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WO2018168447A1 - Agent de déshydratation de boue et procédé de déshydratation de boue - Google Patents

Agent de déshydratation de boue et procédé de déshydratation de boue Download PDF

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Publication number
WO2018168447A1
WO2018168447A1 PCT/JP2018/007354 JP2018007354W WO2018168447A1 WO 2018168447 A1 WO2018168447 A1 WO 2018168447A1 JP 2018007354 W JP2018007354 W JP 2018007354W WO 2018168447 A1 WO2018168447 A1 WO 2018168447A1
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WIPO (PCT)
Prior art keywords
polymer
mol
sludge
monomer
cationic
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Application number
PCT/JP2018/007354
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English (en)
Japanese (ja)
Inventor
詩歩子 関口
哲 竹林
佐藤　茂
渡辺　実
Original Assignee
栗田工業株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2017163494A external-priority patent/JP6737439B2/ja
Application filed by 栗田工業株式会社 filed Critical 栗田工業株式会社
Priority to KR1020197023848A priority Critical patent/KR20190124710A/ko
Priority to US16/489,127 priority patent/US20190375665A1/en
Priority to CN201880012569.6A priority patent/CN110337421A/zh
Priority to EP18766957.7A priority patent/EP3597609B1/fr
Publication of WO2018168447A1 publication Critical patent/WO2018168447A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F11/00—Treatment of sludge; Devices therefor
    • C02F11/12—Treatment of sludge; Devices therefor by de-watering, drying or thickening
    • C02F11/14—Treatment of sludge; Devices therefor by de-watering, drying or thickening with addition of chemical agents
    • C02F11/147—Treatment of sludge; Devices therefor by de-watering, drying or thickening with addition of chemical agents using organic substances
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D21/00—Separation of suspended solid particles from liquids by sedimentation
    • B01D21/01—Separation of suspended solid particles from liquids by sedimentation using flocculating agents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/5272—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using specific organic precipitants
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
    • C02F1/56—Macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • C08F236/14—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated containing elements other than carbon and hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2438/00—Living radical polymerisation
    • C08F2438/03—Use of a di- or tri-thiocarbonylthio compound, e.g. di- or tri-thioester, di- or tri-thiocarbamate, or a xanthate as chain transfer agent, e.g . Reversible Addition Fragmentation chain Transfer [RAFT] or Macromolecular Design via Interchange of Xanthates [MADIX]
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
    • C08F2800/10—Copolymer characterised by the proportions of the comonomers expressed as molar percentages
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
    • C08F2800/20—Copolymer characterised by the proportions of the comonomers expressed as weight or mass percentages
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2810/00—Chemical modification of a polymer
    • C08F2810/20—Chemical modification of a polymer leading to a crosslinking, either explicitly or inherently

Definitions

  • the present invention relates to a sludge dewatering agent suitable for the dewatering treatment of sludge, particularly sludge that is difficult to dewater, and a sludge dewatering method using the sludge dewatering agent.
  • cationic polymer flocculants are used for dewatering sludge mainly composed of excess sludge generated in food factories, chemical factories, human waste processing plants, and the like.
  • dewatering is progressing, and improvement of dewatering effects such as gravity filterability is strongly demanded.
  • Patent Document 1 describes that an ionic water-soluble polymer having a charge inclusion rate of 35 to 90%, which is obtained by granulating a water-in-oil emulsion liquid through a drying process, is used for sludge dewatering treatment.
  • Patent Documents 2 and 3 describe that an aggregating agent combining two types of cross-linkable water-soluble ionic polymers having a high charge inclusion rate and a low charge inclusion rate is applied as a sludge dehydrating agent. Yes.
  • Patent Document 4 discloses a sludge dehydrating agent based on a mixture of an amidine polymer, a crosslinked cationic polymer, and a non-crosslinked cationic polymer
  • Patent Document 5 discloses an amphoteric polymer flocculant after adding an inorganic flocculant. A sludge treatment method in which is added is disclosed.
  • the present inventors have repeatedly studied focusing on the relationship between the molecular spread of the crosslinkable polymer and the coagulation effect on sludge. As a result, it was found that a specific polymer exhibits an excellent dehydrating effect with a small addition amount.
  • an object of the present invention is to provide a sludge dewatering agent excellent in dewatering effect, in particular, floc-forming ability and gravity filterability, and a sludge dewatering method using the sludge dewatering agent even if the amount added is small. .
  • the present invention is based on the finding that a dehydrating agent containing a specific cross-linked polymer and having a specific intrinsic viscosity exhibits excellent floc-forming ability and gravity filterability with a small addition amount. .
  • the present invention provides the following [1] to [5].
  • [1] It contains one or more crosslinked polymers selected from the following polymers A, B and C, and the crosslinked polymer has an intrinsic viscosity at 30 ° C. in a 1.0 N sodium nitrate aqueous solution of 0.5 to 5 A sludge dewatering agent of 0.0 dL / g.
  • Polymer A Crosslink in which the monomer composition of the polymer structural unit is 1-100 mol% of a cationic monomer represented by the following general formula (1) and 0-99 mol% of a nonionic monomer polymer (In the formula (1), R 1 represents .R 2 and R 3 is a hydrogen atom or a methyl group are each independently an alkyl or alkoxy group having 1 to 3 carbon atoms, or .R 4 is a benzyl group , A hydrogen atom, an alkyl or alkoxy group having 1 to 3 carbon atoms, or a benzyl group, A is an oxygen atom or NH group, B is an alkylene group or alkoxylene group having 2 to 4 carbon atoms, X - is an anion).
  • Polymer B Crosslink in which the monomer composition of the polymer structural unit is 1 to 100 mol% of a cationic monomer represented by the following general formula (2) and 0 to 99 mol% of a nonionic monomer polymer (In Formula (2), R 5 and R 6 are each independently a hydrogen atom or a methyl group. X ⁇ is an anion.)
  • Polymer C Anionic monomer having a monomer composition of a polymer constituent unit of 1 to 99 mol% of the cationic monomer represented by the general formula (1) and the following general formula (3) Crosslinked polymer comprising 1 to 99 mol% and nonionic monomer 0 to 98 mol% (In the formula (3), R 7 is a hydrogen atom or CH 2 COOY.
  • R 8 is a hydrogen atom, a methyl group or COOY.
  • Q is SO 3 ⁇ , C 6 H 4 SO 3 ⁇ , CONHC (CH 3 ) 2 CH 2 SO 3 - or COO - is .
  • Y is a hydrogen atom or a cation).
  • a sludge dewatering method in which the sludge dewatering agent according to [1] or [2] is added to sludge to dewater the sludge.
  • the monomer composition of the polymer constituent unit is a cationic monomer represented by the general formula (1) and a cation represented by the general formula (2).
  • the present invention even if the addition amount is small, it is possible to provide a sludge dewatering agent that is excellent in the dewatering effect, in particular, the flock-forming ability and the gravity filterability.
  • an efficient sludge dewatering method using the sludge dewatering agent can be provided.
  • (meth) acryl means “acryl” and / or “methacryl (methacryl)”, and includes “(meth) acrylate” and “(meth) acrylo”. The same applies to the notation.
  • the sludge dehydrating agent of the present invention contains one or more cross-linked polymers selected from Polymer A, Polymer B and Polymer C.
  • the crosslinked polymer has an intrinsic viscosity of 0.5 to 5.0 dL / g at 30 ° C. in a 1.0 N sodium nitrate aqueous solution.
  • Such a sludge dehydrating agent exhibits a dehydrating effect such as excellent floc-forming ability and gravity filterability with an addition amount equal to or less than that of a conventional sludge dehydrating agent.
  • the reason why an excellent dehydrating effect can be obtained is considered to be due to the following mechanisms (1) and (2).
  • the crosslinked polymer having the intrinsic viscosity as described above is highly crosslinked and has a structure in which the molecule is rigid, and thus is not easily distorted. For this reason, the entire surface of the sludge particle is covered by strongly bonding to a plurality of crosslinked polymer molecules without covering the entire surface of the particle surface with one molecule of the crosslinked polymer. As a result, high-density bonds are formed between the sludge particles via the crosslinked polymer, and it is possible to form a hard floc that can withstand a strong share such as stirring.
  • the crosslinked polymer has a cationic charge trapped inside a highly crosslinked structure, and when a physical force such as stirring is applied, the trapped cationic charge is gradually released to the outside. Coarse flocs are easily formed by the sequential reaction between the cationic charge and the sludge particle surface.
  • the crosslinked polymer used for the sludge dehydrating agent is one or more selected from the following polymers A, B, and C. Among these, it may be used alone or in combination of two or more. Among these, it is preferable that the polymer A is included from the viewpoint of obtaining a more excellent dehydration effect.
  • the cross-linked polymer is more preferably polymer A.
  • the sludge dehydrating agent may contain, for example, one or more compounds selected from the group consisting of powder acids such as sulfamic acid and salts such as sodium sulfate.
  • the content of the crosslinked polymer in the sludge dehydrating agent is preferably 90% by mass or more, more preferably 95% by mass or more, and still more preferably 98% by mass or more. It is preferable that it is 100 mass%.
  • Polymer A has a monomer composition of a polymer structural unit represented by the following general formula (1): a cationic monomer (hereinafter simply referred to as “cationic monomer (1)”) 1 It is a crosslinked polymer composed of ⁇ 100 mol% and nonionic monomer 0 to 99 mol%.
  • the method for polymerizing these monomers to form a crosslinked polymer is not particularly limited, but a crosslinking agent is used as necessary.
  • the said crosslinking agent is not contained in the monomer composition of the polymer structural unit said by this invention.
  • R ⁇ 1 > is a hydrogen atom or a methyl group.
  • R 2 and R 3 are each independently an alkyl group or alkoxy group having 1 to 3 carbon atoms, or a benzyl group.
  • R 4 is a hydrogen atom, an alkyl or alkoxy group having 1 to 3 carbon atoms, or a benzyl group.
  • A is an oxygen atom or NH group, and B is an alkylene group or alkoxylene group having 2 to 4 carbon atoms.
  • X ⁇ represents an anion, and preferably chlorine, bromine, iodine, 1 ⁇ 2 ⁇ SO 4 — or CH 3 SO 4 — .
  • Examples of the cationic monomer (1) include (meth) acryloyloxyalkyl groups such as 2-((meth) acryloyloxy) ethyltrimethylammonium chloride and 2-((meth) acryloyloxy) ethyldimethylbenzylammonium chloride. Quaternary ammonium salts; (meth) acryloyloxyalkyl tertiary amine salts such as 2-((meth) acryloyloxy) ethyldimethylamine sulfate or hydrochloride, 3-((meth) acryloyloxy) propyldimethylamine hydrochloride, etc.
  • (meth) acryloylaminoalkyl quaternary ammonium salts such as 3-((meth) acryloylamino) propyltrimethylammonium chloride and 3-((meth) acryloylamino) propyltrimethylammonium methyl sulfate It is. Among these, it may be used alone or in combination of two or more. Of these, (meth) acryloyloxyalkyl quaternary ammonium salts are preferable, and 2- (acryloyloxy) ethyltrimethylammonium chloride is particularly preferable because it is excellent in polymerizability and easily obtains a crosslinked polymer having a strong structure. .
  • the cationic monomer (1) is contained in an amount of 1 to 100 mol% as a polymer structural unit. That is, the polymer A may be all of the constituent monomer may be the cationic monomer (1), or the cationic monomer (1) may be non-ionic with 1 mol% or more and less than 100 mol%. It may be a copolymer composed of 99 mol% or less of a functional monomer. However, since the polymer in which the cationic monomer (1) is 100 mol% has high hygroscopicity, the polymer A is preferably a copolymer from the viewpoint of the dewatering effect and handling properties of the sludge dehydrating agent.
  • the proportion of the cationic monomer (1) in the polymer constituent unit of the copolymer is preferably 30 to 95 mol%, more preferably 50 to 90 mol%, and still more preferably 55 to 85 mol%. %.
  • nonionic monomer examples include amides such as (meth) acrylamide and N, N-dimethyl (meth) acrylamide; vinyl cyanide compounds such as (meth) acrylonitrile; methyl (meth) acrylate, (Meth) acrylic acid alkyl esters such as ethyl (meth) acrylate; vinyl esters such as vinyl acetate; aromatic vinyl compounds such as styrene, ⁇ -methylstyrene, and p-methylstyrene.
  • These nonionic monomers may be used individually by 1 type, or may use 2 or more types together.
  • acrylamide is preferable because it is excellent in water solubility, can easily adjust the monomer composition ratio in the polymer, and can easily obtain a crosslinked polymer having a strong structure.
  • the monomer composition of the polymer structural unit is a cationic monomer represented by the following general formula (2) (hereinafter simply referred to as “cationic monomer (2)”) 1 It is a crosslinked polymer composed of ⁇ 100 mol% and nonionic monomer 0 to 99 mol%.
  • the method for polymerizing these monomers to form a crosslinked polymer is not particularly limited, but a crosslinking agent is used as necessary.
  • R 5 and R 6 are each independently a hydrogen atom or a methyl group.
  • X ⁇ is an anion, which is the same as in the general formula (1).
  • Examples of the cationic monomer (2) include diallyldimethylammonium chloride and dimethallyldimethylammonium chloride. Among these, it may be used alone or in combination of two or more.
  • the cationic monomer (2) is contained in an amount of 1 to 100 mol% as a polymer structural unit. That is, the polymer B may be all of the constituent monomer may be the cationic monomer (2), or alternatively, the cationic monomer may be 1 mol% or more and less than 100 mol%. It may be a copolymer composed of 99 mol% or less of a monomer. From the viewpoint of the dewatering effect of the sludge dewatering agent, the polymer B is preferably a copolymer.
  • the proportion of the cationic monomer (2) in the polymer constituent unit of the copolymer is preferably 30 to 95 mol%, more preferably 50 to 90 mol%, and still more preferably 55 to 85 mol%. %.
  • the nonionic monomer is the same as that for the polymer A described above.
  • Polymer C has a polymer composition unit monomer composition of 1 to 99 mol% of the cationic monomer (1) and an anionic monomer represented by the following general formula (3) (hereinafter referred to as “anion”). This is a cross-linked polymer composed of 1 to 99 mol% and nonionic monomer 0 to 98 mol%.
  • the method of copolymerizing these monomers to form a crosslinked polymer is not particularly limited, but a crosslinking agent is used as necessary.
  • R 7 is a hydrogen atom or CH 2 COOY.
  • R 8 is a hydrogen atom, a methyl group or COOY.
  • Q is SO 3 ⁇ , C 6 H 4 SO 3 ⁇ , CONHC (CH 3 ) 2 CH 2 SO 3 — or COO ⁇ .
  • Y is a hydrogen atom or a cation. Examples of the cation include alkali metal ions.
  • anionic monomer (3) examples include vinyl sulfonic acid, vinyl benzene sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, (meth) acrylic acid, itaconic acid, maleic acid, and alkali metals thereof. Salt. Among these, it may be used alone or in combination of two or more. Of these, acrylic acid is preferred.
  • the polymer C may be a copolymer of the cationic monomer (1) and the anionic monomer (3), or in addition to these monomers, nonionic monomers may also be used. It may be a copolymer as a polymer structural unit.
  • the proportion of the cationic monomer (1) in the polymer constituent units of these copolymers is preferably 30 to 98 mol%, more preferably 50 to 97 mol%, and still more preferably 55 to 95 mol%.
  • the proportion of the anionic monomer (3) is preferably 2 to 70 mol%, more preferably 3 to 50 mol%, still more preferably 5 to 45 mol%.
  • the polymer C is a copolymer of the cationic monomer (1) and the anionic monomer (3), among the polymer constituent units of the copolymer, the cationic monomer (1)
  • the ratio is preferably 30 to 98 mol%, more preferably 50 to 97 mol%, still more preferably 55 to 95 mol%.
  • the polymer C is a copolymer of a cationic monomer (1), an anionic monomer (3), and a nonionic monomer
  • the ratio of the nonionic monomer is 1 to 65. It is preferably mol%, more preferably 5 to 50 mol%, still more preferably 10 to 35 mol%.
  • Particularly preferred ratio ranges of the cationic monomer (1), the anionic monomer (3) and the nonionic monomer are 55 to 80 mol%, 5 to 15 mol%, and 10 to 30 respectively. Mol%.
  • the nonionic monomer is the same as that for the polymer A described above.
  • the crosslinked polymer constituting the sludge dehydrating agent of the present invention has an intrinsic viscosity of 0.5 to 5.0 dL / g at 30 ° C. in a 1.0 N sodium nitrate aqueous solution. Intrinsic viscosity is also an index of molecular weight, and the higher the molecular weight of the polymer, the higher the intrinsic viscosity. However, since the intrinsic viscosity is affected by the structure of the monomer that is a polymer constituent unit, polymerization conditions, and the like, it does not always correspond to the magnitude of the molecular weight. In the present invention, among the crosslinked polymers, those having a specific intrinsic viscosity are used.
  • the intrinsic viscosity of the crosslinked polymer is preferably 0.8 to 4.9 dL / g, more preferably 1.0 to 4.5 dL / g, and still more preferably 1.2 to 4.5 dL / g.
  • the intrinsic viscosity is represented by [ ⁇ ] and is a value calculated using the following Huggins equation.
  • Huggins formula: ⁇ SP / C [ ⁇ ] + k ′ [ ⁇ ] 2 C
  • k ′ Huggins constant
  • C polymer solution concentration
  • ⁇ rel relative viscosity.
  • the cross-linked polymer can be produced by mixing and polymerizing a monomer that becomes a polymer constituent unit, a polymerization initiator, and a cross-linking agent as necessary.
  • polymerization initiator examples include persulfates such as ammonium persulfate and potassium persulfate; organic oxides such as benzoyl peroxide; azobisisobutyronitrile, azobiscyanovaleric acid, 2,2′-azobis ( And azo compounds such as 2-amidinopropane) dihydrochloride and 2,2′-azobis (2,4-dimethylvaleronitrile).
  • persulfates such as ammonium persulfate and potassium persulfate
  • organic oxides such as benzoyl peroxide
  • azobisisobutyronitrile azobiscyanovaleric acid
  • 2,2′-azobis ( And azo compounds such as 2-amidinopropane) dihydrochloride and 2,2′-azobis (2,4-dimethylvaleronitrile).
  • the amount of the polymerization initiator used is usually about 0.001 to 0.1 mol% with respect to the total monomer amount.
  • crosslinking agent examples include N, N′-methylenebis (meth) acrylamide, triallylamine, ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, and the like. Can be mentioned.
  • the addition amount of the crosslinking agent is adjusted so that the intrinsic viscosity of the crosslinked polymer is within the above range. Usually, it is preferably 50 to 500 ppm, more preferably 80 to 300 ppm, still more preferably 100 to 200 ppm based on the total monomer mass excluding the crosslinking agent.
  • the aspect of the polymerization method is not particularly limited, and examples thereof include an aqueous solution polymerization method, an emulsion polymerization method, and a suspension polymerization method.
  • a production method obtained as an emulsion liquid is preferable, and a water-in-oil emulsion (W / O emulsion) is obtained by emulsion polymerization. It is more preferable to obtain a crosslinked polymer as a liquid.
  • a mixed aqueous solution containing a monomer and water as a polymer constituent unit of a cross-linked polymer and a cross-linking agent as necessary is added to an oil layer mixture containing a surfactant and an oily solvent. It can be carried out by stirring and mixing to emulsify and adding a polymerization initiator thereto. By such a method, a crosslinked polymer is obtained as a W / O emulsion liquid.
  • the oily solvent for example, mineral oil such as kerosene and light oil and their refined products such as normal paraffin, isoparaffin, naphthenic oil, etc. can be used, and synthetic oils and vegetable oils having properties equivalent to these oils can be used.
  • animal oils or mixtures thereof can also be used.
  • the surfactant include sorbitan fatty acid esters such as sorbitan monooleate and sorbitan monostearate; and nonionic surfactants such as polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether and pentaoxyethylene oleyl ether. Preferably used.
  • the crosslinked polymer obtained as such an emulsion liquid may be granulated or powdered by spray drying using a spray dryer or the like to obtain a dried granulated body or powder. If it is set as such a form, the handleability of a sludge dehydrating agent can be improved.
  • the sludge dewatering method of the present invention is a method in which the sludge is dehydrated by adding the sludge dehydrating agent to sludge such as excess sludge and mixed sludge from food factories, chemical factories, human waste treatment plants, and the like. Since the sludge dewatering agent of the present invention can exhibit an excellent dewatering effect even in a small amount, the amount added to the sludge can be suppressed, and the operability of the dewatering treatment can be improved and the cost can be reduced.
  • the amount of the sludge dehydrating agent added is preferably 20 to 1600 mg / L, more preferably 50 to 1200 mg / L. More preferably, it is 60 to 800 mg / L.
  • the method for adding the sludge dehydrating agent to the sludge is not particularly limited, and a known method for adding the sludge dehydrating agent can be applied.
  • the sludge dehydrating agent is added to the sludge as an aqueous solution or aqueous dispersion having a cross-linked polymer concentration of 0.01 to 0.5% by mass, preferably 0.03 to 0.3% by mass. In some cases, it may be added in a solid form such as powder.
  • the sludge dewatering agent and a polymer other than the crosslinked polymer may be used in combination.
  • the other polymer used in combination include a polymer having a cationic functional group or an anionic polymer.
  • the polymer having a cationic functional group includes not only a cationic polymer but also an amphoteric polymer.
  • the other polymer that can be used in combination may be a crosslinked type or a non-crosslinked type such as a straight chain, but from the viewpoint of sufficiently exerting the dewatering effect of the sludge dewatering agent, Those are preferred.
  • These other polymers are also preferably added to the sludge as an aqueous solution or aqueous dispersion having a polymer concentration of 0.01 to 0.5% by mass, like the cross-linked polymer of the sludge dehydrating agent, more preferably 0.03 to 0.3% by mass. In some cases, it may be added in the form of a solid such as a powder.
  • the monomer composition of the polymer structural unit is one or more cationic monomers selected from the cationic monomers (1) and (2) ( Hereinafter, it is expressed as “cationic monomer (1) / (2)”.) 1 to 100 mol%, nonionic monomer 0 to 99 mol%, and anionic monomer (3) A polymer composed of 0 to 50 mol% can be used.
  • the polymer may be a linear polymer, or may be a crosslinked polymer having an intrinsic viscosity outside the range of the intrinsic viscosity of the crosslinked polymer described above.
  • all of the constituent monomers may be cationic monomers (1) and (2).
  • the copolymer may be composed of 1 mol% or more and less than 100 mol%, nonionic monomer 0 to 99 mol%, and anionic monomer (3) 0 to 50 mol%.
  • cationic monomers (1) and (2) in the polymer having the cationic functional group include 2-((meth) acryloyloxy, similar to those mentioned for the polymer A or the polymer B. ) (Meth) acryloyloxyalkyl quaternary ammonium salts such as ethyltrimethylammonium chloride, 2-((meth) acryloyloxy) ethyldimethylbenzylammonium chloride; 2-((meth) acryloyloxy) ethyldimethylamine sulfate or hydrochloric acid Salts, (meth) acryloyloxyalkyl tertiary amine salts such as 3-((meth) acryloyloxy) propyldimethylamine hydrochloride; 3-((meth) acryloylamino) propyltrimethylammonium chloride, 3-((meth) Acryloylamino) Pills trimethylammonium (meth) acryl
  • (meth) acryloyloxyalkyl quaternary ammonium salts or (meth) acryloyloxyalkyl tertiary amine salts are preferred.
  • nonionic monomer in the polymer having a cationic functional group examples include, for example, (meth) acrylamide, N, N-dimethyl (meth) acrylamide and the like, as described for the polymer A.
  • it may be used alone or in combination of two or more. Of these, acrylamide is preferred.
  • anionic monomer (3) in the polymer having a cationic functional group examples include, for example, vinyl sulfonic acid, vinyl benzene sulfonic acid, 2-acrylamido-2, as described for the polymer C. -Methylpropanesulfonic acid, (meth) acrylic acid, itaconic acid, maleic acid, and alkali metal salts thereof. Among these, it may be used alone or in combination of two or more. Of these, acrylic acid is preferred.
  • the polymer having a cationic functional group may be mixed with the sludge dewatering agent and added as a single solution, or may be added separately from the sludge dewatering agent simultaneously or sequentially. Good.
  • the mass ratio of the sludge dehydrating agent to be used in combination with the polymer having a cationic functional group is preferably 20:80 to 80:20, more preferably 25:75 to 75:25, and still more preferably 30:70. ⁇ 70: 30.
  • anionic polymer examples include sodium polyacrylate, polyacrylamide partial hydrolyzate, a copolymer of sodium acrylate and acrylamide, partially sulfomethylated polyacrylamide, acrylamide and (2-acrylamide) -2-methylpropanesulfone. And a terpolymer of acrylamide, sodium acrylate, and (2-acrylamide) -2-methylpropanesulfonate.
  • a polyacrylamide partial hydrolyzate or a copolymer of sodium acrylate and acrylamide is preferable.
  • the anionic polymer When used in combination with the sludge dewatering agent, it is preferably added after the sludge dewatering agent is added to the sludge.
  • the mass ratio of the sludge dehydrating agent and the anionic polymer used in combination is preferably 50:50 to 95: 5, more preferably 60:40 to 90:10, and still more preferably 65:35 to 80:20. It is.
  • a mixed aqueous solution of 388 g of 80% by mass aqueous solution of 2- (acryloyloxy) ethyltrimethylammonium chloride (DAA), 28 g of acrylamide (AAM), 0.04 g of N, N′-methylenebisacrylamide as a crosslinking agent, and 222 g of pure water was added to the oil layer mixture and emulsified by stirring with a homogenizer. This was adjusted to 50 ° C. with stirring, and nitrogen gas was blown into the liquid for 30 minutes.
  • DAA 2- (acryloyloxy) ethyltrimethylammonium chloride
  • AAM acrylamide
  • N, N′-methylenebisacrylamide as a crosslinking agent
  • Synthesis Example 2 Synthesis of Polymer (A2)
  • the amount of N, N′-methylenebisacrylamide added was 0.06 g, and spray drying with a spray dryer was not performed.
  • a crosslinked polymer (A2) was obtained as a W / O emulsion liquid.
  • Synthesis Example 3 Synthesis of Polymer (A3)
  • AAM 2- (acryloyloxy) ethyltrimethylammonium chloride
  • AAM acrylamide
  • N, N′-methylenebisacrylamide was changed to 0.05 g.
  • A3 crosslinked polymer
  • Synthesis Example 4 Synthesis of Polymer (A4)
  • the amount of N, N′-methylenebisacrylamide added was 0.035 g, and the rest was the same as Synthesis Example 1 except that the water content was 5% by mass or less.
  • a crosslinked polymer (A4) was obtained.
  • Synthesis Example 8 Synthesis of Polymer (Z1)
  • 0.03 g of N, N′-methylenebisacrylamide and 2,2′-azobis (2, The 4-mass toluene solution of 4-dimethylvaleronitrile) was changed to 1.5 g, and other than that was carried out in the same manner as in Synthesis Example 2 to obtain a crosslinked polymer (Z1) as a W / O emulsion liquid.
  • the W / O emulsion liquid was added to a large excess of acetone for precipitation purification, and this precipitate was vacuum dried. The powder was subjected to intrinsic viscosity measurement.
  • (3-1) For polymers (A1) to (A5), (B1), (C1), (Z1) to (Z4), (Z6) and (Z8), 50 mL of 2N sodium nitrate aqueous solution was added to 50 mL of the filtrate.
  • a 1N sodium nitrate aqueous solution having a polymer concentration of 0.1% by mass was obtained, and this was diluted with a 1N sodium nitrate aqueous solution to be in the range of 0.02 to 0.1% by mass.
  • Polymer sample solutions having 5 levels of concentration were prepared.
  • a 1N sodium nitrate aqueous solution (1N-NaNO 3 ) was used as a blank solution.
  • Z5 For the polymer (Z5), a polymer sample solution was prepared using the 0.2N or 0.1N sodium chloride aqueous solution in place of the 2N or 1N sodium nitrate aqueous solution in the above (3-1).
  • a 0.1N sodium chloride aqueous solution (0.1N-NaCl) was used as a blank solution.
  • a polymer sample solution was prepared using the 2N or 1N sodium chloride aqueous solution instead of the 2N or 1N sodium nitrate aqueous solution in the above (3-1).
  • a 1N sodium chloride aqueous solution (1N-NaCl) was used as a blank solution.
  • Five viscometers were vertically attached in a constant temperature water bath adjusted to a temperature of 30 ° C. (within ⁇ 0.02 ° C.).
  • Table 2 shows the properties of various sludges used in the evaluation test.
  • the abbreviation of each component in the property of sludge and the measuring method are as follows. Further, “%” in the unit notation of each component amount in Table 2 means mass%.
  • SS Suspended Solid: Suspended matter; 100 mL of sludge is centrifuged at 3000 rpm for 10 minutes to remove the supernatant, and the precipitate is poured into a weighed crucible while washing with water, and the mass after drying at 105 to 110 ° C. It is shown as a mass ratio to sludge.
  • VSS Volatile suspended solids: Loss of ignition of suspended solids; After the suspended matter is weighed, the crucible containing suspended matter is ignited at a temperature within the range of 600 ⁇ 25 ° C, weighed after standing to cool, before and after ignition The difference in mass was expressed as a mass ratio with respect to suspended matter.
  • TS Total solids
  • evaporation residue 100 mL of sludge was placed in a weighed crucible, and the mass after drying at 105 to 110 ° C. was shown as a mass ratio to the sludge.
  • VTS Volatile Total Solids: Loss on ignition; after weighing the evaporation residue, the crucible containing the evaporation residue is ignited at a temperature within a range of 600 ⁇ 25 ° C. The difference was expressed as a mass ratio with respect to the evaporation residue.
  • Fiber content 100 mL of sludge was filtered through a 100-mesh sieve, the residue on the sieve was poured into a crucible while washing with water, and the crucible after drying at 105 to 110 ° C. was weighed. Thereafter, the mixture was ignited in a temperature range of 600 ⁇ 25 ° C., allowed to cool and weighed, and the difference in mass before and after ignition was shown as a mass ratio with respect to the suspended matter.
  • Example 1 A 0.2 mass% aqueous solution of polymer (A1) and a 0.2 mass% aqueous solution of polymer (Z4) were mixed at a mass ratio of 50:50 to prepare a sludge dehydrating agent sample (polymer aqueous solution).
  • This sludge dewatering agent sample is added to 1200 mL of sludge 1 collected in a 300 mL beaker at a polymer addition amount of 120 mg / L (0.9 mass% / SS), and stirred at 180 rpm for 30 seconds to form a coagulated floc. It was.
  • Example 2 Examples 2 to 24 and Comparative Examples 1 to 24
  • Example 3 the type of sludge, the type of polymer used, and the amount added were changed as shown in Table 3 below. Otherwise, a sludge dehydrating agent sample was prepared and added to the sludge in the same manner as in Example 1. Thus, an agglomerated floc was formed.
  • Example 25 To 200 mL of sludge 5 collected in a 300 mL beaker, a 0.2 mass% aqueous solution of polymer (A1) was added at a polymer addition amount of 90 mg / L (0.4 mass% / SS), and stirred at 180 rpm for 30 seconds. A 0.1% by mass aqueous solution of polymer (Z9) (anionic polymer) was added at a polymer addition amount of 35 mg / L (0.15% by mass / SS), and further stirred at 180 rpm for 20 seconds to form an aggregated floc. I let you.
  • Example 25 In Example 25, the polymer (Z3) was used in place of the polymer (A1), and other than that, aggregated flocs were formed in the same manner as in Example 25.
  • the evaluation test items and the evaluation method for the sludge dewatering agent sample are as follows. These evaluation results are summarized in Tables 3 and 4 below.
  • ⁇ 20-second filtration rate> A Buchner funnel having an inner diameter of 80 mm and a hole diameter of about 1 mm was placed on a 200 mL measuring cylinder, and a polyvinyl chloride tube having a diameter of 50 mm was placed thereon. In this cylinder, the agglomerated sludge after measuring the floc diameter as described above was poured at once, and the filtration amount after 20 seconds from the injection was read from the scale of the graduated cylinder and measured. It can be said that the greater the amount of filtration, the better the gravity filterability and the better the dehydration effect.
  • ⁇ SS leak amount> After the measurement of the filtration amount for 20 seconds, the solid content of sludge that passed through the Buchner funnel 60 seconds after the injection was read as SS leak amount from the scale of the graduated cylinder and measured. It can be said that the smaller the SS leak amount, the better the floc aggregation performance of the formed floc and the better the dehydration effect.
  • ⁇ Moisture content of cake> After the above SS leak amount measurement, the aggregate remaining on the Buchner funnel was packed in a polyvinyl chloride column having a diameter of 30 mm and a height of 17.5 mm. The column was removed and squeezed at 0.1 MPa for 60 seconds to obtain a dehydrated cake.
  • the mass of the dehydrated cake and the mass after the dehydrated cake was dried at 105 ° C. were measured, and the moisture content of the cake was calculated by regarding the reduced amount as the water content of the dehydrated cake.
  • the moisture content of the cake is about 80 to 85% by mass, the dehydrated cake can be handled in the same manner as in the past, and a lower value is preferable from the viewpoint of drying treatment and the like.
  • the floc diameter is large, the filtration amount is large for 20 seconds, and the SS leak amount is small. Moreover, the moisture content of the cake could be reduced. That is, it was confirmed that the sludge dewatering agent of the present invention is excellent in the dewatering effect. Moreover, when the sludge dehydrating agent of the present invention and other polymers other than that were used in combination, the floc diameter was increased and a tendency to exhibit good cohesiveness was observed.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Water Supply & Treatment (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Hydrology & Water Resources (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Treatment Of Sludge (AREA)
  • Separation Of Suspended Particles By Flocculating Agents (AREA)

Abstract

L'invention concerne : un agent de déshydratation de boue ayant un excellent effet de déshydratation, en particulier une excellente aptitude à la floculation et une excellente propriété de filtration par gravité, même si une quantité ajoutée est faible ; et un procédé de déshydratation de boue utilisant ledit agent de déshydratation de boue. La présente invention concerne un agent de déshydratation de boue et un procédé de déshydratation de boue l'utilisant, l'agent de déshydratation de boue comprenant au moins un polymère réticulé choisi parmi un polymère A, un polymère B et un polymère C, qui contient un monomère représenté par une formule structurale spécifique, le polymère réticulé ayant une viscosité intrinsèque de 0,5 - 5,0 dL/g, telle que mesurée avec du nitrate de sodium 1,0 N.
PCT/JP2018/007354 2017-03-14 2018-02-27 Agent de déshydratation de boue et procédé de déshydratation de boue WO2018168447A1 (fr)

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KR1020197023848A KR20190124710A (ko) 2017-03-14 2018-02-27 오니 탈수제 및 오니 탈수 방법
US16/489,127 US20190375665A1 (en) 2017-03-14 2018-02-27 Sludge dehydrating agent and sludge dehydrating method
CN201880012569.6A CN110337421A (zh) 2017-03-14 2018-02-27 污泥脱水剂及污泥脱水方法
EP18766957.7A EP3597609B1 (fr) 2017-03-14 2018-02-27 Procédé de déshydratation de boue

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WO2021112219A1 (fr) * 2019-12-06 2021-06-10 栗田工業株式会社 Agent de déshydratation de boue et procédé de déshydratation de boue
KR20220002281A (ko) * 2019-04-24 2022-01-06 쿠리타 고교 가부시키가이샤 오니 탈수제 및 오니 탈수 방법
AT525429A4 (de) * 2022-04-14 2023-04-15 Kahr Gottfried Verfahren zum Trocknen von Klärschlamm

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AT525429B1 (de) * 2022-04-14 2023-04-15 Kahr Gottfried Verfahren zum Trocknen von Klärschlamm

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