supplied from the raw water tank 10, and a flow rate adjusting tank 20.
  • the treatment tank 30, the solid-liquid separation tank 40 to which the wastewater after the active sludge treatment is supplied from the biological treatment tank 30, and the microorganisms are cultured in a surfactant-containing culture solution containing the surfactant (B) for wastewater treatment. It is provided with a culture tank 50 for obtaining a culture solution for wastewater and a control device 60 for determining and controlling the supply amount of the culture solution for wastewater and wastewater treatment.
  • the wastewater treatment device 1 there is a drainage flow path 71 between the raw water tank 10 and the flow rate adjusting tank 20, and there is a drainage flow path 72 between the flow rate adjusting tank 20 and the biological treatment tank 30. There is a drainage channel 73 between the 30 and the solid-liquid separation tank 40. A valve 91 is arranged in the drainage flow path 73.
  • the culture tank 50, the raw water tank 10, the flow rate adjusting tank 20, and the biological treatment tank 30 are connected by a pipe 75, and the pipe 75 is connected to the culture tank 50 to the raw water tank 10, the flow rate adjusting tank 20, and the biological treatment tank.
  • a pump 81 for supplying the culture solution for wastewater treatment is arranged in No. 30.
  • a valve 92 is arranged downstream of the pump 81 of the pipe 75.
  • the raw water tank 10 has a function of storing raw water of wastewater containing organic substances.
  • the flow rate adjusting tank 20 controls the amount of wastewater supplied from the raw water tank 10 to the flow rate adjusting tank 20 and the amount of wastewater supplied from the flow rate adjusting tank 20 to the biological treatment tank 30 to control the amount of wastewater supplied from the entire wastewater treatment device 1. It has a function to adjust the flow rate.
  • the biological treatment tank 30 includes an aeration device 31 that supplies a gas for activating microorganisms that decompose organic matter, a pump 82 for discharging excess activated sludge, and a surplus sludge discharge port 32 that is a discharge port thereof. To be equipped.
  • the solid-liquid separation tank 40 has a function of solid-liquid separation of wastewater treated with activated sludge, and is a pump 83 for discharging treated water after solid-liquid separation, and a treated water discharge port 41 which is a discharge port thereof. To be equipped.
  • the control device 60 is used for wastewater treatment, such as dissolved oxygen amount, oxidation-reduction potential, hydrogen ion concentration, sludge concentration, organic matter load amount, etc. of wastewater in the raw water tank 10, the flow rate adjusting tank 20, the biological treatment tank 30, and the culture tank 50. Based on the amount of protein (A) in the culture solution, the function to determine and control the supply amount of wastewater and culture solution for wastewater treatment and other mechanical operations (aeration amount, stirring speed, etc.) related to activated sludge treatment. Have.
  • the wastewater treatment culture solution obtained by performing the wastewater treatment culture solution preparation step is at least one tank selected from the group consisting of the raw water tank 10, the flow rate adjusting tank 20, and the biological treatment tank 30 by the pump 81.
  • the pump 81 serves as a supply means for adding the wastewater treatment culture solution to the wastewater from the culture tank 50.
  • the raw water tank 10 the flow rate adjusting tank 20, the biological treatment tank 30, the solid-liquid separation tank 40, the amount of dissolved oxygen such as wastewater in the culture tank 50, the oxidation-reduction potential, the hydrogen ion concentration, the sludge concentration, and organic matter It is preferable that a measuring instrument for monitoring the load amount and the like is provided.
  • the wastewater treated by the wastewater treatment apparatus 1 is not particularly limited as long as it contains nitrogen and organic substances.
  • domestic wastewater, grain starch manufacturing industry, dairy product manufacturing industry, meat center, sugar manufacturing industry, livestock food products Wastewater from manufacturing industry, livestock farming, meat product manufacturing industry, meat ham / sausage manufacturing industry, fish paste product manufacturing industry, fishery food manufacturing industry, organic chemical industry manufacturing industry, inorganic chemical industry manufacturing industry, etc. can be mentioned.
  • activated sludge containing microorganisms is retained or put into the tank, and the microorganisms in the activated sludge decompose and remove pollutants such as organic substances in the wastewater, and can perform activated sludge treatment.
  • a treatment tank there is no particular limitation.
  • it may be an aerobic tank using aerobic microorganisms such as ammonia-oxidizing bacteria and nitrite-oxidizing bacteria, and an intermittent air-exhaust tank using aerobic microorganisms such as nitrite-oxidizing bacteria and anaerobic microorganisms such as denitrifying bacteria. And so on.
  • FIG. 2 is a schematic view schematically showing an example of the wastewater treatment apparatus of the present invention using the MBR membrane.
  • the wastewater treatment apparatus 2 shown in FIG. 2 has a configuration in which the wastewater treatment apparatus 1 has an MBR (Membrane Bio-Reactor) membrane instead of the solid-liquid separation tank 40.
  • MBR Membrane Bio-Reactor
  • the wastewater treatment device 2 shown in FIG. 2 includes a raw water tank 10, a flow rate adjusting tank 20 in which wastewater is supplied from the raw water tank 10, and a place where wastewater is supplied from the flow rate adjusting tank 20 and the wastewater is treated with active sludge.
  • a control device 60 for determining and controlling a supply amount is provided.
  • the culture tank 50, the raw water tank 10, the flow rate adjusting tank 20, and the biological treatment tank 30 are connected by a pipe 75, and the pipe 75 is connected to the culture tank 50 to the raw water tank 10, the flow rate adjusting tank 20, and the biological treatment tank.
  • a pump 81 for supplying the culture solution for wastewater treatment is arranged in No. 30.
  • a valve 92 is arranged downstream of the pump 81 of the pipe 75.
  • the functions of the raw water tank 10, the flow rate adjusting tank 20 and the culture tank 50 in the wastewater treatment device 2 are the same as the functions of the raw water tank 10, the flow rate adjusting tank 20 and the culture tank 50 in the wastewater treatment device 1.
  • the biological treatment tank 30 includes an aeration device 31 that supplies a gas for activating microorganisms that decompose organic substances, an MBR film 33 that solid-liquid separates wastewater after activated sludge treatment, and a solid-liquid separation from the MBR film 33. It is provided with a pump 84 for discharging the treated water, a treated water discharge port 34 which is a discharge port, a pump 82 for discharging excess activated sludge, and a surplus sludge discharge port 32 which is a discharge port thereof. A valve 93 is arranged downstream of the pump 84.
  • activated sludge containing microorganisms is retained or put into the tank, and the microorganisms in the activated sludge decompose and remove pollutants such as organic substances in the wastewater, and can perform activated sludge treatment.
  • a treatment tank there is no particular limitation.
  • it may be an aerobic tank using aerobic microorganisms such as ammonia-oxidizing bacteria and nitrite-oxidizing bacteria, and an intermittent air-exhaust tank using aerobic microorganisms such as nitrite-oxidizing bacteria and anaerobic microorganisms such as denitrifying bacteria. And so on.
  • the MBR membrane 33 is not particularly limited, but for example, PVDF flat membrane (manufactured by Toray Co., Ltd.), CPE flat membrane (manufactured by Kubota Co., Ltd.), PTFE hollow fiber membrane (manufactured by Sumitomo Electric Co., Ltd.), ceramic flat membrane.
  • Membranes manufactured by Meidensha Co., Ltd.
  • PVDF hollow fiber membranes manufactured by Mitsubishi Chemical Co., Ltd.
  • PE hollow fiber membranes manufactured by Mitsubishi Chemical Co., Ltd.
  • the control device 60 is used for wastewater treatment, such as dissolved oxygen amount, oxidation-reduction potential, hydrogen ion concentration, sludge concentration, organic matter load amount, etc. of wastewater in the raw water tank 10, the flow rate adjusting tank 20, the biological treatment tank 30, and the culture tank 50. Based on the amount of protein (A) in the culture solution, the function to determine and control the supply amount of wastewater and culture solution for wastewater treatment and other mechanical operations (aeration amount, stirring speed, etc.) related to activated sludge treatment. Have.
  • the raw water tank 10 the flow rate adjusting tank 20, the biological treatment tank 30, the solid-liquid separation tank 40, the amount of dissolved oxygen such as wastewater in the culture tank 50, the oxidation-reduction potential, the hydrogen ion concentration, the sludge concentration, and organic matter It is preferable that a measuring instrument for monitoring the load amount and the like is provided.
  • the wastewater treated by the wastewater treatment device 2 is the same as the wastewater treated by the wastewater treatment device 1.
  • the wastewater treatment device 1 and the wastewater treatment device 2 may further have a measuring means for measuring the value of the enzyme activity of the protein (A) in the wastewater treatment culture solution in which the protein (A) is an enzyme. ..
  • the control device 60 determines the amount of the wastewater treatment culture solution added by the pump 81 based on the measured enzyme activity value. Further, it is preferable that the control device 60 has a function of controlling the addition amount of the wastewater treatment culture solution added by the pump 81 based on the determined addition amount. That is, the control device 60 determines the addition amount of the culture solution for wastewater treatment to be added based on the measured enzyme activity value, and the wastewater to be added by the supply means based on the determined addition amount. It is preferable to have a function as a control means for controlling the amount of the culture solution added for treatment.
  • a culture solution for wastewater treatment containing a high concentration of protein (A) can be added to wastewater. Therefore, by using the wastewater treatment apparatus of the present invention, the wastewater treatment efficiency can be improved. In addition, by increasing the wastewater treatment efficiency, the load on organic matter in the biological treatment tank is reduced, and the formation of bulking is easily suppressed. Further, since the power of the aeration device can be reduced by increasing the wastewater treatment efficiency, the power cost for driving the aeration device can be suppressed.
  • the wastewater treatment method of the present invention includes a step of simultaneously presenting a surfactant (B) and a microorganism that secretes and produces a protein (A) to secrete the protein (A) into a culture solution for wastewater treatment.
  • a surfactant (B) and a microorganism that secretes and produces a protein (A) to secrete the protein (A) into a culture solution for wastewater treatment.
  • the microorganism can produce the protein (A) and secrete it into the culture medium for wastewater treatment.
  • the wastewater treatment method of the present invention can be used regardless of the type of protein (A) secreted and produced as long as the microorganism has the ability to secrete and produce protein (A).
  • Production Example 2 ⁇ Production of surfactant (B1-2)>
  • 101 parts of Sanniks PP-3000 [manufactured by Sanyo Chemical Industries, Ltd .; polyoxypropylene glycol (number average molecular weight: 3200)] was used in place of 450 parts of Sanniks PP-2000, and ethylene oxide was used.
  • the same operation was carried out except that the press-fitting amount was changed from 50 parts to 399 parts to obtain a surfactant (B1-2).
  • the number average molecular weight Mn of the surfactants (B1-1) and (B1-2) used in Examples and Comparative Examples was measured by the following method.
  • the number average molecular weight was measured under the following conditions using GPC (Gel Permeation Chromatography) with respect to the soluble content in tetrahydrofuran (hereinafter abbreviated as THF).
  • Measuring device "HLC-8120” manufactured by Tosoh Corporation Columns: “TSKgel GMHXL” manufactured by Tosoh Corporation (2) and “TSKgel Multipore HXL-M” manufactured by Tosoh Corporation (1) Sample solution: 0.25% by mass THF solution Injection amount of sample solution into the column: 100 ⁇ L Flow velocity: 1 mL / min Measurement temperature: 40 ° C Detector: Refractive index detector Reference material: Standard polystyrene (TSK standard POLYSTYRENE) manufactured by Tosoh Corporation 12 points (number average molecular weight: 500, 1050, 2800, 5970, 9100, 18100, 37900, 96400, 190000, 355000, 1090000 , 2890000).
  • Examples 1 to 16 and Comparative Examples 1 to 2 ⁇ Wastewater treatment test using yeast (Yarrowia lipolytica)> A wastewater treatment test was conducted using the wastewater treatment device 1 and the wastewater treatment device 2 (effective volume of the biological treatment tank: 10 L) shown in FIGS. 1 and 2. As the MBR film in FIG. 2, a PVDF flat film (manufactured by Toray Industries, Inc.) was used.
  • the water quality shown in Table 1 was used as the test water to be treated with activated sludge.
  • each wastewater treatment device The operating conditions of each wastewater treatment device are as shown in Tables 2 and 3. Air was aerated in each wastewater treatment device.
  • the types of microorganisms in Tables 2 and 3 are as follows.
  • F Bacillus sp.
  • G Escherichia coli
  • Saccharomyces cerevisiae I Pseudomonas fluoressences
  • Yeast (Yarrowia lipolytica) in YM medium [yeast extract [manufactured by Nihon Pharmaceutical Co., Ltd.] 0.3%, polypeptone [manufactured by Nihon Pharmaceutical Co., Ltd.] 0.5%, malt extract [manufactured by Nihon Pharmaceutical Co., Ltd.] 0. 3%, 1% glucose] 10 mL was inoculated with a loop loop and cultured at 30 ° C. for 15 hours at 200 rpm to prepare a preculture solution.
  • the prepared preculture solution was inoculated into 1 L of YM medium so that the final turbidity (OD) was 0.03 OD / mL, and stirring culture was started in the culture tank of the wastewater treatment device at 30 ° C. and 1000 rpm.
  • the surfactant (B) shown in Table 2 pure water in Comparative Examples 1 and 2 was added to the weight of the culture solution [total of medium, preculture solution and surfactant (B) to be added). Weight] was used as a reference, and the mixture was added so as to be the weight% shown in Table 2, and the stirring culture was continued.
  • the effluent treatment culture solution obtained 30 hours after the start of culturing was added to the effluent of the flow rate adjusting tank at a flow rate of 100 mL / day from the culturing tank via a pump and a valve.
  • the value of this flow rate was determined based on the enzymatic activity of lipase in the culture solution for wastewater treatment.
  • YM medium containing the surfactant (B) in the weight% shown in Table 2 was sequentially added to the culture tank at a flow rate of 100 mL / day, and stirring culture was continued.
  • the turbidity (OD) of the culture solution was calculated by the following measuring method and calculation formula.
  • ⁇ Measurement method of turbidity of culture solution> The turbidity was measured using a turbidity meter [UV-1700, manufactured by Shimadzu Corporation] using a culture solution containing the microorganisms recovered by sampling, using a quartz cell having an optical path length of 1 cm. The culture broth was centrifuged at 1500 rpm for 5 minutes at 4 ° C., and the supernatant was discarded. The precipitate was resuspended in the same amount of physiological saline as the sample solution, diluted with physiological saline so as to have an appropriate absorbance (0.1 to 0.8), and the absorbance at 600 nm was measured. The turbidity of the culture solution was calculated by the following mathematical formula (1). Turbidity of culture solution (OD) (absorbance of diluted culture solution at 600 nm) ⁇ dilution ratio of culture solution (1)
  • TOC removal rate 100 ⁇ [1- (TOC concentration of treated water / TOC concentration of test water)]
  • SVI Sv / S SVI: Volume (mL / g) occupied by 1 g of sludge when the activated sludge mixture in the biological treatment tank is placed in a 1 L graduated cylinder and allowed to stand for 30 minutes to settle the sludge.
  • Sv Sludge volume (mL / L) after the activated sludge mixture in the biological treatment tank was placed in a 1 L graduated cylinder and allowed to stand for 30 minutes to settle the sludge.
  • S Concentration of organic substances, etc.
  • Examples 17-18 ⁇ Wastewater treatment test using bacteria (Pseudomonas fluoressences)> The same procedure as in Example 1 was carried out except that "bacteria (Pseudomonas fluoressences)" were used instead of "yarrowia lipolytica", and the TOC removal rate and bulking formation evaluation according to Examples 17 and 18 were carried out. did. The results are shown in Table 2.
  • the method for measuring and calculating the enzyme activity of lipase is as follows.
  • Example 19 Comparative Example 3 ⁇ Wastewater treatment test using Bacillus subtilis>
  • a wastewater treatment test was conducted using the wastewater treatment device 2 (effective volume of the biological treatment tank: 10 L) shown in FIG.
  • a PVDF flat film manufactured by Toray Industries, Inc.
  • the test water to be treated with activated sludge the water quality shown in Table 1 was used.
  • the operating conditions of each wastewater treatment device are as shown in Table 3.
  • Bacillus subtilis medium [High Polypeptone [Fujifilm Wako Pure Chemical Industries, Ltd.] 1%, Yeast extract [Nippon Pharmaceutical Co., Ltd.] 0.2%, Magnesium sulfate / heptahydrate 0.1 %, pH 7] 10 mL was inoculated with a platinum loop and cultured at 30 ° C. for 15 hours at 200 rpm to prepare a preculture solution.
  • 1 L of medium [High Polypeptone [manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.] 1%, yeast extract [Nihon Pharmaceutical Co., Ltd.] so that the prepared preculture solution has a final turbidity (OD) of 0.03 OD / mL.
  • the effluent treatment culture solution obtained 30 hours after the start of culturing was added to the effluent of the flow rate adjusting tank at a flow rate of 100 mL / day from the culturing tank via a pump and a valve.
  • the value of this flow rate was determined based on the enzymatic activity of amylase in the culture solution for wastewater treatment.
  • the culture medium containing the surfactant (B) at a rate of 100 mL / day in the weight% shown in Table 3 [High Polypeptone [manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.] 1%, yeast extract [Nihon Pharmaceutical Co., Ltd. (Nippon Pharmaceutical Co., Ltd.) Co., Ltd.] 0.2%, magnesium sulfate / heptahydrate 0.1%, pH7] were sequentially added, and stirring culture was continued.
  • TOC removal rate 100 ⁇ [1- (TOC concentration of treated water / TOC concentration of test water)]
  • ⁇ Valking formation evaluation> The degree of bulking formation in the biological treatment tank 16 days after the start of culture was evaluated according to the following evaluation criteria. The results are shown in Table 3.
  • Example 20 ⁇ Wastewater treatment test using bacteria (Pseudomonas sp.)> The same operation as in Example 19 was carried out except that "bacteria (Pseudomonas sp.)" Was used instead of "Bacillus subtilis", and the TOC removal rate and bulking formation evaluation according to Example 20 were carried out. did. The results are shown in Table 3.
  • amylase activity in Examples 19 and 20 and Comparative Example 3 was analyzed using an ⁇ -amylase measurement kit (manufactured by Kikkoman Biochemifa).
  • amylase activity when the synthetic substrate N3-G5- ⁇ -CNP was used as a substrate, the amount of enzyme producing 1 ⁇ mol of 2-chloro-2-nitrophenol per minute at 30 ° C. was defined as 1 unit.
  • Example 21 and Comparative Example 4 ⁇ Wastewater treatment test using Bacillus subtilis>
  • a wastewater treatment test was conducted using the wastewater treatment device 2 (effective volume of the biological treatment tank: 10 L) shown in FIG.
  • a PVDF flat film manufactured by Toray Industries, Inc.
  • the test water to be treated with activated sludge the water quality shown in Table 1 was used.
  • the operating conditions of each wastewater treatment device are as shown in Table 3.
  • Bacillus subtilis medium [High Polypeptone [Fujifilm Wako Pure Chemical Industries, Ltd.] 1%, Yeast extract [Nippon Pharmaceutical Co., Ltd.] 0.2%, Magnesium sulfate / heptahydrate 0.1 %, pH 7] 10 mL was inoculated with a platinum loop and cultured at 30 ° C. for 15 hours at 200 rpm to prepare a preculture solution.
  • 1 L of medium [High Polypeptone [manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.] 1%, yeast extract [Nihon Pharmaceutical Co., Ltd.] so that the prepared preculture solution has a final turbidity (OD) of 0.03 OD / mL.
  • the value of this flow rate was determined based on the enzymatic activity of cellulase in the culture solution for wastewater treatment.
  • TOC removal rate 100 ⁇ [1- (TOC concentration of treated water / TOC concentration of test water)]
  • ⁇ Valking formation evaluation> The degree of bulking formation in the biological treatment tank 16 days after the start of culture was evaluated according to the following evaluation criteria. The results are shown in Table 3.
  • Example 22 ⁇ Wastewater treatment test using bacteria (Xanthomonas sp. EC102)> The procedure was the same as in Example 21 except that "Bacteria (Xanthomonas sp. EC102)" was used instead of “Bacillus subtilis", and the TOC removal rate and bulking formation evaluation according to Example 22 were evaluated. Carried out. The results are shown in Table 3.
  • Example 23 and Comparative Example 5 ⁇ Wastewater treatment test using Bacillus sp.> A wastewater treatment test was conducted using the wastewater treatment device 2 (effective volume of the biological treatment tank: 10 L) shown in FIG. As the MBR film in FIG. 2, a PVDF flat film (manufactured by Toray Industries, Inc.) was used. As the test water to be treated with activated sludge, the water quality shown in Table 1 was used. The operating conditions of each wastewater treatment device are as shown in Table 3. Bacillus sp.
  • the value of this flow rate was determined based on the enzymatic activity of the protease in the culture solution for wastewater treatment.
  • TOC removal rate 100 ⁇ [1- (TOC concentration of treated water / TOC concentration of test water)]
  • ⁇ Valking formation evaluation> The degree of bulking formation in the biological treatment tank 16 days after the start of culture was evaluated according to the following evaluation criteria. The results are shown in Table 3.
  • Example 24 ⁇ Wastewater treatment test using bacteria (Escherichia coli)> The same operation as in Example 23 was carried out except that "Bacteria (Escherichia coli)" was used instead of "Bacillus sp.”, And the TOC removal rate and bulking formation evaluation according to Example 24 were carried out. did. The results are shown in Table 3.
  • protease activity was evaluated from the fluorescence intensity increased by the degradation of the protease using the fluorescently labeled casein as a substrate.
  • Example 25 and Comparative Example 6 ⁇ Wastewater treatment test using yeast (Saccharomyces cerevisiae)> A wastewater treatment test was conducted using the wastewater treatment device 2 (effective volume of the biological treatment tank: 10 L) shown in FIG. As the MBR film in FIG. 2, a PVDF flat film (manufactured by Toray Industries, Inc.) was used. As the test water to be treated with activated sludge, the water quality shown in Table 1 was used. The operating conditions of each wastewater treatment device are as shown in Table 3.
  • Yeast (Saccharomyces cerevisiae) in YM medium [yeast extract [manufactured by Nihon Pharmaceutical Co., Ltd.] 0.3%, polypeptone [manufactured by Nihon Pharmaceutical Co., Ltd.] 0.5%, malt extract [manufactured by Nihon Pharmaceutical Co., Ltd.] 0. 3%, 1% glucose] 10 mL was inoculated with a loop loop and cultured at 30 ° C. for 15 hours at 200 rpm to prepare a preculture solution.
  • the prepared preculture solution was inoculated into 1 L of YM medium so that the final turbidity (OD) was 0.03 OD / mL, and stirring culture was started in the culture tank of the wastewater treatment device at 30 ° C. and 1000 rpm.
  • the surfactant (B) shown in Table 3 was added to the culture solution by weight [total weight of medium, preculture solution and added surfactant (B)].
  • the effluent treatment culture solution obtained 30 hours after the start of culturing was added to the effluent of the flow rate adjusting tank at a flow rate of 100 mL / day from the culturing tank via a pump and a valve.
  • the value of this flow rate was determined based on the enzymatic activity of aldehyde dehydrogenase in the culture solution for wastewater treatment.
  • YM medium containing the surfactant (B) in the weight% shown in Table 3 was sequentially added to the culture tank at a rate of 100 mL / day, and stirring culture was continued.
  • TOC removal rate 100 ⁇ [1- (TOC concentration of treated water / TOC concentration of test water)]
  • ⁇ Valking formation evaluation> The degree of bulking formation in the biological treatment tank 16 days after the start of culture was evaluated according to the following evaluation criteria. The results are shown in Table 3.
  • Example 26 ⁇ Wastewater treatment test using bacteria (Pseudomonas fluoressences)> The same procedure as in Example 25 was carried out except that "Gluconobacter oxidans” was used instead of "Yeast (Saccharomyces cerevisiae)", and the TOC removal rate and bulking formation evaluation according to Example 26 were carried out. .. The results are shown in Table 3.
  • Aldehyde dehydrogenase activity in Examples 25-26 and Comparative Example 6 was analyzed using Aldehyde Dehydrogenase Assay Assay Kit (manufactured by Cayman Chemical). The aldehyde dehydrogenase activity was measured using acetaldehyde as a substrate. When acetaldehyde was oxidized and decomposed into acetic acid, NAD + was reduced to NADH, and the fluorescence generated by the reaction of NADH generated at this time with a fluorescent probe was measured.
  • the wastewater treatment method and wastewater treatment apparatus of the present invention can be used in a wastewater treatment facility having a biological treatment tank for treating wastewater containing organic substances such as domestic wastewater and industrial wastewater.
  • a biological treatment tank for treating wastewater containing organic substances such as domestic wastewater and industrial wastewater.

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Abstract

L'invention a pour objet de fournir un procédé et un dispositif de traitement des eaux résiduaires qui tout en abaissant la charge d'une cuve de traitement biologique dans le cadre d'un traitement des eaux résiduaires, et en inhibant la formation de gonflement des boues, du fait d'une élévation de l'activité enzymatique à l'aide de microorganismes, permettent de diminuer le coût énergétique d'une cuve d'aération par amélioration du traitement des eaux résiduaires.　Le procédé de traitement des eaux résiduaires de l'invention inclut : une étape de fabrication de solution de culture pour traitement des eaux résiduaires au cours de laquelle les microorganismes qui produisent par sécrétion une protéine (A) contribuant à la décomposition de substances organiques contenues dans les eaux résiduaires, sont cultivés dans une solution de culture comprenant un tensio-actif qui contient un tensio-actif (B), dans une cuve de culture, ladite protéine (A) est ainsi produite par sécrétion par lesdits microorganismes, et une solution de culture pour traitement des eaux résiduaires contenant lesdits microorganismes, ladite protéine (A) et ledit tensio-actif (B), est ainsi fabriquée ; une étape d'addition de solution de culture au cours de laquelle ladite solution de culture pour traitement des eaux résiduaires est additionnée aux eaux résiduaires depuis ladite cuve de culture ; et une étape de traitement des eaux résiduaires au cours de laquelle un traitement par boues activées desdites eaux résiduaires, est effectué en présence de ladite solution de culture pour traitement des eaux résiduaires, dans la cuve de traitement biologique.
PCT/JP2020/048101 2019-12-26 2020-12-23 Procédé et dispositif de traitement des eaux résiduaires Ceased WO2021132304A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5420189A (en) * 1977-07-18 1979-02-15 Lion Corp Culturing of surfactant-decomposing bactria
JPS5743686A (en) * 1975-12-11 1982-03-11 Eastman Kodak Co Production of cholesterol esterase
JPH1147783A (ja) * 1997-07-30 1999-02-23 Nippon Soda Co Ltd 活性汚泥の活性化方法
JP2000186272A (ja) * 1998-10-16 2000-07-04 Sanrou Tachibana 有害化合物分解剤、汚染材料の処理方法、及び汚染材料の処理装置
JP2006247566A (ja) * 2005-03-11 2006-09-21 Kurita Water Ind Ltd 有機性廃水の生物処理方法
JP2019170202A (ja) * 2018-03-27 2019-10-10 三洋化成工業株式会社 有用物質の生産方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5743686A (en) * 1975-12-11 1982-03-11 Eastman Kodak Co Production of cholesterol esterase
JPS5420189A (en) * 1977-07-18 1979-02-15 Lion Corp Culturing of surfactant-decomposing bactria
JPH1147783A (ja) * 1997-07-30 1999-02-23 Nippon Soda Co Ltd 活性汚泥の活性化方法
JP2000186272A (ja) * 1998-10-16 2000-07-04 Sanrou Tachibana 有害化合物分解剤、汚染材料の処理方法、及び汚染材料の処理装置
JP2006247566A (ja) * 2005-03-11 2006-09-21 Kurita Water Ind Ltd 有機性廃水の生物処理方法
JP2019170202A (ja) * 2018-03-27 2019-10-10 三洋化成工業株式会社 有用物質の生産方法

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