WO2016158632A1 - Flocculant for treating waste water, and method for flocculation treatment of waste water - Google Patents

Flocculant for treating waste water, and method for flocculation treatment of waste water Download PDF

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WO2016158632A1
WO2016158632A1 PCT/JP2016/059291 JP2016059291W WO2016158632A1 WO 2016158632 A1 WO2016158632 A1 WO 2016158632A1 JP 2016059291 W JP2016059291 W JP 2016059291W WO 2016158632 A1 WO2016158632 A1 WO 2016158632A1
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flocculant
waste water
basicity
pac
amount
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PCT/JP2016/059291
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French (fr)
Japanese (ja)
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征国 李
麦林　裕弘
平尾　孝典
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栗田工業株式会社
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    • 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
    • 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

Definitions

  • the present invention relates to a wastewater treatment flocculant and a wastewater flocculant treatment method using the wastewater treatment flocculant.
  • the present invention provides a wastewater treatment flocculant capable of effectively aggregating colored wastewater to obtain high-quality treated water with sufficiently reduced chromaticity, and wastewater using the wastewater treatment flocculant.
  • the present invention relates to a coagulation treatment method.
  • inorganic flocculants such as polyaluminum chloride (PAC), sulfuric acid band, and ferric chloride are used for wastewater treatment.
  • PAC polyaluminum chloride
  • sulfuric acid band sulfuric acid band
  • ferric chloride ferric chloride
  • the inorganic flocculant has a positive charge due to the metal ions (Al, Fe) contained in the inorganic flocculant, and this charge generally reduces the surface charge of the suspended matter that is negatively charged. Neutralizes and reduces electrical repulsion, and the metal ions form an insoluble hydroxide salt in the wastewater to enclose suspended matter and form fine aggregates (primary flocs). Applying a nonionic or anionic polyacrylamide polymer flocculant to the formed primary flocs to form coarse flocs (secondary flocs) and precipitate separation is a common method for flocculation and solid-liquid separation of wastewater. It is processing.
  • Inorganic flocculants such as PAC and sulfuric acid band need to be added in large quantities to remove soluble COD, which is a causative substance, for wastewater with high chromaticity generated in food factories and chemical factories. .
  • the inorganic flocculant is acidic, adding a large amount to remove chromaticity lowers the pH of the agglomerated treated water and cannot satisfy the drainage standard value of the pH value as it is. It must be neutralized with an alkaline agent and discharged. The problem is that a large amount of an alkali agent is required for the neutralization, and that the addition of the alkali agent makes chromaticity removal insufficient.
  • the inorganic flocculant contains corrosive ions (Cl ⁇ , SO 4 2 ⁇ ), the corrosive ion concentration increases with an increase in the amount of the inorganic flocculant, and there is a problem that the drainage equipment is corroded.
  • the inorganic flocculant also has a problem of increasing the amount of sludge generated by the metal hydroxide derived from the inorganic flocculant.
  • Japanese Patent Application Laid-Open No. 2007-167721 discusses a method of using an inorganic flocculant and an organic coagulant in combination as a method for reducing the amount of inorganic flocculant added.
  • the combined use of PAC and a dimethylamine / epichlorohydrin copolymer ((—N + (CH 3 ) 2 ) 2 Cl ⁇ —CH 2 —CH (OH) —CH 2 —) n ) has been proposed.
  • Japanese Patent Application Laid-Open No. 2007-167721 is characterized in that a PAC having a basicity of 58% or more is used, and a sufficient effect cannot be obtained if the basicity of the PAC is less than 58%.
  • the coagulation treatment agent disclosed in Japanese Patent Application Laid-Open No. 2007-167721 is inferior in treatment effect and removes chromaticity, coagulation precipitation Insufficient performance.
  • the present invention effectively agglomerates wastewater such as colored wastewater having chromaticity derived from soluble COD discharged from food / beverage manufacturing factories, chemical factories, etc., and has high water quality with sufficiently reduced chromaticity. It is an object of the present invention to provide a coagulant for wastewater treatment and a method for coagulation treatment of wastewater from which the treated water can be obtained.
  • the present inventors have found that the above-described problems can be solved by using polyaluminum chloride (PAC) having a basicity of less than 50% and a dimethyldiallylammonium chloride (DADMAC) polymer in combination.
  • PAC polyaluminum chloride
  • DMDMAC dimethyldiallylammonium chloride
  • a flocculant for wastewater treatment comprising polyaluminum chloride having a basicity of less than 50% and a dimethyldiallylammonium chloride-based polymer.
  • the dimethyldiallylammonium chloride polymer is a homopolymer or copolymer of dimethyldiallylammonium chloride, having an intrinsic viscosity of 0.1 to 3 dL / g and a colloid equivalent of 4.0 meq. / G or more of a flocculant for wastewater treatment.
  • a wastewater treatment flocculant comprising the mixture of polyaluminum chloride having a basicity of less than 50% and a dimethyldiallylammonium chloride polymer in [1] or [2].
  • [6] A method for aggregating wastewater, wherein the wastewater treatment flocculant according to any one of [1] to [5] is added to the wastewater for agglomeration.
  • waste water in particular, waste water such as colored waste water having a chromaticity derived from soluble COD discharged from a food / beverage manufacturing factory, chemical factory, etc. is effectively agglomerated, and the chromaticity is sufficient. It is possible to obtain treated water with high water quality reduced to a very low level.
  • the present invention it is possible to reduce the amount of the inorganic flocculant added to the wastewater by the synergistic effect of the aggregating action by using together the polyaluminum chloride having a basicity of less than 50% and the dimethyldiallylammonium chloride-based polymer.
  • the corrosion of the drainage equipment can be suppressed, and the generation amount of the coagulated sludge can be reduced.
  • a low basicity polyaluminum chloride having a basicity of less than 50% is excellent in stability when mixed with a dimethyldiallylammonium chloride polymer and is advantageous in terms of formulation.
  • Waste wastewater There is no restriction
  • the present invention relates to colored wastewater such as dye wastewater, chemical factory wastewater, food / beverage manufacturing factory wastewater, biological wastewater for wastewater treatment, particularly soluble COD-derived chromaticity discharged from food / beverage manufacturing factory, chemical factory, etc. It is effective for the coagulation treatment of colored wastewater having According to the present invention, these colored wastewater can be agglomerated to obtain high-quality treated water with sufficiently reduced chromaticity.
  • These colored wastewaters have a chromaticity (chromaticity measured by absorbance at a wavelength of 420 nm as described in the Examples section below) of about 100 to 10,000.
  • such colored waste water can be agglomerated to obtain agglomerated water having a chromaticity of 100 or less.
  • PAC polyaluminum chloride
  • Basic PAC is represented by the general formula [Al 2 (OH) n Cl 6-n ] m (0 ⁇ n ⁇ 6, m ⁇ 10).
  • the basicity can be calculated as (n / 6) ⁇ 100 (%).
  • the basicity calculated by this calculation method is less than 50%.
  • PACs with a basicity of less than 50% have a weak floc-forming ability, but a high charge neutralization ability results in high reactivity with the chromaticity component.
  • Sufficient chromaticity in combination with dimethyldiallylammonium chloride polymers It is possible to obtain coagulated water having a high water quality reduced to a very low level.
  • PACs with a basicity of less than 50% have less hydroxide ions (OH ⁇ ) and water-soluble than JIS standard PACs with a basicity of 45-65% and so-called high basicity PACs with a basicity of 58% or more.
  • OH ⁇ hydroxide ions
  • JIS standard PACs with a basicity of 45-65% hydroxide ions
  • high basicity PACs with a basicity of 58% or more for the reason that the aluminum salt hardly precipitates, there is an advantage that the stability when mixed with the organic coagulant is high, and the aggregated coagulant is difficult to separate.
  • the basicity of the PAC is preferably 50% or less.
  • the dimethyldiallylammonium chloride (DADMAC) -based polymer used in the present invention may be a DADMAC homopolymer or a copolymer of DADMAC and other copolymerization components.
  • DADMAC polymer is a copolymer
  • other copolymerization components include amides such as acrylamide, methacrylamide, N, N-dimethylacrylamide and N, N-dimethylmethacrylamide, and cyanation such as acrylonitrile and methacrylonitrile.
  • the DADMAC copolymer preferably does not contain a hydrophobic group such as a benzyl group from the viewpoint of solubility with a low basicity PAC.
  • DADMAC DADMAC
  • a DADMAC homopolymer or a copolymer satisfying the colloidal equivalent described later is preferable, and a DADMAC homopolymer (polyDADMAC) is particularly preferable.
  • the DADMAC polymer used in the present invention preferably has an intrinsic viscosity of 0.1 to 3 dL / g, particularly 0.5 to 2 dL / g.
  • the intrinsic viscosity is less than the above lower limit, the cohesive force tends to decrease.
  • the intrinsic viscosity exceeds the above upper limit, neutralization of surface charge of the turbidity component is high in viscosity, inferior in reactivity and low in compatibility with low basicity PAC, so that the processing efficiency tends to be low. is there.
  • the intrinsic viscosity of the DADMAC polymer is a value measured at 30 ° C. using a 1.0 N sodium nitrate aqueous solution as a solvent.
  • the DADMAC polymer used in the present invention has a colloid equivalent of 4.0 meq. / G or more, especially 5.0 meq. / G or more is preferable.
  • Colloidal equivalent is 4.0 meq. If it is less than / g, the charge neutralization force becomes weak, and the amount required to obtain the desired aggregation effect increases.
  • the upper limit of the colloidal equivalent of the DADMAC polymer is 6.5 meq. / G.
  • the colloidal equivalent of the DADMAC polymer is measured by “colloidal titration method” (written by Keiichi Sente, Nankodo Co., Ltd. (published in November S44)).
  • the PAC having a basicity of less than 50% used in the present invention can usually be used as an aqueous solution having an Al 2 O 3 equivalent concentration of about 7 to 11% by weight.
  • the low basicity PAC and the DADMAC polymer may be added separately to the waste water, or may be added as a single agent in advance. In the case of a single agent, as described above, it is difficult to separate them and a flocculant having excellent stability can be obtained.
  • the amount of the active ingredient of the DADMAC-based polymer is 100 parts by weight of the low basicity PAC equivalent of Al 2 O 3 with respect to the aqueous solution of the low basicity PAC equivalent to the Al 2 O 3 equivalent concentration as described above. It is preferable to use the mixture so as to be 1 to 50 parts by weight. This mixing ratio is based on a suitable use ratio at the time of agglomeration treatment described later.
  • a low-basic PAC and a DADMAC polymer are added to wastewater such as colored wastewater for agglomeration treatment.
  • the low basicity PAC and the DADMAC-based polymer may be mixed in advance and added as a single agent formulation, or may be added separately. However, in the case of separate addition, after adding the low basicity PAC, DADMAC It is preferable to add a polymer or to add a low basicity PAC and a DADMAC polymer simultaneously.
  • the amount of the low basicity PAC added to the wastewater varies depending on the properties of the wastewater to be treated and the basicity of the low basicity PAC used, but is usually 20 to 500 mg / L in terms of Al 2 O 3 , especially 50 to 300 mg / L is preferable. If the addition amount of the low basicity PAC is less than this range, a sufficient flocculation treatment effect cannot be obtained, and adding more than this range is not preferable for the purpose of the present invention to reduce the amount of inorganic flocculant used.
  • the DADMAC polymer is preferably added so that the amount of the active ingredient is about 2 to 50 mg / L with respect to the waste water.
  • the DADMAC polymer is preferably added in an amount of 1 to 50 parts by weight based on 100 parts by weight of the low basicity PAC in terms of Al 2 O 3 addition.
  • treated water After the flocculation treatment, treated water can be obtained by solid-liquid separation by sedimentation separation, filtration or the like according to a conventional method.
  • PAC [PAC] PAC (60): Trade name “PAC300A” manufactured by Taki Chemical Co., Ltd. (Basicity: 60%, 10.5% by weight aqueous solution in terms of Al 2 O 3 concentration)
  • Each of the above PACs was used as an aqueous PAC solution having an Al 2 O 3 equivalent concentration of 10.5% by weight.
  • the PAC addition amount in the following experimental examples, examples, and comparative examples indicates the addition amount as this PAC aqueous solution.
  • PolyDADMAC homopolymer of dimethyldiallylammonium chloride (Intrinsic viscosity: 0.7 dL / g, colloidal equivalent: 5.9 meq./g)
  • DEAP Dimethylamine / epichlorohydrin copolymer (Intrinsic viscosity: 0.1 dL / g, colloidal equivalent: 6.8 meq./g)
  • the pH of the wastewater was measured by the glass electrode method. Turbidity was determined by measuring the absorbance at a wavelength of 660 nm using a “U-1800 spectrophotometer” manufactured by Hitachi, Ltd. The chromaticity was similarly determined by measuring the absorbance at a wavelength of 420 nm.
  • each PAC was added so as to have the addition amount shown in Table 2 (as a PAC aqueous solution with an Al 2 O 3 equivalent concentration of 10.5 wt%), and rapid stirring was performed at 150 rpm for 2 minutes. Thereafter, 5 mg / L of an anionic polyacrylamide polymer flocculant (“Cliff Rock PA-612” manufactured by Kurita Kogyo Co., Ltd.) was added and rapidly stirred at 150 rpm for 1 minute, followed by slow stirring at 50 rpm for 2 minutes. I went for a minute. Then, after leaving still for 3 minutes, the chromaticity of supernatant water (treated water) was measured. The results are shown in Table 2.
  • Example 1 Comparative Examples 1 to 4
  • the same colored wastewater as that used in the coagulation test in Experimental Example 1 was used.
  • 100 g of PAC shown in Table 3 (as a PAC aqueous solution with an Al 2 O 3 equivalent concentration of 10.5 wt%) and the organic shown in Table 3 were used.
  • a coagulant mixed with 0.5 g of a coagulant is added to 1200 mg / L, agglomerated by rapid stirring at 150 rpm for 2 minutes, and then allowed to stand for 3 minutes, and then supernatant water (treated water) The chromaticity of was measured. The results are shown in Table 3.
  • Example 1 in which PAC (20) and polyDADMAC are used in combination, treated water with low chromaticity can be obtained.
  • Comparative Example 1 corresponds to the flocculant disclosed in JP-A No. 2007-167721, but treated water with low chromaticity cannot be obtained.
  • Examples 2 to 6, Comparative Example 5 The same colored wastewater as that used in the coagulation test in Experimental Example 1 was used. To this colored wastewater, 100 g of PAC shown in Table 4 (as a PAC aqueous solution with an Al 2 O 3 equivalent concentration of 10.5 wt%) and the organic shown in Table 4 were used. The flocculant mixed in the amount shown in Table 4 into a single agent was added at 900 mg / L, rapidly stirred at 150 rpm for 2 minutes to agglomerate, then allowed to stand for 3 minutes, and then supernatant water (treated water) ) was measured. The results are shown in Table 4.
  • Comparative Example 5 corresponds to the flocculant described in JP-A No. 2007-167721, but treated water with low chromaticity cannot be obtained.
  • a good aggregation effect can be obtained by using a PAC having a basicity of less than 50%.
  • PAC (50) tends to be inferior in aggregation effect to PAC (60). This is thought to be due to the fact that equilibrium occurred and cohesion decreased.

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  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
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Abstract

It becomes possible to achieve an effective flocculation treatment of waste water such as colored waste water discharged from food/beverage production factories, chemical factories and the like and having chromaticity resulting from soluble COD to thereby produce high-quality treated water having satisfactorily reduced chromaticity. A flocculant for treating waste water, comprising poly(aluminum chloride) having a degree of basicity of less than 50% and a dimethyl diallyl ammonium chloride-type polymer. A method for the flocculation treatment of waste water, comprising adding the flocculant for treating waste water to waste water such as colored waste water. It is possible to reduce the amount of the flocculant to be added to the waste water, and it is also possible to reduce the amount of corrosive ions to prevent the corrosion of a water discharge facility, and it is also possible to reduce the amount of flocculated sludge produced. By using poly(aluminum chloride) having a degree of basicity of as low as less than 50%, the pH value of the flocculation-treated water can fall within a nearly neutral range and therefore the use of a neutralizing agent becomes unnecessary or the amount of a neutralizing agent to be added can be reduced.

Description

排水処理用凝集剤及び排水の凝集処理方法Flocculant for waste water treatment and waste water agglomeration method
　本発明は、排水処理用凝集剤と、この排水処理用凝集剤を用いた排水の凝集処理方法に関する。本発明は、着色排水を効果的に凝集処理して、色度が十分に低減された高水質の処理水を得ることができる排水処理用凝集剤と、この排水処理用凝集剤を用いた排水の凝集処理方法に関する。 The present invention relates to a wastewater treatment flocculant and a wastewater flocculant treatment method using the wastewater treatment flocculant. The present invention provides a wastewater treatment flocculant capable of effectively aggregating colored wastewater to obtain high-quality treated water with sufficiently reduced chromaticity, and wastewater using the wastewater treatment flocculant. The present invention relates to a coagulation treatment method.
　排水の処理には、一般的にポリ塩化アルミニウム（ＰＡＣ）、硫酸バンド、塩化第二鉄などの無機凝集剤が使用されている。 In general, inorganic flocculants such as polyaluminum chloride (PAC), sulfuric acid band, and ferric chloride are used for wastewater treatment.
　無機凝集剤は、無機凝集剤中に含まれる金属イオン（Ａｌ，Ｆｅ）に起因する正の荷電を持っており、この電荷によって、一般的に負に帯電している懸濁物質の表面電荷を中和し、電気的な反発を低減するとともに、その金属イオンが排水中で不溶性の水酸化物塩を形成して懸濁物質を包括し、微細な凝集物（一次フロック）を形成する。形成された一次フロックにノニオン性又はアニオン性ポリアクリルアミド系高分子凝集剤を適用し、粗大なフロック（二次フロック）を形成させて沈殿分離する方法が、一般的な排水の凝集、固液分離処理である。 The inorganic flocculant has a positive charge due to the metal ions (Al, Fe) contained in the inorganic flocculant, and this charge generally reduces the surface charge of the suspended matter that is negatively charged. Neutralizes and reduces electrical repulsion, and the metal ions form an insoluble hydroxide salt in the wastewater to enclose suspended matter and form fine aggregates (primary flocs). Applying a nonionic or anionic polyacrylamide polymer flocculant to the formed primary flocs to form coarse flocs (secondary flocs) and precipitate separation is a common method for flocculation and solid-liquid separation of wastewater. It is processing.
　ＰＡＣ、硫酸バンドなどの無機凝集剤は、食品工場や化学工場等において発生する色度が高い排水に対しては、その原因物質である溶解性ＣＯＤを除去するために大量に添加する必要がある。 Inorganic flocculants such as PAC and sulfuric acid band need to be added in large quantities to remove soluble COD, which is a causative substance, for wastewater with high chromaticity generated in food factories and chemical factories. .
　無機凝集剤は酸性であるため、色度を除去するために大量に添加すると、凝集処理水のｐＨが低下し、そのままではｐＨ値の排水基準値を満たすことができないことから、凝集処理水をアルカリ剤で中和して放流する必要がある。その中和にアルカリ剤を大量に必要とすること、このアルカリ剤の添加で色度除去が不十分となることが課題である。 Since the inorganic flocculant is acidic, adding a large amount to remove chromaticity lowers the pH of the agglomerated treated water and cannot satisfy the drainage standard value of the pH value as it is. It must be neutralized with an alkaline agent and discharged. The problem is that a large amount of an alkali agent is required for the neutralization, and that the addition of the alkali agent makes chromaticity removal insufficient.
　更に、無機凝集剤は腐食性イオン（Ｃｌ－、ＳＯ４ ２－）を含むため、その添加量の増加に伴い、腐食性イオン濃度も増加し、排水設備を腐食させる課題もある。無機凝集剤は、無機凝集剤由来の金属水酸化物により汚泥発生量を増大させる課題もある。 Furthermore, since the inorganic flocculant contains corrosive ions (Cl − , SO 4 2− ), the corrosive ion concentration increases with an increase in the amount of the inorganic flocculant, and there is a problem that the drainage equipment is corroded. The inorganic flocculant also has a problem of increasing the amount of sludge generated by the metal hydroxide derived from the inorganic flocculant.
　排水処理に際して無機凝集剤の必要添加量を低減することは、薬剤コスト、廃棄物処理コスト、その他の処理コストの削減につながるため、排水処理に必要な無機凝集剤の添加量の低減が望まれている。 Reducing the amount of inorganic flocculant added during wastewater treatment leads to reduction in chemical costs, waste disposal costs, and other treatment costs. Therefore, it is desirable to reduce the amount of inorganic flocculants required for wastewater treatment. ing.
　特開２００７－１６７７２１では、無機凝集剤添加量を低減する方法として、無機凝集剤と有機凝結剤とを併用する方法が検討されている。例えば、ＰＡＣとジメチルアミン・エピクロルヒドリン共重合体（（－Ｎ＋（ＣＨ３）２）２Ｃｌ－－ＣＨ２－ＣＨ（ＯＨ）－ＣＨ２－）ｎ）との併用が提案されている。特開２００７－１６７７２１では、ＰＡＣとして塩基度５８％以上のものを用いることを特徴とし、ＰＡＣの塩基度が５８％未満では十分な効果が得られないとされている。 Japanese Patent Application Laid-Open No. 2007-167721 discusses a method of using an inorganic flocculant and an organic coagulant in combination as a method for reducing the amount of inorganic flocculant added. For example, the combined use of PAC and a dimethylamine / epichlorohydrin copolymer ((—N + (CH 3 ) 2 ) 2 Cl − —CH 2 —CH (OH) —CH 2 —) n ) has been proposed. Japanese Patent Application Laid-Open No. 2007-167721 is characterized in that a PAC having a basicity of 58% or more is used, and a sufficient effect cannot be obtained if the basicity of the PAC is less than 58%.
　食品・飲料製造工場や化学工場等から排出される溶解性ＣＯＤ由来の色度を有する着色排水の処理においては、特開２００７－１６７７２１の凝集処理剤では処理効果が劣り、色度除去、凝集沈殿性能が不十分である。 In the treatment of colored wastewater having chromaticity derived from soluble COD discharged from food / beverage manufacturing factories, chemical factories, etc., the coagulation treatment agent disclosed in Japanese Patent Application Laid-Open No. 2007-167721 is inferior in treatment effect and removes chromaticity, coagulation precipitation Insufficient performance.
特開２００７－１６７７２１JP2007-167721
　本発明は、食品・飲料製造工場や化学工場等から排出される溶解性ＣＯＤ由来の色度を有する着色排水等の排水を効果的に凝集処理して、色度が十分に低減された高水質の処理水を得ることができる排水処理用凝集剤及び排水の凝集処理方法を提供することを課題とする。 The present invention effectively agglomerates wastewater such as colored wastewater having chromaticity derived from soluble COD discharged from food / beverage manufacturing factories, chemical factories, etc., and has high water quality with sufficiently reduced chromaticity. It is an object of the present invention to provide a coagulant for wastewater treatment and a method for coagulation treatment of wastewater from which the treated water can be obtained.
　本発明者らは、塩基度５０％未満のポリ塩化アルミニウム（ＰＡＣ）とジメチルジアリルアンモニウムクロライド（ＤＡＤＭＡＣ）系ポリマーとを併用することにより、上記の課題を解決することができることを見出した。
　本発明は以下を要旨とする。 The present inventors have found that the above-described problems can be solved by using polyaluminum chloride (PAC) having a basicity of less than 50% and a dimethyldiallylammonium chloride (DADMAC) polymer in combination.
The gist of the present invention is as follows.
［１］　塩基度５０％未満のポリ塩化アルミニウムと、ジメチルジアリルアンモニウムクロライド系ポリマーとを含有してなることを特徴とする排水処理用凝集剤。 [1] A flocculant for wastewater treatment comprising polyaluminum chloride having a basicity of less than 50% and a dimethyldiallylammonium chloride-based polymer.
［２］　［１］において、前記ジメチルジアリルアンモニウムクロライド系ポリマーが、ジメチルジアリルアンモニウムクロライドのホモポリマー又はコポリマーであり、固有粘度が０．１～３ｄＬ／ｇで、コロイド当量が４．０ｍｅｑ．／ｇ以上であることを特徴とする排水処理用凝集剤。 [2] In [1], the dimethyldiallylammonium chloride polymer is a homopolymer or copolymer of dimethyldiallylammonium chloride, having an intrinsic viscosity of 0.1 to 3 dL / g and a colloid equivalent of 4.0 meq. / G or more of a flocculant for wastewater treatment.
［３］　［１］又は［２］において、前記塩基度５０％未満のポリ塩化アルミニウムとジメチルジアリルアンモニウムクロライド系ポリマーとの混合物よりなることを特徴とする排水処理用凝集剤。 [3] A wastewater treatment flocculant comprising the mixture of polyaluminum chloride having a basicity of less than 50% and a dimethyldiallylammonium chloride polymer in [1] or [2].
［４］　［１］ないし［３］のいずれかにおいて、前記塩基度５０％未満のポリ塩化アルミニウムのＡｌ２Ｏ３換算量１００重量部に対して、前記ジメチルジアリルアンモニウムクロライド系ポリマーを１～５０重量部含むことを特徴とする排水処理用凝集剤。 [4] In any one of [1] to [3], 1 to 50 of the dimethyldiallylammonium chloride-based polymer is used per 100 parts by weight of the polyaluminum chloride having a basicity of less than 50% in terms of Al 2 O 3. A flocculant for wastewater treatment characterized by containing a weight part.
［５］　［１］ないし［４］のいずれかにおいて、着色排水処理用の凝集剤であることを特徴とする排水処理用凝集剤。 [5] The wastewater treatment flocculant according to any one of [1] to [4], which is a flocculant for colored wastewater treatment.
［６］　排水に、［１］ないし［５］のいずれかに記載の排水処理用凝集剤を添加して凝集処理することを特徴とする排水の凝集処理方法。 [6] A method for aggregating wastewater, wherein the wastewater treatment flocculant according to any one of [1] to [5] is added to the wastewater for agglomeration.
［７］　［６］において、排水に、前記塩基度５０％未満のポリ塩化アルミニウムをＡｌ２Ｏ３換算の添加量として２０～５００ｍｇ／Ｌ、前記ジメチルジアリルアンモニウムクロライド系ポリマーを有効成分量の添加量として２～５０ｍｇ／Ｌとなるように、前記排水処理用凝集剤を添加することを特徴とする排水処理用凝集剤。 [7] In [6], 20 to 500 mg / L of polyaluminum chloride having a basicity of less than 50% as an added amount in terms of Al 2 O 3 is added to the waste water, and the dimethyldiallylammonium chloride-based polymer is added in an active ingredient amount. The wastewater treatment flocculant, wherein the wastewater treatment flocculant is added so that the amount is 2 to 50 mg / L.
　本発明によれば、排水、特に、食品・飲料製造工場や化学工場等から排出される溶解性ＣＯＤ由来の色度を有する着色排水等の排水を効果的に凝集処理して、色度が十分に低減された高水質の処理水を得ることができる。 According to the present invention, waste water, in particular, waste water such as colored waste water having a chromaticity derived from soluble COD discharged from a food / beverage manufacturing factory, chemical factory, etc. is effectively agglomerated, and the chromaticity is sufficient. It is possible to obtain treated water with high water quality reduced to a very low level.
　本発明によれば、塩基度５０％未満のポリ塩化アルミニウムとジメチルジアリルアンモニウムクロライド系ポリマーとを併用することによる凝集作用の相乗効果で、排水に添加する無機凝集剤量の低減を図ることができ、腐食性イオン量を低減して排水設備の腐食を抑制すると共に、凝集汚泥の発生量を低減することができる。 According to the present invention, it is possible to reduce the amount of the inorganic flocculant added to the wastewater by the synergistic effect of the aggregating action by using together the polyaluminum chloride having a basicity of less than 50% and the dimethyldiallylammonium chloride-based polymer. In addition to reducing the amount of corrosive ions, the corrosion of the drainage equipment can be suppressed, and the generation amount of the coagulated sludge can be reduced.
　塩基度５０％未満の低塩基度のポリ塩化アルミニウムは、ジメチルジアリルアンモニウムクロライド系ポリマーと混合して一剤化した際の安定性にも優れ、製剤化の面でも有利である。 A low basicity polyaluminum chloride having a basicity of less than 50% is excellent in stability when mixed with a dimethyldiallylammonium chloride polymer and is advantageous in terms of formulation.
　以下に本発明の実施の形態を詳細に説明する。 Hereinafter, embodiments of the present invention will be described in detail.
［処理対象排水］
　本発明で凝集処理する排水としては特に制限はない。本発明は、染色排水、化学工場排水、食品・飲料製造工場排水、排水の生物処理水等の着色排水、特に、食品・飲料製造工場や化学工場等から排出される溶解性ＣＯＤ由来の色度を有する着色排水の凝集処理に有効である。本発明によれば、これらの着色排水を凝集処理して、色度を十分に低減した高水質の処理水を得ることができる。 [Treatment wastewater]
There is no restriction | limiting in particular as waste_water | drain which carries out the aggregation process by this invention. The present invention relates to colored wastewater such as dye wastewater, chemical factory wastewater, food / beverage manufacturing factory wastewater, biological wastewater for wastewater treatment, particularly soluble COD-derived chromaticity discharged from food / beverage manufacturing factory, chemical factory, etc. It is effective for the coagulation treatment of colored wastewater having According to the present invention, these colored wastewater can be agglomerated to obtain high-quality treated water with sufficiently reduced chromaticity.
　これらの着色排水は、色度（後掲の実施例の項に記載されるように波長４２０ｎｍの吸光度で測定した色度）が１００～１００００程度である。本発明によれば、このような着色排水を凝集処理して、色度１００以下の凝集処理水を得ることができる。 These colored wastewaters have a chromaticity (chromaticity measured by absorbance at a wavelength of 420 nm as described in the Examples section below) of about 100 to 10,000. According to the present invention, such colored waste water can be agglomerated to obtain agglomerated water having a chromaticity of 100 or less.
［塩基度５０％未満のＰＡＣ］
　本発明では、ポリ塩化アルミニウム（ＰＡＣ）として塩基度５０％未満のＰＡＣ（以下「低塩基度ＰＡＣ」と称す場合がある。）を用いる。塩基性ＰＡＣは、一般式［Ａｌ２（ＯＨ）ｎＣｌ６－ｎ］ｍ（０＜ｎ＜６，ｍ≦１０）で示される。塩基度は（ｎ／６）×１００（％）として計算することができる。本発明ではこの計算方法により算出した塩基度が５０％未満のものを用いる。 [PAC less than 50% basicity]
In the present invention, PAC having a basicity of less than 50% (hereinafter sometimes referred to as “low basicity PAC”) is used as polyaluminum chloride (PAC). Basic PAC is represented by the general formula [Al 2 (OH) n Cl 6-n ] m (0 <n <6, m ≦ 10). The basicity can be calculated as (n / 6) × 100 (%). In the present invention, the basicity calculated by this calculation method is less than 50%.
　ＰＡＣの塩基度が５０％以上であると、凝集処理により、十分に色度を低減した凝集処理水を得ることができない。 When the basicity of the PAC is 50% or more, it is impossible to obtain a coagulated water having a sufficiently reduced chromaticity by the coagulation process.
　塩基度５０％未満のＰＡＣはフロック形成力は弱くなるが、荷電中和力が強くなることにより色度成分との反応性が高く、ジメチルジアリルアンモニウムクロライド系ポリマーとの併用において、色度が十分に低減された高水質の凝集処理水を得ることができる。 PACs with a basicity of less than 50% have a weak floc-forming ability, but a high charge neutralization ability results in high reactivity with the chromaticity component. Sufficient chromaticity in combination with dimethyldiallylammonium chloride polymers It is possible to obtain coagulated water having a high water quality reduced to a very low level.
　塩基度５０％未満のＰＡＣは、塩基度４５～６５％のＪＩＳ規格のＰＡＣや塩基度５８％以上の所謂高塩基度のＰＡＣと比較して水酸化物イオン（ＯＨ－）が少なく、水溶性アルミニウム塩が析出しにくいという理由から、有機凝結剤と混合した際の安定性が高く、一剤化した凝集剤が分離しにくいという利点もある。 PACs with a basicity of less than 50% have less hydroxide ions (OH − ) and water-soluble than JIS standard PACs with a basicity of 45-65% and so-called high basicity PACs with a basicity of 58% or more. For the reason that the aluminum salt hardly precipitates, there is an advantage that the stability when mixed with the organic coagulant is high, and the aggregated coagulant is difficult to separate.
　凝集効果及び一剤化した凝集剤の安定性の面から、ＰＡＣの塩基度は、５０％以下であることが好ましい。 From the viewpoint of the aggregating effect and the stability of the agglomerated agent, the basicity of the PAC is preferably 50% or less.
［ＤＡＤＭＡＣ系ポリマー］
　本発明で用いるジメチルジアリルアンモニウムクロライド（ＤＡＤＭＡＣ）系ポリマーは、ＤＡＤＭＡＣのホモポリマーであってもよく、ＤＡＤＭＡＣと他の共重合成分とのコポリマーであってもよい。ＤＡＤＭＡＣ系ポリマーがコポリマーである場合、他の共重合成分としては、アクリルアミド、メタクリルアミド、Ｎ，Ｎ－ジメチルアクリルアミド、Ｎ，Ｎ－ジメチルメタクリルアミドなどのアミド類、アクリロニトリル、メタクリロニトリルなどのシアン化ビニル系化合物、アクリル酸メチル、アクリル酸エチル、メタクリル酸メチル、メタクリル酸エチルなどの（メタ）アクリル酸のアルキルエステル類、酢酸ビニルなどのビニルエステル類、スチレン、α－メチルスチレン、ｐ－メチルスチレンなどの芳香族ビニル系化合物などのノニオン性ビニルモノマーの１種又は２種以上が挙げられる。ＤＡＤＭＡＣ系コポリマーは、低塩基度ＰＡＣとの溶解性の面から、ベンジル基等の疎水基を含まないことが好ましい。 [DADMAC polymer]
The dimethyldiallylammonium chloride (DADMAC) -based polymer used in the present invention may be a DADMAC homopolymer or a copolymer of DADMAC and other copolymerization components. When the DADMAC polymer is a copolymer, other copolymerization components include amides such as acrylamide, methacrylamide, N, N-dimethylacrylamide and N, N-dimethylmethacrylamide, and cyanation such as acrylonitrile and methacrylonitrile. Vinyl compounds, alkyl esters of (meth) acrylic acid such as methyl acrylate, ethyl acrylate, methyl methacrylate and ethyl methacrylate, vinyl esters such as vinyl acetate, styrene, α-methylstyrene, p-methylstyrene 1 type, or 2 or more types of nonionic vinyl monomers, such as aromatic vinyl type compounds, etc. are mentioned. The DADMAC copolymer preferably does not contain a hydrophobic group such as a benzyl group from the viewpoint of solubility with a low basicity PAC.
　ＤＡＤＭＡＣ系ポリマーとしては、ＤＡＤＭＡＣホモポリマー、或いは、後述のコロイド当量を満たすコポリマーが好ましく、特に好ましくはＤＡＤＭＡＣホモポリマー（ポリＤＡＤＭＡＣ）である。 As the DADMAC polymer, a DADMAC homopolymer or a copolymer satisfying the colloidal equivalent described later is preferable, and a DADMAC homopolymer (polyDADMAC) is particularly preferable.
　本発明で用いるＤＡＤＭＡＣ系ポリマーは、固有粘度が０．１～３ｄＬ／ｇ、特に０．５～２ｄＬ／ｇであることが好ましい。固有粘度が上記下限未満であると、凝集力が低下する傾向がある。固有粘度が上記上限を超えると濁度成分の表面荷電の中和には粘度が高く、反応性が劣ると共に、低塩基度ＰＡＣとの相溶性が低くなることから、処理効率が低くなる傾向がある。 The DADMAC polymer used in the present invention preferably has an intrinsic viscosity of 0.1 to 3 dL / g, particularly 0.5 to 2 dL / g. When the intrinsic viscosity is less than the above lower limit, the cohesive force tends to decrease. When the intrinsic viscosity exceeds the above upper limit, neutralization of surface charge of the turbidity component is high in viscosity, inferior in reactivity and low in compatibility with low basicity PAC, so that the processing efficiency tends to be low. is there.
　ＤＡＤＭＡＣ系ポリマーの固有粘度は、１．０Ｎの硝酸ナトリウム水溶液を溶媒として３０℃で測定した値である。 The intrinsic viscosity of the DADMAC polymer is a value measured at 30 ° C. using a 1.0 N sodium nitrate aqueous solution as a solvent.
　本発明で用いるＤＡＤＭＡＣ系ポリマーは、コロイド当量が４．０ｍｅｑ．／ｇ以上、特に５．０ｍｅｑ．／ｇ以上であることが好ましい。コロイド当量が４．０ｍｅｑ．／ｇ未満では荷電中和力が弱くなり、目的の凝集効果を得るための必要添加量が多くなる。ＤＡＤＭＡＣ系ポリマーのコロイド当量の上限は６．５ｍｅｑ．／ｇである。 The DADMAC polymer used in the present invention has a colloid equivalent of 4.0 meq. / G or more, especially 5.0 meq. / G or more is preferable. Colloidal equivalent is 4.0 meq. If it is less than / g, the charge neutralization force becomes weak, and the amount required to obtain the desired aggregation effect increases. The upper limit of the colloidal equivalent of the DADMAC polymer is 6.5 meq. / G.
　ＤＡＤＭＡＣ系ポリマーのコロイド当量は「コロイド滴定法」（千手諒一著、南江堂（株）（Ｓ４４年１１月発行））により測定される。 The colloidal equivalent of the DADMAC polymer is measured by “colloidal titration method” (written by Keiichi Sente, Nankodo Co., Ltd. (published in November S44)).
［凝集剤の形態］
　本発明で用いる塩基度５０％未満のＰＡＣは、通常、Ａｌ２Ｏ３換算濃度で７～１１重量％程度の水溶液として用いることができる。 [Form of flocculant]
The PAC having a basicity of less than 50% used in the present invention can usually be used as an aqueous solution having an Al 2 O 3 equivalent concentration of about 7 to 11% by weight.
　低塩基度ＰＡＣとＤＡＤＭＡＣ系ポリマーとは、排水に別々に添加してもよく、予め一剤化して添加してもよい。一剤化した場合、前述の通り、これらが分離し難く、安定性に優れた凝集剤とすることができる。 The low basicity PAC and the DADMAC polymer may be added separately to the waste water, or may be added as a single agent in advance. In the case of a single agent, as described above, it is difficult to separate them and a flocculant having excellent stability can be obtained.
　この場合、上述のようなＡｌ２Ｏ３換算濃度の低塩基度ＰＡＣの水溶液に対して、低塩基度ＰＡＣのＡｌ２Ｏ３換算量１００重量部に対して、ＤＡＤＭＡＣ系ポリマーの有効成分量が１～５０重量部となるように混合して使用することが好ましい。この混合割合は、後述の凝集処理時の好適な使用割合に基づくものである。 In this case, the amount of the active ingredient of the DADMAC-based polymer is 100 parts by weight of the low basicity PAC equivalent of Al 2 O 3 with respect to the aqueous solution of the low basicity PAC equivalent to the Al 2 O 3 equivalent concentration as described above. It is preferable to use the mixture so as to be 1 to 50 parts by weight. This mixing ratio is based on a suitable use ratio at the time of agglomeration treatment described later.
［凝集処理］
　本発明の排水の凝集処理方法では、着色排水等の排水に低塩基度ＰＡＣとＤＡＤＭＡＣ系ポリマーを添加して凝集処理する。 [Aggregation treatment]
In the wastewater agglomeration treatment method of the present invention, a low-basic PAC and a DADMAC polymer are added to wastewater such as colored wastewater for agglomeration treatment.
　低塩基度ＰＡＣとＤＡＤＭＡＣ系ポリマーとは、予め混合して一剤製剤として添加してもよく、別々に添加してもよいが、別々に添加する場合は、低塩基度ＰＡＣを添加した後ＤＡＤＭＡＣ系ポリマーを添加するか、或いは、低塩基度ＰＡＣとＤＡＤＭＡＣ系ポリマーを同時に添加することが好ましい。 The low basicity PAC and the DADMAC-based polymer may be mixed in advance and added as a single agent formulation, or may be added separately. However, in the case of separate addition, after adding the low basicity PAC, DADMAC It is preferable to add a polymer or to add a low basicity PAC and a DADMAC polymer simultaneously.
　排水への低塩基度ＰＡＣの添加量は、処理する排水の性状や用いる低塩基度ＰＡＣの塩基度等によっても異なるが、通常Ａｌ２Ｏ３換算での添加量として２０～５００ｍｇ／Ｌ、特に５０～３００ｍｇ／Ｌとすることが好ましい。この範囲よりも低塩基度ＰＡＣの添加量が少ないと十分な凝集処理効果が得られず、この範囲より多く添加することは、無機凝集剤使用量を低減する本発明の目的から好ましくない。 The amount of the low basicity PAC added to the wastewater varies depending on the properties of the wastewater to be treated and the basicity of the low basicity PAC used, but is usually 20 to 500 mg / L in terms of Al 2 O 3 , especially 50 to 300 mg / L is preferable. If the addition amount of the low basicity PAC is less than this range, a sufficient flocculation treatment effect cannot be obtained, and adding more than this range is not preferable for the purpose of the present invention to reduce the amount of inorganic flocculant used.
　ＤＡＤＭＡＣ系ポリマーの添加量は、少な過ぎると、十分な凝集効果を得ることができず、多過ぎると凝集処理水の色度が上昇する傾向がある。ＤＡＤＭＡＣ系ポリマーは、有効成分量として排水に対して２～５０ｍｇ／Ｌ程度となるように添加することが好ましい。ＤＡＤＭＡＣ系ポリマーは、低塩基度ＰＡＣのＡｌ２Ｏ３換算添加量１００重量部に対して１～５０重量部となるように添加することが好ましい。 If the amount of the DADMAC polymer added is too small, a sufficient coagulation effect cannot be obtained, and if it is too large, the chromaticity of the coagulated water tends to increase. The DADMAC polymer is preferably added so that the amount of the active ingredient is about 2 to 50 mg / L with respect to the waste water. The DADMAC polymer is preferably added in an amount of 1 to 50 parts by weight based on 100 parts by weight of the low basicity PAC in terms of Al 2 O 3 addition.
　排水に低塩基度ＰＡＣとＤＡＤＭＡＣ系ポリマーとを同時に或いは予め混合して添加する場合は、本発明の凝集剤の所定量を排水に添加した後１００～２００ｒｐｍで２～５分程度撹拌して凝集処理することが好ましい。 When adding low basicity PAC and DADMAC polymer to wastewater simultaneously or mixed in advance, add a predetermined amount of the flocculant of the present invention to the wastewater and then stir at 100 to 200 rpm for about 2 to 5 minutes to agglomerate It is preferable to process.
　低塩基度ＰＡＣを添加した後ＤＡＤＭＡＣ系ポリマーを添加する場合は、排水に低塩基度ＰＡＣを添加して１００～２００ｒｐｍで２～５分程度撹拌した後、ＤＡＤＭＡＣ系ポリマーを添加して１００～２００ｒｐｍで２～５分程度撹拌することが好ましい。 When adding a DADMAC polymer after adding a low basicity PAC, add the low basicity PAC to the waste water and stirring at 100 to 200 rpm for about 2 to 5 minutes, then add the DADMAC polymer and add 100 to 200 rpm. It is preferable to stir for 2 to 5 minutes.
　凝集処理後は、常法に従って、沈降分離、濾過等で固液分離することで処理水を得ることができる。 After the flocculation treatment, treated water can be obtained by solid-liquid separation by sedimentation separation, filtration or the like according to a conventional method.
　以下に、実験例、実施例及び比較例を挙げて本発明をより具体的に説明するが、本発明はその要旨を超えない限り、以下の実施例に限定されるものではない。 Hereinafter, the present invention will be described more specifically with reference to experimental examples, examples, and comparative examples. However, the present invention is not limited to the following examples as long as the gist thereof is not exceeded.
　以下の実験例、実施例及び比較例において、ＰＡＣ及び有機凝結剤としては、以下のものを用いた。 In the following experimental examples, examples and comparative examples, the following were used as the PAC and the organic coagulant.
［ＰＡＣ］
　ＰＡＣ（６０）：多木化学（株）製商品名「ＰＡＣ３００Ａ」
　（塩基度：６０％，Ａｌ２Ｏ３換算濃度で１０．５重量％の水溶液）
　ＰＡＣ（５０）：多木化学（株）製商品名「ＰＡＣ２５０Ａ」
　（塩基度：５０％，Ａｌ２Ｏ３換算濃度で１０．５重量％の水溶液）
　ＰＡＣ（４８）：東信化学（株）製商品名「東信ＰＡＣ」
　（塩基度：４８％，Ａｌ２Ｏ３換算濃度で１０．５重量％の水溶液）
　ＰＡＣ（２０）：東信化学（株）製商品名「ＷＰＡＣ」
　（塩基度：２０％，Ａｌ２Ｏ３換算濃度で１０．５重量％の水溶液） [PAC]
PAC (60): Trade name “PAC300A” manufactured by Taki Chemical Co., Ltd.
(Basicity: 60%, 10.5% by weight aqueous solution in terms of Al 2 O 3 concentration)
PAC (50): Trade name “PAC250A” manufactured by Taki Chemical Co., Ltd.
(Basicity 50%, aqueous solution of 10.5 wt% in terms of Al 2 O 3 concentration)
PAC (48): Toshin Chemical Co., Ltd. trade name “Toshin PAC”
(Basicity: 48%, 10.5 wt% aqueous solution in terms of Al 2 O 3 concentration)
PAC (20): Toshin Chemical Co., Ltd. product name “WPAC”
(Basicity: 20%, 10.5% by weight aqueous solution in terms of Al 2 O 3 concentration)
　上記のＰＡＣは、いずれもＡｌ２Ｏ３換算濃度１０．５重量％のＰＡＣ水溶液として用いた。以下の実験例、実施例及び比較例におけるＰＡＣ添加量は、このＰＡＣ水溶液としての添加量を示す。 Each of the above PACs was used as an aqueous PAC solution having an Al 2 O 3 equivalent concentration of 10.5% by weight. The PAC addition amount in the following experimental examples, examples, and comparative examples indicates the addition amount as this PAC aqueous solution.
［有機凝結剤］
　ポリＤＡＤＭＡＣ：ジメチルジアリルアンモニウムクロライドのホモポリマー
　（固有粘度：０．７ｄＬ／ｇ，コロイド当量：５．９ｍｅｑ．／ｇ）
　ＤＥＡＰ：ジメチルアミン・エピクロルヒドリン共重合体
　（固有粘度：０．１ｄＬ／ｇ，コロイド当量：６．８ｍｅｑ．／ｇ） [Organic coagulant]
PolyDADMAC: homopolymer of dimethyldiallylammonium chloride (Intrinsic viscosity: 0.7 dL / g, colloidal equivalent: 5.9 meq./g)
DEAP: Dimethylamine / epichlorohydrin copolymer (Intrinsic viscosity: 0.1 dL / g, colloidal equivalent: 6.8 meq./g)
　排水のｐＨはガラス電極法で測定した。濁度は日立製作所社製「Ｕ－１８００分光光度計」を用いて波長６６０ｎｍの吸光度を測定することで求めた。色度は、同様に波長４２０ｎｍの吸光度を測定することで求めた。 The pH of the wastewater was measured by the glass electrode method. Turbidity was determined by measuring the absorbance at a wavelength of 660 nm using a “U-1800 spectrophotometer” manufactured by Hitachi, Ltd. The chromaticity was similarly determined by measuring the absorbance at a wavelength of 420 nm.
［実験例１］
　ポリＤＡＤＭＡＣとＰＡＣとの混合製剤の安定性を評価するために、表１に示すＰＡＣ（Ａｌ２Ｏ３換算濃度１０．５重量％のＰＡＣ水溶液）とポリＤＡＤＭＡＣをＰＡＣ／ポリＤＡＤＭＡＣ＝９９／１の重量比で混合して一剤化したものの経時安定性を目視評価した。結果を表１に示す。 [Experimental Example 1]
In order to evaluate the stability of the mixed preparation of polyDADMAC and PAC, the PAC shown in Table 1 (PAC aqueous solution with an Al 2 O 3 equivalent concentration of 10.5% by weight) and polyDADMAC were converted into PAC / polyDADMAC = 99/1. The stability over time of the mixture obtained by mixing at a weight ratio of 1 was evaluated visually. The results are shown in Table 1.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　表１より、塩基度４８％のＰＡＣの方が、塩基度６０％のＰＡＣよりもポリＤＡＤＭＡＣと混合した際の安定性が高く、一剤製剤とした場合、分離し難く、経時安定性に優れることが分かる。 From Table 1, PAC with a basicity of 48% is more stable when mixed with polyDADMAC than PAC with a basicity of 60%. I understand that.
［実験例２］
　下記性状の飲料製造工場から排出された着色排水を用いて、凝集試験を行った。 [Experiment 2]
An agglomeration test was conducted using colored wastewater discharged from a beverage manufacturing plant having the following properties.
＜着色排水性状＞
　ｐＨ：６．６
　濁度：５１５
　色度：４０４８ <Colored drainage properties>
pH: 6.6
Turbidity: 515
Chromaticity: 4048
　この着色排水を５００ｍＬ採取し、表２に示す添加量（Ａｌ２Ｏ３換算濃度１０．５重量％のＰＡＣ水溶液として）となるように各ＰＡＣを添加して１５０ｒｐｍで急速撹拌を２分間行い、その後アニオン性ポリアクリルアミド系高分子凝集剤（栗田工業（株）製「クリフロック　ＰＡ－６１２」）を５ｍｇ／Ｌ添加して１５０ｒｐｍで急速撹拌を１分行った後、５０ｒｐｍで緩速撹拌を２分行った。その後、３分静置した後、上澄み水（処理水）の色度の測定を行った。結果を表２に示す。 500 mL of this colored wastewater was collected, each PAC was added so as to have the addition amount shown in Table 2 (as a PAC aqueous solution with an Al 2 O 3 equivalent concentration of 10.5 wt%), and rapid stirring was performed at 150 rpm for 2 minutes. Thereafter, 5 mg / L of an anionic polyacrylamide polymer flocculant (“Cliff Rock PA-612” manufactured by Kurita Kogyo Co., Ltd.) was added and rapidly stirred at 150 rpm for 1 minute, followed by slow stirring at 50 rpm for 2 minutes. I went for a minute. Then, after leaving still for 3 minutes, the chromaticity of supernatant water (treated water) was measured. The results are shown in Table 2.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　表２より、塩基度５０％未満のＰＡＣを用いることで、処理水の色度を低減できることが分かる。 From Table 2, it can be seen that the chromaticity of the treated water can be reduced by using a PAC having a basicity of less than 50%.
［実施例１、比較例１～４］
　実験例１で凝集試験に供したものと同じ着色排水を用い、この着色排水に、表３に示すＰＡＣ１００ｇ（Ａｌ２Ｏ３換算濃度１０．５重量％のＰＡＣ水溶液として）と表３に示す有機凝結剤０．５ｇとを混合して一剤化した凝集剤を、１２００ｍｇ／Ｌ添加し、１５０ｒｐｍで２分間急速撹拌して凝集処理し、その後３分静置した後、上澄み水（処理水）の色度の測定を行った。結果を表３に示す。 [Example 1, Comparative Examples 1 to 4]
The same colored wastewater as that used in the coagulation test in Experimental Example 1 was used. To this colored wastewater, 100 g of PAC shown in Table 3 (as a PAC aqueous solution with an Al 2 O 3 equivalent concentration of 10.5 wt%) and the organic shown in Table 3 were used. A coagulant mixed with 0.5 g of a coagulant is added to 1200 mg / L, agglomerated by rapid stirring at 150 rpm for 2 minutes, and then allowed to stand for 3 minutes, and then supernatant water (treated water) The chromaticity of was measured. The results are shown in Table 3.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　表３より明らかなように、ＰＡＣ（２０）とポリＤＡＤＭＡＣを併用した実施例１では、色度の低い処理水を得ることができる。 As is apparent from Table 3, in Example 1 in which PAC (20) and polyDADMAC are used in combination, treated water with low chromaticity can be obtained.
　比較例１は、特開２００７－１６７７２１の凝集剤に相当するが、色度の低い処理水を得ることはできない。 Comparative Example 1 corresponds to the flocculant disclosed in JP-A No. 2007-167721, but treated water with low chromaticity cannot be obtained.
　比較例１及び比較例４と実施例１との対比より、ＤＥＡＰに対しては塩基度の高いＰＡＣが有効であり、塩基度の低いＰＡＣは、特にポリＤＡＤＭＡＣとの組み合わせにおいて有効であることが分かる。 From the comparison between Comparative Example 1 and Comparative Example 4 and Example 1, PAC with high basicity is effective for DEAP, and PAC with low basicity is effective particularly in combination with polyDADMAC. I understand.
［実施例２～６、比較例５］
　実験例１で凝集試験に供したものと同じ着色排水を用い、この着色排水に、表４に示すＰＡＣ１００ｇ（Ａｌ２Ｏ３換算濃度１０．５重量％のＰＡＣ水溶液として）と表４に示す有機凝結剤を表４に示す量混合して一剤化した凝集剤を、９００ｍｇ／Ｌ添加し、１５０ｒｐｍで２分間急速撹拌して凝集処理し、その後３分静置した後、上澄み水（処理水）の色度の測定を行った。結果を表４に示す。 [Examples 2 to 6, Comparative Example 5]
The same colored wastewater as that used in the coagulation test in Experimental Example 1 was used. To this colored wastewater, 100 g of PAC shown in Table 4 (as a PAC aqueous solution with an Al 2 O 3 equivalent concentration of 10.5 wt%) and the organic shown in Table 4 were used. The flocculant mixed in the amount shown in Table 4 into a single agent was added at 900 mg / L, rapidly stirred at 150 rpm for 2 minutes to agglomerate, then allowed to stand for 3 minutes, and then supernatant water (treated water) ) Was measured. The results are shown in Table 4.
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
　表４より次のことが分かる。 Table 4 shows the following.
　比較例５は特開２００７－１６７７２１の凝集剤に相当するが、色度の低い処理水を得ることができない。 Comparative Example 5 corresponds to the flocculant described in JP-A No. 2007-167721, but treated water with low chromaticity cannot be obtained.
　これに対して、本発明の凝集剤を添加した実施例２～６では色度が十分に低減された処理水を得ることができた。ポリＤＡＤＭＡＣの添加量は多い程、処理水の色度は良好となるが、実施例６のように多過ぎると色度が悪くなるので、適度な添加量で凝集処理することが好ましい。 On the other hand, in Examples 2 to 6 to which the flocculant of the present invention was added, treated water with sufficiently reduced chromaticity could be obtained. The greater the amount of polyDADMAC added, the better the chromaticity of the treated water. However, if too much is added as in Example 6, the chromaticity will deteriorate, so it is preferable to agglomerate with an appropriate amount of addition.
　本発明によれば、塩基度５０％未満のＰＡＣを用いることで、良好な凝集効果が得られる。上記の実験例や比較例において、ＰＡＣ（５０）はＰＡＣ（６０）よりも凝集効果が劣る傾向があるが、これはＰＡＣ（５０）が凝集処理時に、フロック形成力と荷電中和力の不均衡が生じ、凝集性が低下したことによると考えられる。 According to the present invention, a good aggregation effect can be obtained by using a PAC having a basicity of less than 50%. In the above experimental examples and comparative examples, PAC (50) tends to be inferior in aggregation effect to PAC (60). This is thought to be due to the fact that equilibrium occurred and cohesion decreased.
　本発明を特定の態様を用いて詳細に説明したが、本発明の意図と範囲を離れることなく様々な変更が可能であることは当業者に明らかである。
　本出願は、２０１５年３月３１日付で出願された日本特許出願２０１５－０７２９５７に基づいており、その全体が引用により援用される。

  Although the present invention has been described in detail using specific embodiments, it will be apparent to those skilled in the art that various modifications can be made without departing from the spirit and scope of the invention.
This application is based on Japanese Patent Application No. 2015-072957 filed on March 31, 2015, which is incorporated by reference in its entirety.

Claims (7)

  1. 　塩基度５０％未満のポリ塩化アルミニウムと、ジメチルジアリルアンモニウムクロライド系ポリマーとを含有してなることを特徴とする排水処理用凝集剤。 A flocculant for wastewater treatment comprising polyaluminum chloride having a basicity of less than 50% and a dimethyldiallylammonium chloride-based polymer.
  2. 　請求項１において、前記ジメチルジアリルアンモニウムクロライド系ポリマーが、ジメチルジアリルアンモニウムクロライドのホモポリマー又はコポリマーであり、固有粘度が０．１～３ｄＬ／ｇで、コロイド当量が４．０ｍｅｑ．／ｇ以上であることを特徴とする排水処理用凝集剤。 In Claim 1, the dimethyldiallylammonium chloride polymer is a homopolymer or copolymer of dimethyldiallylammonium chloride, has an intrinsic viscosity of 0.1 to 3 dL / g, and a colloid equivalent of 4.0 meq. / G or more of a flocculant for wastewater treatment.
  3. 　請求項１又は２において、前記塩基度５０％未満のポリ塩化アルミニウムとジメチルジアリルアンモニウムクロライド系ポリマーとの混合物よりなることを特徴とする排水処理用凝集剤。 3. The wastewater treatment flocculant according to claim 1, comprising a mixture of the polyaluminum chloride having a basicity of less than 50% and a dimethyldiallylammonium chloride-based polymer.
  4. 　請求項１ないし３のいずれか１項において、前記塩基度５０％未満のポリ塩化アルミニウムのＡｌ２Ｏ３換算量１００重量部に対して、前記ジメチルジアリルアンモニウムクロライド系ポリマーを１～５０重量部含むことを特徴とする排水処理用凝集剤。 In any one of claims 1 to 3, relative to the terms of Al 2 O 3 per 100 parts by weight of polyaluminum chloride is less than the basicity of 50%, including the dimethyldiallylammonium chloride-based polymer 1 to 50 parts by weight A flocculant for wastewater treatment characterized by this.
  5. 　請求項１ないし４のいずれか１項において、着色排水処理用の凝集剤であることを特徴とする排水処理用凝集剤。 The wastewater treatment flocculant according to any one of claims 1 to 4, which is a flocculant for colored wastewater treatment.
  6. 　排水に、請求項１ないし５のいずれか１項に記載の排水処理用凝集剤を添加して凝集処理することを特徴とする排水の凝集処理方法。 A wastewater agglomeration treatment method, characterized in that the wastewater treatment flocculant according to any one of claims 1 to 5 is added to the wastewater for agglomeration treatment.
  7. 　請求項６において、排水に、前記塩基度５０％未満のポリ塩化アルミニウムをＡｌ２Ｏ３換算の添加量として２０～５００ｍｇ／Ｌ、前記ジメチルジアリルアンモニウムクロライド系ポリマーを有効成分量の添加量として２～５０ｍｇ／Ｌとなるように、前記排水処理用凝集剤を添加することを特徴とする排水処理用凝集剤。 7. The waste water according to claim 6, wherein the polyaluminum chloride having a basicity of less than 50% is added in an amount of 20 to 500 mg / L in terms of Al 2 O 3 and the dimethyldiallylammonium chloride-based polymer is added in an amount of 2 The wastewater treatment flocculant, wherein the wastewater treatment flocculant is added so as to be ˜50 mg / L.
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