JP2013255863A - Flocculant and sludge dehydration method using the same - Google Patents
Flocculant and sludge dehydration method using the same Download PDFInfo
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- JP2013255863A JP2013255863A JP2012131462A JP2012131462A JP2013255863A JP 2013255863 A JP2013255863 A JP 2013255863A JP 2012131462 A JP2012131462 A JP 2012131462A JP 2012131462 A JP2012131462 A JP 2012131462A JP 2013255863 A JP2013255863 A JP 2013255863A
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- water
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- 239000010802 sludge Substances 0.000 title claims abstract description 74
- 238000000034 method Methods 0.000 title claims description 26
- 230000018044 dehydration Effects 0.000 title description 3
- 238000006297 dehydration reaction Methods 0.000 title description 3
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- 239000000178 monomer Substances 0.000 claims abstract description 73
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- 125000002091 cationic group Chemical group 0.000 claims abstract description 40
- 239000000203 mixture Substances 0.000 claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
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- 229910052739 hydrogen Inorganic materials 0.000 claims description 19
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 15
- 125000000217 alkyl group Chemical group 0.000 claims description 14
- 125000004432 carbon atom Chemical group C* 0.000 claims description 14
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 10
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- 239000007864 aqueous solution Substances 0.000 claims description 3
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- 125000004430 oxygen atom Chemical group O* 0.000 claims description 3
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- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
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- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
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- 239000003350 kerosene Substances 0.000 description 1
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- 125000005395 methacrylic acid group Chemical group 0.000 description 1
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- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
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- SRSFOMHQIATOFV-UHFFFAOYSA-N octanoyl octaneperoxoate Chemical compound CCCCCCCC(=O)OOC(=O)CCCCCCC SRSFOMHQIATOFV-UHFFFAOYSA-N 0.000 description 1
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- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
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- RRHXZLALVWBDKH-UHFFFAOYSA-M trimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)OCC[N+](C)(C)C RRHXZLALVWBDKH-UHFFFAOYSA-M 0.000 description 1
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Landscapes
- Separation Of Suspended Particles By Flocculating Agents (AREA)
- Treatment Of Sludge (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
本発明は、凝集処理剤およびそれを用いた汚泥脱水方法に関するものであり、詳しくは特定の単量体を重合して得たカチオン性水溶性高分子（Ａ）と両性水溶性高分子（Ｂ）およびビニルアミン構造単位を有する水溶性高分子（Ｃ）を含有する凝集処理剤、およびそれを使用した汚泥脱水方法に関する。 The present invention relates to a coagulation treatment agent and a sludge dewatering method using the same, and more specifically, a cationic water-soluble polymer (A) and an amphoteric water-soluble polymer (B) obtained by polymerizing a specific monomer. ) And a water-soluble polymer (C) having a vinylamine structural unit, and a sludge dewatering method using the same.
汚泥の脱水性を改良するために様々な水溶性高分子が凝集剤として使用されている。中でもビニルアミン系水溶性高分子は、特定の汚泥に対して優れた効果を発揮するため使用されているが、価格は高く処理ｐＨ域も非常に限られるといった問題が指摘されている。そのためビニルアミン系水溶性高分子の一部そのまま使用し、市販品として汎用されている（メタ）アクリル系水溶性高分子を混合あるいは併用する水溶性高分子凝集剤が多数開示されている。特許文献１では、カチオン性（メタ）アクリル系水溶性高分子とビニルアミン系水溶性高分子のブレンドを使用する汚泥脱水方法、特許文献２では、ビニルアミン系水溶性高分子とアニオンリッチ両性アクリル系水溶性高分子とを併用する脱水用凝集剤、特許文献３では、ビニルアミン系水溶性高分子と架橋性イオン性水溶性高分子からなる凝集処理剤、特許文献４では、ビニルアミン系水溶性高分子とアクリル系水溶性高分子のブレンド添加後、アニオン性水溶性高分子を添加する凝集処理剤の使用方法、特許文献５では、ビニルアミン系水溶性高分子と両性水溶性ポリマーをブレンドした汚泥脱水剤、特許文献６では、ビニルアミン系水溶性高分子とアニオン性有機高分子凝集剤を組み合わせた汚泥脱水剤がそれぞれ開示されている。しかし、カチオン性アクリル系水溶性高分子と両性アクリル系水溶性高分子およびビニルアミン系水溶性高分子の三種をブレンドした凝集剤の例は見当たらない。
本発明の課題は、下水処理場における下水混合生汚泥や下水余剰汚泥、下水消化汚泥、各種余剰汚泥に対して良好な凝集とケーキ含水率低下能の高い汚泥脱水剤を開発することである。具体的にはビニルアミン構造単位を有する水溶性高分子は、種々の余剰汚泥には優れた効果を発揮するが、価格は高く処理ｐＨ域も非常に限られている。そのためビニルアミン構造単位を有する水溶性高分子の一部そのまま使用し、市販品として汎用されている（メタ）アクリル系水溶性高分子により置き換える処方を検討する。 An object of the present invention is to develop a sludge dewatering agent having a high flocculation and cake moisture content reducing ability for sewage mixed raw sludge, sewage surplus sludge, sewage digested sludge, and various surplus sludge in a sewage treatment plant. Specifically, a water-soluble polymer having a vinylamine structural unit exhibits excellent effects on various surplus sludges, but is expensive and has a very limited treatment pH range. Therefore, a part of the water-soluble polymer having a vinylamine structural unit is used as it is, and a prescription for replacement with a commercially available (meth) acrylic water-soluble polymer is examined.
上記課題を解決するため本発明者は、鋭意検討した結果、以下に述べる発明に到達した。すなわち、下記（Ａ）で表されるカチオン性水溶性高分子と下記（Ｂ）で表される両性水溶性高分子および下記（Ｃ）で表されるビニルアミン構造単位を有する水溶性高分子を含有することを特徴とする凝集処理剤によって、課題を解決できることが分かり本発明に達した。
（Ａ）；下記一般式（１）あるいは（２）で表される単量体を１０〜１００モル％、非イオン性単量体を０〜９０モル％からなる該単量体あるいは該単量体混合物を、重合したカチオン性水溶性高分子。
（Ｂ）；下記一般式（１）あるいは（２）で表される単量体を１０〜９０モル％、下記一般式（３）で表される単量体を１０〜６０モル％、非イオン性単量体を０〜８０モル％からなる該単量体あるいは該単量体混合物を重合した両性水溶性高分子。
（Ｃ）；下記一般式（４）で表されるビニルアミン構造単位を１０〜９０モル％有する水溶性高分子。
一般式（１）
（Ｒ１は水素又はメチル基、Ｒ２、Ｒ３は水素、炭素数１〜３のアルキルあるいはアルコキシル基であり、同種でも異種でも良い、Ｒ４は炭素数１〜３のアルキルあるいはアルコキシル基、７〜２０のアルキル基あるいはアリール基、Ａは酸素原子またはＮＨ、Ｂは炭素数２〜４のアルキレン基またはアルコキシレン基を表わす、Ｘ１ −は陰イオンをそれぞれ表わす）
（Ｒ５は水素又はメチル基、Ｒ６、Ｒ７は炭素数１〜３のアルキル基、アルコキシ基、Ｘ２ −は陰イオンをそれぞれ表わす）
（Ｒ８は水素、メチル基またはカルボキシメチル基、ＱはＳＯ３ −、Ｃ６Ｈ４ＳＯ３ −、ＣＯＮＨＣ（ＣＨ３）２ＣＨ２ＳＯ３ −、Ｃ６Ｈ４ＣＯＯ−あるいはＣＯＯ−、
Ｒ９は水素またはＣＯＯ−、Ｙ１ ＋は水素イオンまたは陽イオンをそれぞれ表す）
Ｒ１０は水素またはメチル基、Ｈ＋Ｚ−は無機酸および／または有機酸を表し、未中和時Ｈ＋Ｚ−＝０である。
As a result of intensive investigations to solve the above problems, the present inventors have reached the invention described below. That is, a cationic water-soluble polymer represented by the following (A), an amphoteric water-soluble polymer represented by the following (B), and a water-soluble polymer having a vinylamine structural unit represented by the following (C) It was found that the problem can be solved by the aggregating agent characterized in that the present invention has been achieved.
(A): the monomer represented by the following general formula (1) or (2): 10 to 100 mol%, and the nonionic monomer consisting of 0 to 90 mol% or the monomer A cationic water-soluble polymer obtained by polymerizing a body mixture.
(B): 10 to 90 mol% of a monomer represented by the following general formula (1) or (2), 10 to 60 mol% of a monomer represented by the following general formula (3), nonionic An amphoteric water-soluble polymer obtained by polymerizing the monomer or the monomer mixture comprising 0 to 80 mol% of the polymerizable monomer.
(C): A water-soluble polymer having 10 to 90 mol% of vinylamine structural units represented by the following general formula (4).
General formula (1)
(R 1 is hydrogen or a methyl group, R 2 and R 3 are hydrogen, an alkyl or alkoxyl group having 1 to 3 carbon atoms, which may be the same or different, and R 4 is an alkyl or alkoxyl group having 1 to 3 carbon atoms, alkyl group or an aryl group of 7 to 20, a represents an oxygen atom or NH, B represents an alkylene group or an alkoxylene group having 2 to 4 carbon atoms, X 1 - represents respectively an anion)
(R 5 represents hydrogen or a methyl group, R 6 and R 7 each represent an alkyl group having 1 to 3 carbon atoms, an alkoxy group, and X 2 − represents an anion)
(R 8 is hydrogen, methyl or carboxymethyl group, Q represents SO 3 -, C 6 H 4 SO 3 -, CONHC (CH 3) 2 CH 2 SO 3 -, C 6 H 4 COO - or COO -,
R 9 represents hydrogen or COO − , and Y 1 + represents a hydrogen ion or a cation, respectively)
R 10 represents hydrogen or a methyl group, H + Z − represents an inorganic acid and / or an organic acid, and H + Z − = 0 when not neutralized.
前記カチオン性水溶性高分子（Ａ）と前記両性水溶性高分子（Ｂ）および前記ビニルアミン構造単位を有する水溶性高分子（Ｃ）の形態は油中水型エマルジョンであり、油中水型エマルジョン同士で配合することができる。また、それぞれの形態は粉末状でも良く、粉末同士で配合することができる。 The cationic water-soluble polymer (A), the amphoteric water-soluble polymer (B) and the water-soluble polymer (C) having the vinylamine structural unit are water-in-oil emulsions, and water-in-oil emulsions. They can be blended together. Moreover, each form may be a powder form and can mix | blend with powder.
本発明の凝集処理剤は、特定の（メタ）アクリル系カチオン性単量体を必須として含有する単量体あるいは単量体混合物を重合した（メタ）アクリル系カチオン性水溶性高分子（Ａ）と、特定の（メタ）アクリル系カチオン性単量体およびアニオン性単量体を必須として含有する単量体あるいは単量体混合物を重合した（メタ）アクリル系両性水溶性高分子（Ｂ）およびビニルアミン構造単位を有する水溶性高分子（Ｃ）の配合物からなる。カチオン性水溶性高分子（Ａ）あるいは両性水溶性高分子（Ｂ）のみの場合や、カチオン性水溶性高分子（Ａ）と両性水溶性高分子（Ｂ）をブレンドした場合、汚泥脱水時のケーキ含水率を低下させることはできるが、添加量が増加し処理コスト高になる。更に汚泥性状の変動に対応できないこともある。またビニルアミン構造単位を有する（Ｃ）のみでは、下水混合生汚泥や余剰汚泥脱水時のケーキ含水率を低下させることはできるが、ビニルアミン構造単位を有する水溶性高分子（Ｃ）自体の価格が高く処理コストが嵩む。また汚泥ｐＨが８前後と高い消化汚泥などでは、凝集性能が著しく低下し対応できない。そのため（Ａ）と（Ｂ）および（Ｃ）を配合することにより、ケーキ含水率の低下だけでなく処理コストの低減と対応可能な汚泥種類を広げることができる。 The aggregating agent of the present invention is a (meth) acrylic cationic water-soluble polymer (A) obtained by polymerizing a monomer or monomer mixture containing a specific (meth) acrylic cationic monomer as an essential component. And a (meth) acrylic amphoteric water-soluble polymer (B) obtained by polymerizing a monomer or monomer mixture containing a specific (meth) acrylic cationic monomer and an anionic monomer as essential It consists of a blend of a water-soluble polymer (C) having a vinylamine structural unit. When only the cationic water-soluble polymer (A) or the amphoteric water-soluble polymer (B), or when the cationic water-soluble polymer (A) and the amphoteric water-soluble polymer (B) are blended, during sludge dewatering Although the moisture content of the cake can be reduced, the amount of addition increases and the processing cost increases. Furthermore, it may not be possible to cope with fluctuations in sludge properties. In addition, only (C) having a vinylamine structural unit can reduce the moisture content of the cake during dewatering of sewage mixed raw sludge and excess sludge, but the price of the water-soluble polymer (C) itself having a vinylamine structural unit is high. Processing costs increase. In addition, digested sludge having a sludge pH as high as about 8 cannot significantly cope with the aggregation performance. Therefore, by blending (A), (B), and (C), it is possible to expand the types of sludge that can cope with not only a reduction in the moisture content of the cake but also a reduction in the processing cost.
ビニルアミン系水溶性高分子は、下水の混合生汚泥、同余剰汚泥、あるいは食品加工・水産加工排水の余剰汚泥など微生物処理の過程で発生した低分子化された有機物を不溶化・凝集する性能に特徴があると考えられるが、従来この作用を（メタ）アクリル系カチオン性あるいは両性高分子または両者の配合によって処理することは、なかなか困難であった。この理由の一つに（メタ）アクリル系カチオン性あるいは両性高分子は、分子量が非常に高く、架橋吸着作用による大きく強度の高いフロックを生成するには適していたが、微生物処理の過程で発生する汚泥は、親水性が高くしかも繊維分が少ない。このような汚泥を凝集させるには表面電荷の中和を必ずしも伴わない不溶化機能が必要と推定される。この機能に必要な要素は分子量、カチオン当量、親水性・疎水性のバランスなどが関係していると考えられるが、本発明においては、カチオン性水溶性高分子と両性水溶性高分子の分子量の調節、イオン性のバランス、更にビニルアミン構造単位を有する水溶性高分子を配合することにより達成できたと考えられる。 Vinylamine water-soluble polymers are characterized by their ability to insolubilize and agglomerate low-molecular-weight organic substances generated in the process of microorganisms, such as mixed raw sludge, sewage sludge, or excess sludge from food processing / fishery processing wastewater. However, it has been difficult to treat this action with a (meth) acrylic cationic or amphoteric polymer or a combination of both. One reason for this is that (meth) acrylic cationic or amphoteric polymers have a very high molecular weight and are suitable for producing large, high-strength flocs due to cross-linking and adsorption, but they are generated during microbial treatment. The sludge is highly hydrophilic and has a low fiber content. In order to agglomerate such sludge, it is presumed that an insolubilizing function not necessarily accompanied by neutralization of the surface charge is necessary. The elements necessary for this function are thought to be related to molecular weight, cation equivalent, balance between hydrophilicity and hydrophobicity, etc., but in the present invention, the molecular weights of the cationic water-soluble polymer and the amphoteric water-soluble polymer are It is thought that this could be achieved by blending a water-soluble polymer having a regulation, an ionic balance, and a vinylamine structural unit.
カチオン性水溶性高分子（Ａ）あるいは両性水溶性高分子（Ｂ）のみ、または両者の混合では、ビニルアミン構造単位を有する水溶性高分子に較べ良好な脱水状態に要する薬剤添加量は、２倍〜３倍要する。ビニルアミン構造単位を有する水溶性高分子（Ｃ）のみでは、薬品添加コストが多くなり、汚泥ｐＨの変動に対処できない場合がある。しかし、カチオン性水溶性高分子と両性水溶性高分子およびビニルアミン構造単位を有する水溶性高分子を配合すると、ビニルアミン構造単位を有する水溶性高分子と同等、あるいはそれ以上の脱水性を有することができ薬品コストが抑えられ、汚泥性状の変動に対しても安定して処理できる。この原因として以下の理由が考えられる。カチオン性水溶性高分子（Ａ）あるいは両性水溶性高分子（Ｂ）が、高分子間でコンプレックスを形成し、そのコンプレックスが汚泥中の親水性のコロイド成分に吸着して疎水化し微細なフロックを形成させ、その後ビニルアミン構造単位を有する水溶性高分子（Ｃ）がより大きくしかも緻密で強固なフロックに成長させるという構図が考えられる。 When the cationic water-soluble polymer (A) or the amphoteric water-soluble polymer (B) alone or a mixture of both, the amount of drug required for dehydration better than that of the water-soluble polymer having a vinylamine structural unit is doubled. It takes ~ 3 times. Only the water-soluble polymer (C) having a vinylamine structural unit increases the cost of chemical addition and may not be able to cope with fluctuations in sludge pH. However, when a cationic water-soluble polymer, an amphoteric water-soluble polymer, and a water-soluble polymer having a vinylamine structural unit are blended, the water-soluble polymer having a vinylamine structural unit may have a dehydrating property equal to or higher than that. The cost of chemicals can be reduced, and it is possible to stably treat sludge properties. The following reasons can be considered as this cause. The cationic water-soluble polymer (A) or the amphoteric water-soluble polymer (B) forms a complex between the polymers, and the complex adsorbs to the hydrophilic colloid component in the sludge to hydrophobize and form fine flocs. It can be considered that the water-soluble polymer (C) having a vinylamine structural unit is grown into a larger, more dense and strong floc.
本発明のカチオン性水溶性高分子（Ａ）と両性水溶性高分子（Ｂ）およびビニルアミン構造単位を有する水溶性高分子（Ｃ）の配合物からなる凝集処理剤のうちカチオン性水溶性高分子（Ａ）は、カチオン性単量体と必要により非イオン性単量体を含有させ、これら単量体混合物を重合し製造することができる。又、両性水溶性高分子（Ｂ）の場合は、カチオン性単量体とアニオン性単量体と必要により非イオン性単量体を含有させ、これら単量体混合物を重合し製造することができる。製品形態は、油中水型エマルジョン、粉末、塩水中分散液など特に限定はないが、特に好ましい形態は、油中水型エマルジョンあるいは粉末状タイプである。 The cationic water-soluble polymer of the aggregation treatment agent comprising the blend of the cationic water-soluble polymer (A) of the present invention, the amphoteric water-soluble polymer (B) and the water-soluble polymer (C) having a vinylamine structural unit (A) contains a cationic monomer and, if necessary, a nonionic monomer, and can be produced by polymerizing these monomer mixtures. In the case of the amphoteric water-soluble polymer (B), a cationic monomer, an anionic monomer and, if necessary, a nonionic monomer may be contained, and a mixture of these monomers may be polymerized. it can. The product form is not particularly limited, such as a water-in-oil emulsion, powder, or a dispersion in salt water, but a particularly preferred form is a water-in-oil emulsion or a powder type.
前記カチオン性水溶性高分子と両性水溶性高分子およびビニルアミン構造単位を有する水溶性高分子は、同様な形態であると配合が容易である。例えば三者が粉末である場合や、水と非混和性の炭化水素を連続相、前記カチオン性または両性水溶性高分子あるいはビニルアミン構造単位を有する水溶性高分子が、水溶性高分子水溶液を分散相とする油中水型エマルジョンである場合である。粉末の製造方法としては、単量体混合物をラジカル重合開始剤あるいは光増感剤と紫外光あるいは可視光、電子線などの照射によって重合を開始し重合物を得る。重合物の形態は、シートなど薄膜状のものあるいは直方体など厚みのある形態に重合し、その後粗砕し、ミートチョッパーなどのよって造粒し、乾燥、乾燥物の粉砕、篩い分けなどの工程を経て粉末状にすることが一般的である。又、前記油中水型エマルジョンを製造後、噴霧乾燥機中に油中水型エマルジョンを噴霧し、乾燥する方法がある。これは操作が簡便であり容易であるが、粒径が細かくなり、更に粒径調節の加工が必要である。また油中水型エマルジョンを直接乾燥機に入れ、一定時間乾燥し、塊状物を粉砕する方法もある。この方法は、乾燥温度や乾燥時間の管理に注意する必要がある。乾燥時間を長くしすぎる場合、あるいは乾燥温度が高すぎる場合などは、水溶性高分子に架橋反応が発生して水に溶解しなくなることがある。又、油中水型エマルジョンをエマルジョンブレイクすることにより塊状化させ、乾燥後細粒化した粉末状とすることもできる。前記カチオン性または両性水溶性高分子の粉末化の方法と、ビニルアミン構造単位を有する水溶性高分子は、別の方法により粉末化したものを配合することも可能である。 The cationic water-soluble polymer, the amphoteric water-soluble polymer, and the water-soluble polymer having a vinylamine structural unit can be easily blended in the same form. For example, when the three are powders, water is a water-immiscible hydrocarbon continuous phase, the cationic or amphoteric water-soluble polymer or a water-soluble polymer having a vinylamine structural unit is dispersed in a water-soluble polymer aqueous solution This is the case when the phase is a water-in-oil emulsion. As a method for producing the powder, the monomer mixture is polymerized by irradiation with a radical polymerization initiator or photosensitizer and ultraviolet light, visible light, electron beam or the like to obtain a polymer. The polymer form is polymerized into a thin form such as a sheet or a thick form such as a rectangular parallelepiped, then crushed, granulated with a meat chopper, etc., dried, pulverized dry matter, sieving, etc. After that, it is common to form a powder. There is also a method in which after the water-in-oil emulsion is produced, the water-in-oil emulsion is sprayed into a spray dryer and dried. This is simple and easy to operate, but the particle size becomes fine and further processing for adjusting the particle size is necessary. There is also a method in which a water-in-oil emulsion is directly put into a dryer and dried for a certain period of time to crush the lump. In this method, it is necessary to pay attention to the management of the drying temperature and the drying time. If the drying time is too long or the drying temperature is too high, a cross-linking reaction may occur in the water-soluble polymer and it may not be dissolved in water. Alternatively, the water-in-oil emulsion may be agglomerated by emulsion breaking, and dried to obtain a finely divided powder. The method of pulverizing the cationic or amphoteric water-soluble polymer and the water-soluble polymer having a vinylamine structural unit can be blended by pulverization by another method.
本発明のカチオン性水溶性高分子（Ａ）あるいは両性水溶性高分子（Ｂ）を製造するために、重合時に構造改質剤、すなわち高分子を構造変性する架橋性単量体を使用しても良い。この架橋性単量体は、単量体総量に対し質量で２０〜３００ｐｐｍ、また好ましくは５０〜３００ｐｐｍ存在させる。架橋性単量体の例としては、Ｎ，Ｎ−メチレンビス（メタ）アクリルアミド、トリアリルアミン、ジメタクリル酸エチレングリコール、ジメタクリル酸ジエチレングリコール、ジメタクリル酸トリエチレングリコール、ジメタクリル酸テトラエチレングリコール、ジメタクリル酸−１，３−ブチレングリコール、ジ（メタ）アクリル酸ポリエチレングリコール、Ｎ−ビニル（メタ）アクリルアミド、Ｎ−メチルアリルアクリルアミド、アクリル酸グリシジル、ポリエチレングリコールジグリシジルエーテル、アクロレイン、グリオキザール、ビニルトリメトキシシランなどがあるが、この場合の架橋剤としては、水溶性ポリビニル化合物がより好ましく、最も好ましいのはＮ，Ｎ−メチレンビス（メタ）アクリルアミドである。またギ酸ナトリウム、イソプロピルアルコール、メタリルスルホン酸ナトリウム等の連鎖移動剤を併用することも架橋性を調節する手法として効果的である。添加量としては、単量体総量に対し質量で０．００１〜１．０％、好ましくは０．０１〜０．１％存在させる。 In order to produce the cationic water-soluble polymer (A) or the amphoteric water-soluble polymer (B) of the present invention, a structural modifier, that is, a crosslinkable monomer that structurally modifies the polymer is used during polymerization. Also good. This crosslinkable monomer is present in a mass of 20 to 300 ppm, preferably 50 to 300 ppm, based on the total amount of monomers. Examples of the crosslinkable monomer include N, N-methylenebis (meth) acrylamide, triallylamine, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, and dimethacrylic acid. Acid-1,3-butylene glycol, polyethylene glycol di (meth) acrylate, N-vinyl (meth) acrylamide, N-methylallylacrylamide, glycidyl acrylate, polyethylene glycol diglycidyl ether, acrolein, glyoxal, vinyltrimethoxysilane In this case, the crosslinking agent is more preferably a water-soluble polyvinyl compound, and most preferably N, N-methylenebis (meth) acrylamide. Also, using a chain transfer agent such as sodium formate, isopropyl alcohol, sodium methallyl sulfonate, etc. is also effective as a method for adjusting the cross-linking property. The amount added is 0.001 to 1.0% by mass, preferably 0.01 to 0.1% by mass relative to the total amount of monomers.
本発明で使用するカチオン性単量体は、以下の様なものがある。すなわち、カチオン性水溶性高分子（Ａ）あるいは両性水溶性高分子（Ｂ）の重合時使用する単量体は、（メタ）アクリル酸ジメチルアミノエチルやジメチルアミノプロピル（メタ）アクリルアミドを炭素数１〜３のアルキル基、塩化ベンジルあるいは炭素数７〜２０のアルキル基あるいはアリール基を有するハロゲン化物による四級化物である。その例として一般式（１）であらわされる単量体は、（メタ）アクリロイルオキシエチルトリメチルアンモニウム塩化物、（メタ）アクリロイルオキシ−２−ヒドロキシプロピルトリメチルアンモニウム塩化物、（メタ）アクリロイルアミノプロピルトリメチルアンモニウム塩化物、（メタ）アクリロイルオキシエチルベンジルジメチルアンモニウム塩化物、（メタ）アクリロイルオキシ−２−ヒドロキシプロピルベンジルジメチルアンモニウム塩化物、（メタ）アクリロイルアミノプロピルベンジルジメチルアンモニウム塩化物、などである。また一般式（２）であらわされる単量体は、ジアリルメチルアンモニウム塩化物、ジアリルジメチルアンモニウム塩化物などがある。 The cationic monomers used in the present invention include the following. That is, the monomer used when polymerizing the cationic water-soluble polymer (A) or the amphoteric water-soluble polymer (B) is dimethylaminoethyl (meth) acrylate or dimethylaminopropyl (meth) acrylamide having 1 carbon atom. It is a quaternized product of a halide having an alkyl group of ˜3, benzyl chloride, an alkyl group of 7 to 20 carbon atoms or an aryl group. Examples of the monomer represented by the general formula (1) include (meth) acryloyloxyethyltrimethylammonium chloride, (meth) acryloyloxy-2-hydroxypropyltrimethylammonium chloride, (meth) acryloylaminopropyltrimethylammonium. Chloride, (meth) acryloyloxyethylbenzyldimethylammonium chloride, (meth) acryloyloxy-2-hydroxypropylbenzyldimethylammonium chloride, (meth) acryloylaminopropylbenzyldimethylammonium chloride, and the like. Examples of the monomer represented by the general formula (2) include diallylmethylammonium chloride and diallyldimethylammonium chloride.
両性水溶性高分子（Ｂ）を製造する場合は、上記ビニル系カチオン性単量体の他、ビニル系アニオン性単量体を併用する。その例としてはビニルスルホン酸、ビニルベンゼンスルホン酸あるいは２−アクリルアミド−２−メチルプロパンスルホン酸、メタクリル酸、アクリル酸、イタコン酸、マレイン酸、フタル酸あるいはｐ−カルボキシスチレン酸等が挙げられる。 When the amphoteric water-soluble polymer (B) is produced, a vinyl anionic monomer is used in combination with the vinyl cationic monomer. Examples thereof include vinyl sulfonic acid, vinyl benzene sulfonic acid or 2-acrylamido-2-methylpropane sulfonic acid, methacrylic acid, acrylic acid, itaconic acid, maleic acid, phthalic acid, and p-carboxystyrene acid.
また非イオン性単量体を共重合する場合は、（メタ）アクリルアミド、Ｎ,Ｎ−ジメチルアクリルアミド、アクリロニトリル、（メタ）アクリル酸−２−ヒドロキシエチル、ジアセトンアクリルアミド、Ｎ−ビニルピロリドン、Ｎ−ビニルホルムアミド、Ｎ−ビニルアセトアミド、アクリロイルモルホリン等が挙げられる。 When copolymerizing nonionic monomers, (meth) acrylamide, N, N-dimethylacrylamide, acrylonitrile, 2-hydroxyethyl (meth) acrylate, diacetone acrylamide, N-vinylpyrrolidone, N- Vinylformamide, N-vinylacetamide, acryloylmorpholine and the like can be mentioned.
これら単量体の共重合比率は、以下のようである。カチオン性単量体２０〜１００モル％、アニオン性単量体０〜２０モル％、非イオン性単量体０〜２０モル％である。しかし本発明では懸濁粒子の表面電荷の中和作用を第一の機能とするため、カチオン性は高いことが好ましく、カチオン性単量体９０〜１００モル％、アニオン性単量体０〜１０モル％、非イオン性単量体０〜１０モル％であることが更に好ましい。 The copolymerization ratio of these monomers is as follows. The cationic monomer is 20 to 100 mol%, the anionic monomer is 0 to 20 mol%, and the nonionic monomer is 0 to 20 mol%. However, in the present invention, since the neutralizing action of the surface charge of the suspended particles is the first function, the cationic property is preferably high, and the cationic monomer is 90 to 100 mol%, the anionic monomer is 0 to 10 It is more preferable that they are mol% and a nonionic monomer 0-10 mol%.
本発明のカチオン性水溶性高分子（Ａ）あるいは両性水溶性高分子（Ｂ）は、光散乱法による重量平均分子量で１００万〜１０００万が好ましく、より好ましくは１００万〜８００万、さらに好ましくは３００万〜６００万である。汚泥脱水剤は、親水性コロイドの表面電荷の中和が大きな役割としてあり、この作用には必ずしも超巨大な高分子量の水溶性高分子は必要なく、カチオン当量値が重要な役割を示す。しかし同時に架橋吸着による凝集作用によって締まった強固なフロックを形成させることも必要であり、一定以上の分子量が必要である。そのため重量平均分子量は、上記の範囲となる。 The cationic water-soluble polymer (A) or amphoteric water-soluble polymer (B) of the present invention preferably has a weight average molecular weight of 1,000,000 to 10,000,000, more preferably 1,000,000 to 8,000,000, still more preferably. Is 3 to 6 million. The sludge dehydrating agent plays a major role in neutralizing the surface charge of the hydrophilic colloid, and this action does not necessarily require a super-high molecular weight water-soluble polymer, and the cation equivalent value plays an important role. However, at the same time, it is necessary to form a strong floc that is tightened by aggregating action due to cross-linking adsorption, and a molecular weight higher than a certain level is required. Therefore, a weight average molecular weight becomes said range.
ビニルアミン構造単位を有する水溶性高分子（Ｃ）の製造法に関しては、特開平６−６５３２９号公報に開示されている。本発明で使用するポリビニルアミンおよびポリビニルアミン繰り返し単位を有する水溶性共重合物は、Ｎ−ビニルホルムアミド重合物あるいは共重合物を重合体中のホルミル基を変性することにより容易に得ることができる。すなわちＮ−ビニルホルムアミドと他の共重合可能な単量体とのモル比が、通常２０：８０〜１００：０の混合物、好ましくは、４０：６０〜１００：０の混合物をラジカル重合開始剤の存在下、重合することにより製造される。 A method for producing a water-soluble polymer (C) having a vinylamine structural unit is disclosed in JP-A-6-65329. The water-soluble copolymer having a polyvinylamine and a polyvinylamine repeating unit used in the present invention can be easily obtained by modifying a formyl group in the polymer with an N-vinylformamide polymer or copolymer. That is, the molar ratio of N-vinylformamide to other copolymerizable monomer is usually a mixture of 20:80 to 100: 0, preferably 40:60 to 100: 0. It is produced by polymerizing in the presence.
酸あるいはアルカリによりホルミル基を加水分解するため、共重合する単量体の一部も加水分解され、カルボキシル基が生成する場合が多い。そのため共重合する場合は、アクリロニトリルなどが共重合する場合便利である。その他アクリルアミド、アクリル酸メチル、アクリル酸エチル、アクリル酸ｎプロピル、アクリル酸−２−ヒドロキシエチル、メタクリル酸エチル、メタクリル酸ｎプロピル、メタクリル酸イソプロピル、メタクリル酸ｎブチル、メタクリル酸イソブチル、メタクリル酸−ｓｅｃブチル、メタクリル酸−２−ヒドロキシエチルなどがあげられる。これら単量体は、アニオン性基が生成するので、共重合体中のモル比は、２０モル％未満であることが好ましい。 Since the formyl group is hydrolyzed with an acid or alkali, a part of the copolymerized monomer is also hydrolyzed to generate a carboxyl group in many cases. Therefore, when copolymerizing, it is convenient when acrylonitrile or the like is copolymerized. Other acrylamide, methyl acrylate, ethyl acrylate, n-propyl acrylate, 2-hydroxyethyl acrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, methacrylic acid-sec Examples thereof include butyl and 2-hydroxyethyl methacrylate. Since these monomers generate anionic groups, the molar ratio in the copolymer is preferably less than 20 mol%.
上記のＮ−ビニルホルムアミド共重合物を製造する重合方法としては、塊状重合、水および種々の有機溶媒を用いる溶液重合、沈殿重合のいずれも用いる事が出来る。好ましい重合溶媒としては、水、沸点６０〜１１０℃の有機溶媒および、水と沸点６０〜１１０℃の親水性有機溶媒の混合物が使用される。単量体を溶液状で重合する場合には、目的とする重合体の分子量、重合発熱を考慮して単量体の濃度、重合方法、および重合反応器の形状が適宜選択され、例えば以下の方法によって重合が行われる。すなわち、単量体濃度５〜２０質量％の溶液状で重合を開始し、重合体を溶液状または、沈殿物として得る方法、単量体濃度２０〜６０質量％の条件下重合を開始し、重合物と溶媒を含むゲル状物または析出物として得る方法、単量体濃度２０〜６０質量％の溶液を、単量体が溶解しない溶媒中で乳化または分散状態で重合する方法等が例示される。 As a polymerization method for producing the above N-vinylformamide copolymer, any of bulk polymerization, solution polymerization using water and various organic solvents, and precipitation polymerization can be used. As a preferable polymerization solvent, water, an organic solvent having a boiling point of 60 to 110 ° C., and a mixture of water and a hydrophilic organic solvent having a boiling point of 60 to 110 ° C. are used. When the monomer is polymerized in the form of a solution, the monomer concentration, polymerization method, and shape of the polymerization reactor are appropriately selected in consideration of the molecular weight of the target polymer and polymerization heat generation. Polymerization is carried out by the method. That is, polymerization is started in the form of a solution having a monomer concentration of 5 to 20% by mass, a method for obtaining the polymer as a solution or as a precipitate, polymerization is started under the conditions of a monomer concentration of 20 to 60% by mass, Examples include a method of obtaining a gel or a precipitate containing a polymer and a solvent, and a method of polymerizing a solution having a monomer concentration of 20 to 60% by mass in an emulsified or dispersed state in a solvent in which the monomer is not dissolved. The
ラジカル重合開始剤としては、通常水溶性または親水性の単量体の重合に用いられる一般的な開始剤のいずれもが使用されるが、重合体を収率良く得る為には、アゾ化合物が好ましい。重合溶媒に水を使用する場合、水溶性のアゾ化合物が好ましく、その例としては、２，２′−アゾビス−２−アミジノプロパンの塩酸塩および酢酸塩、４，４′−アゾビス−４−シアノ吉草酸のナトリウム塩、アゾビス−Ｎ，Ｎ′−ジメチレンイソブチルアミジンの塩酸塩および硫酸塩が挙げられる。これら重合開始剤の使用量は、通常単量体の重量に対して０．０１〜１質量％の範囲である。また、重合反応は、一般に、不活性ガス気流下、３０〜１００℃の温度で実施される。 As the radical polymerization initiator, any of general initiators usually used for the polymerization of water-soluble or hydrophilic monomers is used. In order to obtain a polymer in good yield, an azo compound is used. preferable. When water is used as the polymerization solvent, a water-soluble azo compound is preferable, and examples thereof include 2,2'-azobis-2-amidinopropane hydrochloride and acetate, 4,4'-azobis-4-cyano. Examples include sodium salt of valeric acid, hydrochloride and sulfate of azobis-N, N'-dimethyleneisobutylamidine. The amount of these polymerization initiators used is usually in the range of 0.01 to 1% by mass with respect to the weight of the monomer. The polymerization reaction is generally performed at a temperature of 30 to 100 ° C. under an inert gas stream.
得られたＮ−ビニルホルムアミド共重合体は、そのままの溶液状もしくは分散状で、あるいは希釈、もしくは、公知の方法で脱水または乾燥して粉末状としたのち変性することにより、新規なるビニルアミン共重合体とすることができる。この際に用いられる変性方法としては、Ｎ−ビニルホルムアミド共重合体を塩基性および酸性条件下変性するいずれの方法も用いることができる。水中で塩基性加水分解すると重合体中のエステル基がカルボキシル基に変わり、アニオン性基を多く含有する両性共重合体を生ずる傾向があり、水溶性の良い両性重合体の勝れた製造法となる。しかし、疎水性を付与したポリビニルアミンを製造するためには、酸性条件下で変性することが好ましい。Ｎ−ビニルホルムアミド共重合体の好ましい変性方法としては、水中で酸性加水分解する方法、水を含有するアルコールなどの親水性溶媒中で酸性加水分解する方法、酸性条件下、加アルコール分解し、ホルミル基をギ酸エステルとして分離しつつ変性する方法などが例示されるが、特に好ましいのは、酸性条件下の加アルコール分解である。この方法により、カルボキシル基を実質的に含有しないビニルアミン共重合体を得ることができる。 The obtained N-vinylformamide copolymer can be used in the form of a new vinylamine copolymer by modification in the form of a solution or dispersion as it is, or by dilution or dehydration or drying by a known method to form a powder. Can be combined. As the modification method used in this case, any method of modifying the N-vinylformamide copolymer under basic and acidic conditions can be used. When basic hydrolysis is carried out in water, the ester group in the polymer tends to be converted to a carboxyl group, which tends to yield an amphoteric copolymer containing a large amount of anionic groups. Become. However, in order to produce a polyvinylamine imparted with hydrophobicity, it is preferably modified under acidic conditions. As a preferable modification method of the N-vinylformamide copolymer, there are a method of acid hydrolysis in water, a method of acid hydrolysis in a hydrophilic solvent such as alcohol containing water, alcoholysis under acidic conditions, and formyl. Examples thereof include a method of modifying the group while separating it as a formate ester, and particularly preferred is alcoholysis under acidic conditions. By this method, a vinylamine copolymer substantially free of carboxyl groups can be obtained.
また、酸性変性に使用される変性剤としては、強酸性に作用する化合物ならばいずれも使用することが可能であり、例えば、塩酸、臭素酸、フッ化水素酸、硫酸、硝酸、燐酸、スルファミン酸、アルカンスルホン酸等が挙げられる。変性剤の使用量は、重合体中のホルミル基に対して、通常０．１〜２倍モルの範囲から目的の変性率に応じて適宜選択される。また、変性反応は通常４０〜１００℃の条件で実施される。 As the modifier used for acid modification, any compound that acts on strong acid can be used, for example, hydrochloric acid, bromic acid, hydrofluoric acid, sulfuric acid, nitric acid, phosphoric acid, sulfamine. Examples include acids and alkane sulfonic acids. The usage-amount of modifier | denaturant is suitably selected according to the target modification | denaturation rate from the range of 0.1-2 times mole normally with respect to the formyl group in a polymer. Further, the denaturation reaction is usually carried out at 40 to 100 ° C.
上記ビニルアミン構造単位を有する水溶性高分子（Ｃ）中のビニルアミン構造単位の全構成に対する比率は、１０〜９０モル％であることが好ましく、３０〜７５モル％であることが更に好ましい。また光散乱法による重量平均分子量は、１００万〜１０００万が好ましく、より好ましくは３００万〜７００万である。 The ratio of the vinylamine structural unit in the water-soluble polymer (C) having the vinylamine structural unit to the total constitution is preferably 10 to 90 mol%, and more preferably 30 to 75 mol%. The weight average molecular weight by the light scattering method is preferably 1 million to 10 million, more preferably 3 million to 7 million.
カチオン性水溶性高分子（Ａ）と両性水溶性高分子（Ｂ）およびビニルアミン構造単位を有する水溶性高分子（Ｃ）とも油中水型エマルジョンを製造する場合の分散媒として使用する炭化水素からなる油状物質の例としては、パラフィン類あるいは灯油、軽油、中油等の鉱油、あるいはこれらと実質的に同じ範囲の沸点や粘度等の特性を有する炭化水素系合成油、あるいはこれらの混合物があげられる。含有量としては、油中水型エマルジョン全量に対して２０質量％〜５０質量％の範囲であり、好ましくは２０質量％〜３５質量％の範囲である。 The cationic water-soluble polymer (A), the amphoteric water-soluble polymer (B), and the water-soluble polymer (C) having a vinylamine structural unit are both used as a dispersion medium in the production of a water-in-oil emulsion. Examples of such oily substances include paraffins, mineral oils such as kerosene, light oil, and middle oil, or hydrocarbon synthetic oils having characteristics such as boiling point and viscosity in substantially the same range as these, or mixtures thereof. . As content, it is the range of 20 mass%-50 mass% with respect to the water-in-oil type emulsion whole quantity, Preferably it is the range of 20 mass%-35 mass%.
油中水型エマルジョンを形成するに有効な量とＨＬＢを有する少なくとも一種類の界面活性剤の例としては、ＨＬＢ３〜１１のノニオン性界面活性剤であり、その具体例としては、ソルビタンモノオレート、ソルビタンモノステアレート、ソルビタンモノパルミテート、ポリオキシエチレンノニルフェニルエーテル等が挙げられる。これら界面活性剤の添加量としては、油中水型エマルジョン全量に対して０．５〜１０質量％であり、好ましくは1〜５質量％の範囲である。 Examples of at least one surfactant having an amount effective to form a water-in-oil emulsion and HLB are HLB 3-11 nonionic surfactants, specific examples of which include sorbitan monooleate, Examples include sorbitan monostearate, sorbitan monopalmitate, and polyoxyethylene nonylphenyl ether. The amount of these surfactants to be added is 0.5 to 10% by mass, preferably 1 to 5% by mass, based on the total amount of the water-in-oil emulsion.
重合後は、転相剤と呼ばれる親水性界面活性剤を添加して油の膜で被われたエマルジョン粒子が水になじみ易くし、中の水溶性高分子が溶解しやすくする処理を行ない、水で希釈しそれぞれの用途に用いる。親水性界面活性剤の例としては、カチオン性界面活性剤やＨＬＢ９〜１５のノ二オン性界面活性剤であり、ポリオキシエチレンポリオキシプロピレンアルキルエーテル系、ポリオキシエチレンアルコールエーテル系等である。 After the polymerization, a hydrophilic surfactant called a phase inversion agent is added to make the emulsion particles covered with the oil film easy to adjust to water, and the water-soluble polymer therein is easily dissolved. Dilute with and use for each application. Examples of hydrophilic surfactants are cationic surfactants and HLB 9-15 nonionic surfactants, such as polyoxyethylene polyoxypropylene alkyl ethers and polyoxyethylene alcohol ethers.
重合条件は通常、使用する単量体や共重合モル％によって適宜決めていき、温度としては０〜１００℃の範囲で行なう。特に油中水型エマルジョン重合法を適用する場合は、２０〜８０℃、好ましくは２０〜６０℃の範囲で行なう。重合開始はラジカル重合開始剤を使用する。これら開始剤は油溶性あるいは水溶性のどちらでも良く、アゾ系、過酸化物系、レドックス系何れでも重合することが可能である。油溶性アゾ系開始剤の例としては、２、２’−アゾビスイソブチロニトリル、１、１−アゾビスシクロヘキサンカルボニトリル、２、２’−アゾビス−２−メチルブチロニトリル、２、２’−アゾビス−２−メチルプロピオネート、４、４’−アゾビス−（４−メトキシ−２、４−ジメチル）バレロニトリル等が挙げられる。 The polymerization conditions are usually appropriately determined depending on the monomer used and the copolymerization mol%, and the temperature is in the range of 0 to 100 ° C. In particular, when the water-in-oil emulsion polymerization method is applied, it is carried out in the range of 20 to 80 ° C, preferably 20 to 60 ° C. For the initiation of polymerization, a radical polymerization initiator is used. These initiators may be either oil-soluble or water-soluble, and can be polymerized by any of azo, peroxide, and redox systems. Examples of oil-soluble azo initiators are 2,2′-azobisisobutyronitrile, 1,1-azobiscyclohexanecarbonitrile, 2,2′-azobis-2-methylbutyronitrile, 2,2 Examples include '-azobis-2-methylpropionate, 4,4'-azobis- (4-methoxy-2,4-dimethyl) valeronitrile.
水溶性アゾ開始剤の例としては、２、２’−アゾビス（アミジノプロパン）二塩化水素化物、２、２’−アゾビス[２−（５−メチル−イミダゾリン−２−イル）プロパン]二塩化水素化物、４、４’−アゾビス（４−シアノ吉草酸）等が挙げられる。またレドックス系の例としては、ペルオキソ二硫酸アンモニウムと亜硫酸ナトリウム、亜硫酸水素ナトリウム、トリメチルアミン、テトラメチルエチレンジアミン等との組み合わせが挙げられる。更に過酸化物の例としては、ペルオキソ二硫酸アンモニウムあるいはカリウム、過酸化水素、ベンゾイルペルオキサイド、ラウロイルペルオキサイド、オクタノイルペルオキサイド、サクシニックペルオキサイド、ｔ−ブチルペルオキシ−２−エチルヘキサノエート等を挙げることができる。 Examples of water soluble azo initiators are 2,2'-azobis (amidinopropane) dichloride, 2,2'-azobis [2- (5-methyl-imidazolin-2-yl) propane] hydrogen dichloride And 4,4′-azobis (4-cyanovaleric acid). Examples of redox systems include a combination of ammonium peroxodisulfate and sodium sulfite, sodium hydrogen sulfite, trimethylamine, tetramethylethylenediamine and the like. Examples of peroxides include ammonium or potassium peroxodisulfate, hydrogen peroxide, benzoyl peroxide, lauroyl peroxide, octanoyl peroxide, succinic peroxide, t-butylperoxy-2-ethylhexanoate, and the like. Can be mentioned.
本発明の凝集処理剤は、特定の単量体を重合したカチオン性水溶性高分子と両性水溶性高分子およびビニルアミン構造単位を有する水溶性高分子との配合物である。また本発明の水溶性高分子の処理対象として推奨される汚泥は、消化汚泥や各産業排水の微生物処理より発生する余剰汚泥など繊維分の少ない汚泥である。あるいは余剰汚泥と生汚泥の混合物など親水性コロイドなど親水性の高い成分を多く含む汚泥である。これら繊維分の少ない汚泥に対して、カチオン性水溶性高分子のカチオン性基と両性水溶性高分子のアニオン性基が高分子間でイオンコンプレックスを形成する。このイオンコンプレックスが汚泥中の親水性のコロイド成分に吸着して疎水化し微細なフロックを形成させ、更にビニルアミン系水溶性高分子により、フロックがより大きく、且つ緻密で強固なフロックに成長させると考えられる。カチオン性水溶性高分子と両性水溶性高分子のみでは、ある一定以上の添加量で含水率は低下しなくなるがビニルアミン構造単位を有する水溶性高分子を配合することにより、添加量を増加しても含水率が更に低下する。ビニルアミン構造単位を有する水溶性高分子と両性水溶性高分子でも添加量増加による含水率低減効果は認められるもののビニルアミン構造単位を有する水溶性高分子の添加コストが掛かることになり、効率的ではない。カチオン性水溶性高分子と両性水溶性高分子およびビニルアミン構造単位を有する水溶性高分子の三者を配合することにより効率的な良好な含水率低減効果が得られる。 The aggregation treatment agent of the present invention is a blend of a cationic water-soluble polymer obtained by polymerizing a specific monomer, an amphoteric water-soluble polymer and a water-soluble polymer having a vinylamine structural unit. Moreover, the sludge recommended as a treatment target of the water-soluble polymer of the present invention is sludge having a low fiber content such as digested sludge and surplus sludge generated by microbial treatment of each industrial wastewater. Or it is a sludge which contains many highly hydrophilic components, such as hydrophilic colloids, such as a mixture of surplus sludge and raw sludge. For sludge having a low fiber content, the cationic group of the cationic water-soluble polymer and the anionic group of the amphoteric water-soluble polymer form an ion complex between the polymers. The ion complex is adsorbed on the hydrophilic colloidal component in the sludge to be hydrophobized to form fine flocs, and further, the vinylamine water-soluble polymer will cause the flocs to grow into dense, strong flocs. It is done. With only the cationic water-soluble polymer and the amphoteric water-soluble polymer, the water content does not decrease at a certain amount or more, but by adding a water-soluble polymer having a vinylamine structural unit, the amount added can be increased. However, the water content is further reduced. Water-soluble polymers with vinylamine structural units and amphoteric water-soluble polymers are not efficient, although the water content reduction effect by increasing the amount added is recognized, but the cost of adding water-soluble polymers with vinylamine structural units increases. . By blending a cationic water-soluble polymer, an amphoteric water-soluble polymer, and a water-soluble polymer having a vinylamine structural unit, an efficient and good moisture content reduction effect can be obtained.
ビニルアミン構造単位を有する水溶性高分子は、下水の混合生汚泥、同余剰汚泥、あるいは食品加工・水産加工排水の余剰汚泥など微生物処理の過程で発生した低分子化された有機物を不溶化・凝集する性能に特徴があると考えられるが、従来この作用を（メタ）アクリル系カチオン性あるいは両性高分子によって処理することは、なかなか困難であった。この理由の一つに（メタ）アクリル系カチオン性あるいは両性高分子は、分子量が非常に高く、架橋吸着作用による大きく強度の高いフロックを生成するには適していたが、微生物処理の過程で発生する親水性の高い汚泥を、表面電荷の中和や必ずしも表面電荷の中和を伴わない不溶化機能は低かった。これには分子量、カチオン当量、親水性・疎水性のバランスなど影響していると考えられるが、本発明においては、これらの因子を分子量の調節、イオン性のバランス、更にビニルアミン構造単位を有する水溶性高分子を配合することにより疎水化し調節することができたと考えられる。 Water-soluble polymers with vinylamine structural units insolubilize and agglomerate low molecular weight organic substances generated during microbial treatment, such as mixed raw sludge of sewage, excess sludge, or excess sludge from wastewater from food processing and fishery processing. Although it is thought that there is a characteristic in performance, it has been difficult to treat this action with a (meth) acrylic cationic or amphoteric polymer. One reason for this is that (meth) acrylic cationic or amphoteric polymers have a very high molecular weight and are suitable for producing large, high-strength flocs due to cross-linking and adsorption, but they are generated during microbial treatment. The insolubilizing function of the highly hydrophilic sludge that does not involve neutralization of the surface charge or necessarily neutralization of the surface charge was low. This is thought to have an effect on molecular weight, cation equivalent, hydrophilic / hydrophobic balance, etc. In the present invention, these factors are used to control molecular weight, balance ionicity, and water-soluble water containing vinylamine structural units. It is thought that it was able to be hydrophobized and adjusted by adding a functional polymer.
本発明の水溶性高分子からなる凝集処理剤は、下水、し尿、産業排水の処理で生じる有機性汚泥（いわゆる生汚泥、余剰汚泥、混合生汚泥、消化汚泥、凝沈・浮上汚泥およびこれらの混合物）に通常０．１〜０．２質量％水溶液として添加される。添加量は、対汚泥固形分として０．２〜２質量％であり、好ましくは０．３〜１．０質量％である。対象とする汚泥に特に限定されないが、繊維分の少ない汚泥、有機分含有量（ＶＳＳ／ＳＳ）の高い汚泥、腐敗度の高い汚泥に対し特に有効であり好ましい。 The coagulation treatment agent comprising the water-soluble polymer of the present invention is an organic sludge (so-called raw sludge, surplus sludge, mixed raw sludge, digested sludge, coagulation / floating sludge, and these sludges generated by the treatment of sewage, human waste, and industrial wastewater. The mixture is usually added as a 0.1 to 0.2% by mass aqueous solution. The addition amount is 0.2 to 2% by mass, preferably 0.3 to 1.0% by mass, as solid content with respect to sludge. Although not particularly limited to the target sludge, it is particularly effective and preferable for sludge having a low fiber content, sludge having a high organic content (VSS / SS), and sludge having a high degree of spoilage.
カチオン性水溶性高分子（Ａ）と両性水溶性高分子（Ｂ）の配合比は質量で、１０：９０〜９０：１０の範囲である。カチオン性水溶性高分子（Ａ）および両性水溶性高分子（Ｂ）とビニルアミン構造単位を有する水溶性高分子（Ｃ）の配合比は質量で、（Ａ）＋（Ｂ）：（Ｃ）＝２０：８０〜８０：２０が好ましく、より好ましくは（Ａ）＋（Ｂ）：（Ｃ）＝３０：７０〜７０：３０である（いずれも質量％表示）。ビニルアミン構造単位を有する水溶性高分子（Ｃ）が全体に対し２０質量％未満では脱水ケーキ含水率が低下せず、８０質量％より高くなると薬品コストが掛かることになり効率的ではない。 The mixing ratio of the cationic water-soluble polymer (A) and the amphoteric water-soluble polymer (B) is in the range of 10:90 to 90:10 by mass. The mixing ratio of the cationic water-soluble polymer (A) and the amphoteric water-soluble polymer (B) to the water-soluble polymer (C) having a vinylamine structural unit is expressed by mass, and (A) + (B) :( C) = 20: 80-80: 20 are preferable, More preferably, it is (A) + (B) :( C) = 30: 70-70: 30 (all are mass% display). If the water-soluble polymer (C) having a vinylamine structural unit is less than 20% by mass with respect to the whole, the moisture content of the dehydrated cake does not decrease, and if it exceeds 80% by mass, the chemical cost is increased and it is not efficient.
本発明では両性水溶性高分子（Ｂ）を配合するため溶液ｐＨが約５〜約９の範囲でイオンコンプレックスを形成し溶液が白濁するが、このイオンコンプレックスが生成した状態で汚泥など処理対照に添加すると、性能が低下する。これは、ｐＨが５付近より高い範囲では本発明で使用する（メタ）アクリル系水溶性高分子が加水分解を受け、劣化しやすくなることが原因である。これを防ぐために酸性物質を配合する酸性物質としては、無機酸、有機酸いずれも可能であり、塩酸、硫酸、硝酸、スルファミン酸、コハク酸、クエン酸、アジピン酸などが例示でき、特にスルファミン酸、コハク酸、クエン酸、アジピン酸など単体で固体の酸性物質が好ましく、添加量として水溶性高分子の固形分換算として、５〜２０質量％であり、好ましくは７〜１５質量％の範囲であり、０．１質量％濃度に溶解してもｐＨが４以下を確保するよう添加量を調整することが好ましい。 In the present invention, since the amphoteric water-soluble polymer (B) is blended, an ion complex is formed when the solution pH is in the range of about 5 to about 9, and the solution becomes cloudy. When added, performance decreases. This is because the (meth) acrylic water-soluble polymer used in the present invention is subject to hydrolysis and easily deteriorates when the pH is higher than about 5. In order to prevent this, the acidic substance can be an inorganic acid or an organic acid, and examples thereof include hydrochloric acid, sulfuric acid, nitric acid, sulfamic acid, succinic acid, citric acid, and adipic acid. , Succinic acid, citric acid, adipic acid, and the like are preferably solid acidic substances. The addition amount is 5 to 20% by mass, preferably 7 to 15% by mass in terms of solid content of the water-soluble polymer. Yes, it is preferable to adjust the addition amount so as to ensure that the pH is 4 or less even when dissolved to a concentration of 0.1% by mass.
また本発明の汚泥脱水剤は、単独で汚泥脱水に使用しても良いが、無機凝集剤と併用することにより脱水効果がより向上する場合がある。該無機凝集剤としては、塩鉄、硫鉄、ポリ鉄、ＰＡＣ、硫酸バンドなどが挙げられる。汚泥に対する添加量は、通常汚泥固形分に対し０．１〜２質量％、好ましくは０．３〜１．０質量％である。 The sludge dewatering agent of the present invention may be used alone for sludge dewatering, but the dewatering effect may be further improved by using it together with an inorganic flocculant. Examples of the inorganic flocculant include salt iron, iron sulfate, polyiron, PAC, and sulfuric acid band. The addition amount with respect to sludge is 0.1-2 mass% normally with respect to sludge solid content, Preferably it is 0.3-1.0 mass%.
使用する脱水機の種類は、ベルトプレス、遠心脱水機、スクリュープレス、多重円板脱水機、ロータリープレスなどに対応できる。 The type of dehydrator used can correspond to a belt press, a centrifugal dehydrator, a screw press, a multi-disc dehydrator, a rotary press, and the like.
以下に実施例をあげて本発明を詳細に説明するが、本発明はこれら実施例により限定されるものではない。 EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples.
カチオン性水溶性高分子（Ａ）として試料−１〜７、１２〜１８、両性水溶性高分子（Ｂ）として試料−８〜１１、１９〜２２、ビニルアミン構造単位を有する水溶性高分子（Ｃ）として試料−２３〜２６を用意し表１に示した。 Samples 1 to 7 and 12 to 18 as the cationic water-soluble polymer (A), Samples 8 to 11 and 19 to 22 as the amphoteric water-soluble polymer (B), a water-soluble polymer having a vinylamine structural unit (C Samples 23 to 26 were prepared as shown in Table 1.
（表１）
ＤＭＱ；アクリロイルオキシエチルトリメチルアンモニウムクロリド
ＤＭＣ；メタクリロイルオキシエチルトリメチルアンモニウムクロリド
ＤＭＢＺ；アクリロイルオキシエチルジメチルベンジルアンモニウムクロリド
ＤＤ；ジアリルジメチルアンモニウムクロリド
ＡＡＣ；アクリル酸
ＡＡＭ；アクリルアミド
ＶＡＭ；ビニルアミン構造単位含有量（モル％）
ＥＭ；油中水型エマルジョン
Ｐ ；粉末
(Table 1)
DMQ; acryloyloxyethyltrimethylammonium chloride DMC; methacryloyloxyethyltrimethylammonium chloride DMBZ; acryloyloxyethyldimethylbenzylammonium chloride DD; diallyldimethylammonium chloride AAC; acrylic acid AAM; acrylamide VAM; vinylamine structural unit content (mol%)
EM; water-in-oil emulsion P; powder
（カチオン性水溶性高分子（Ａ）と両性水溶性高分子（Ｂ）およびビニルアミン構造単位を有する水溶性高分子の配合）
カチオン性水溶性高分子（Ａ）試料−１〜７と両性水溶性高分子（Ｂ）試料−８〜１1およびビニルアミン構造単位を有する水溶性高分子（Ｃ）を配合し本発明の凝集処理剤を調製した。結果を表２に示す。
(Composition of cationic water-soluble polymer (A), amphoteric water-soluble polymer (B) and water-soluble polymer having a vinylamine structural unit)
Aggregation treatment agent of the present invention by blending cationic water-soluble polymer (A) samples -1 to 7, amphoteric water-soluble polymer (B) samples -8 to 11 and water-soluble polymer (C) having a vinylamine structural unit Was prepared. The results are shown in Table 2.
（比較例１）
カチオン性水溶性高分子（Ａ）と両性水溶性高分子（Ｂ）およびビニルアミン構造単位を有する水溶性高分子（Ｃ）の内、何れか二種を配合し比較試料−１〜８の凝集処理剤を調製した。結果を表２に示す。
(Comparative Example 1)
Aggregation treatment of Comparative Samples 1 to 8 by mixing any two of the cationic water-soluble polymer (A), the amphoteric water-soluble polymer (B) and the water-soluble polymer (C) having a vinylamine structural unit An agent was prepared. The results are shown in Table 2.
（表２）
配合比；質量比
(Table 2)
Mixing ratio; mass ratio
下水消化汚泥（ｐＨ７．７５、ＳＳ分２８，１００ｍｇ／Ｌ）を用い、本発明の両性水溶性高分子を用い汚泥脱水試験を実施した。２００ｍＬをポリビ−カ−に採取し、表２の試料−２７〜４０をそれぞれ対汚泥ＳＳ分０．８０％（懸濁粒子質量％）加え、ビーカー移し替え攪拌２０回行った後、Ｔ−１１７９Ｌの濾布（ナイロン製）により濾過し、１０秒後の濾液量の測定、及びフロック強度（大きさ）を目視により測定した。その後５０秒間濾過した汚泥をプレス圧３Ｋｇ／ｍ2で１分間脱水する。その後、濾布剥離性を目視によりチェックし、ケ−キ含水率（１０５℃で２０ｈｒ乾燥）を測定した。結果を表３に示す。 A sludge dewatering test was conducted using sewage digested sludge (pH 7.75, SS content 28, 100 mg / L) using the amphoteric water-soluble polymer of the present invention. 200 mL was collected in a polyvinylcer, and samples 27 to 40 in Table 2 were added to each sludge SS content 0.80% (mass% of suspended particles), transferred to a beaker and stirred 20 times, and then T-1179L. The filter cloth (made of nylon) was filtered, and the amount of filtrate after 10 seconds and the floc strength (size) were measured visually. Thereafter, the sludge filtered for 50 seconds is dehydrated at a press pressure of 3 kg / m 2 for 1 minute. Thereafter, the filter cloth peelability was visually checked, and the cake water content (dried at 105 ° C. for 20 hours) was measured. The results are shown in Table 3.
(比較例１)実施例２と同様な操作により、比較試料−１〜８に関して試験を実施した。結果を表３に示す。 (Comparative Example 1) By the same operation as in Example 2, the test was performed on Comparative Samples 1 to 8. The results are shown in Table 3.
（表３）
フロック径：ｍｍ、１０秒後濾液量：ｍＬ、ケーキ含水率：質量％
(Table 3)
Flock diameter: mm, 10 seconds later Filtrate: mL, cake moisture content: mass%
試作−２７〜４０は、比較試料−１〜８に比べて濾液量（凝集機能に関係）、ケーキ含水率とも処理効果が向上していることが分かる。 It can be seen that trial manufactures -27 to 40 have improved treatment effects with respect to the filtrate amount (related to the coagulation function) and the cake moisture content as compared with comparative samples -1 to 8.
下水混合生汚泥（ｐＨ６．６１、ＳＳ分２１，３００ｍｇ／Ｌ）を用い、本発明の水溶性高分子組成物を用い汚泥脱水試験を実施した。２００ｍＬをポリビ−カ−に採取し、表４の粉末化した試料−２７〜４０をそれぞれ対汚泥ＳＳ分０．７５％（懸濁粒子質量％）加え、ビーカー移し替え攪拌２０回行った後、Ｔ−１１７９Ｌの濾布（ナイロン製）により濾過し、１０秒後の濾液量の測定、及びフロック強度（大きさ）を目視により測定した。その後５０秒間濾過した汚泥をプレス圧３Ｋｇ／ｍ2で１分間脱水する。その後、濾布剥離性を目視によりチェックし、ケ−キ含水率（１０５℃で２０ｈｒ乾燥）を測定した。結果を表６に示す。 Using sludge mixed raw sludge (pH 6.61, SS content 21,300 mg / L), a sludge dewatering test was carried out using the water-soluble polymer composition of the present invention. After 200 mL was collected in a polycarbonate, powdered samples 27 to 40 in Table 4 were added to each sludge SS content 0.75% (suspension particle mass%), the beaker was transferred and stirred 20 times, The mixture was filtered through a T-1179L filter cloth (made of nylon), and the filtrate amount after 10 seconds and the floc strength (size) were measured visually. Thereafter, the sludge filtered for 50 seconds is dehydrated at a press pressure of 3 kg / m 2 for 1 minute. Thereafter, the filter cloth peelability was visually checked, and the cake water content (dried at 105 ° C. for 20 hours) was measured. The results are shown in Table 6.
(比較例２)
実施例３と同様な操作により、比較試料−１〜８に関して試験を実施した。結果を表４に示す。
(Comparative Example 2)
Tests were performed on Comparative Samples 1 to 8 in the same manner as in Example 3. The results are shown in Table 4.
（表４）
フロック径：ｍｍ、１０秒後濾液量：ｍＬ、ケーキ含水率：質量％
(Table 4)
Flock diameter: mm, 10 seconds later Filtrate: mL, cake moisture content: mass%
本発明の範囲である試料−２７〜４０は、比較試料−１〜８に比べて濾液量（凝集機能に関係）、ケーキ含水率とも処理効果が向上していることが分かる。 It can be seen that Samples -27 to 40, which are within the scope of the present invention, have improved treatment effects with respect to the filtrate amount (related to the coagulation function) and the cake moisture content as compared with Comparative Samples -1 to 8.
Claims (4)
（Ａ）；下記一般式（１）あるいは（２）で表される単量体を１０〜１００モル％、非イオン性単量体を０〜９０モル％からなる該単量体あるいは該単量体混合物を、重合したカチオン性水溶性高分子。
（Ｂ）；下記一般式（１）あるいは（２）で表される単量体を１０〜９０モル％、下記一般式（３）で表される単量体を１０〜６０モル％、非イオン性単量体を０〜８０モル％からなる該単量体あるいは該単量体混合物を重合した両性水溶性高分子。
（Ｃ）下記一般式（４）で表されるビニルアミン構造単位を１０〜９０モル％有する水溶性高分子。
一般式（１）
（Ｒ１は水素又はメチル基、Ｒ２、Ｒ３は水素、炭素数１〜３のアルキルあるいはアルコキシル基であり、同種でも異種でも良い、Ｒ４は炭素数１〜３のアルキルあるいはアルコキシル基、７〜２０のアルキル基あるいはアリール基、Ａは酸素原子またはＮＨ、Ｂは炭素数２〜４のアルキレン基またはアルコキシレン基を表わす、Ｘ１ −は陰イオンをそれぞれ表わす）
（Ｒ５は水素又はメチル基、Ｒ６、Ｒ７は炭素数１〜３のアルキル基、アルコキシ基、Ｘ２ −は陰イオンをそれぞれ表わす）
（Ｒ８は水素、メチル基またはカルボキシメチル基、ＱはＳＯ３ −、Ｃ６Ｈ４ＳＯ３ −、ＣＯＮＨＣ（ＣＨ３）２ＣＨ２ＳＯ３ −、Ｃ６Ｈ４ＣＯＯ−あるいはＣＯＯ−、
Ｒ９は水素またはＣＯＯ−、Ｙ１ ＋は水素イオンまたは陽イオンをそれぞれ表す）
Ｒ１０は水素またはメチル基、Ｈ＋Ｚ−は無機酸および／または有機酸を表し、未中和時Ｈ＋Ｚ−＝０である。 An aggregation treatment agent comprising the following (A), the following (B) and the following (C).
(A): the monomer represented by the following general formula (1) or (2): 10 to 100 mol%, and the nonionic monomer consisting of 0 to 90 mol% or the monomer A cationic water-soluble polymer obtained by polymerizing a body mixture.
(B): 10 to 90 mol% of a monomer represented by the following general formula (1) or (2), 10 to 60 mol% of a monomer represented by the following general formula (3), nonionic An amphoteric water-soluble polymer obtained by polymerizing the monomer or the monomer mixture comprising 0 to 80 mol% of the polymerizable monomer.
(C) A water-soluble polymer having 10 to 90 mol% of a vinylamine structural unit represented by the following general formula (4).
General formula (1)
(R 1 is hydrogen or a methyl group, R 2 and R 3 are hydrogen, an alkyl or alkoxyl group having 1 to 3 carbon atoms, which may be the same or different, and R 4 is an alkyl or alkoxyl group having 1 to 3 carbon atoms, alkyl group or an aryl group of 7 to 20, a represents an oxygen atom or NH, B represents an alkylene group or an alkoxylene group having 2 to 4 carbon atoms, X 1 - represents respectively an anion)
(R 5 represents hydrogen or a methyl group, R 6 and R 7 each represent an alkyl group having 1 to 3 carbon atoms, an alkoxy group, and X 2 − represents an anion)
(R 8 is hydrogen, methyl or carboxymethyl group, Q represents SO 3 -, C 6 H 4 SO 3 -, CONHC (CH 3) 2 CH 2 SO 3 -, C 6 H 4 COO - or COO -,
R 9 represents hydrogen or COO − , and Y 1 + represents a hydrogen ion or a cation, respectively)
R 10 represents hydrogen or a methyl group, H + Z − represents an inorganic acid and / or an organic acid, and H + Z − = 0 when not neutralized.
（Ａ）；下記一般式（１）あるいは（２）で表される単量体を１０〜１００モル％、非イオン性単量体を０〜９０モル％からなる該単量体あるいは該単量体混合物を、重合したカチオン性水溶性高分子。
（Ｂ）；下記一般式（１）あるいは（２）で表される単量体を１０〜９０モル％、下記一般式（３）で表される単量体を１０〜６０モル％、非イオン性単量体を０〜８０モル％からなる該単量体あるいは該単量体混合物を重合した両性水溶性高分子。
（Ｃ）；下記一般式（４）で表されるビニルアミン構造単位を１０〜９０モル％有する水溶性高分子。
一般式（１）
（Ｒ１は水素又はメチル基、Ｒ２、Ｒ３は水素、炭素数１〜３のアルキルあるいはアルコキシル基であり、同種でも異種でも良い、Ｒ４は炭素数１〜３のアルキルあるいはアルコキシル基、７〜２０のアルキル基あるいはアリール基、Ａは酸素原子またはＮＨ、Ｂは炭素数２〜４のアルキレン基またはアルコキシレン基を表わす、Ｘ１ −は陰イオンをそれぞれ表わす）
（Ｒ５は水素又はメチル基、Ｒ６、Ｒ７は炭素数１〜３のアルキル基、アルコキシ基、Ｘ２ −は陰イオンをそれぞれ表わす）
（Ｒ８は水素、メチル基またはカルボキシメチル基、ＱはＳＯ３ −、Ｃ６Ｈ４ＳＯ３ −、ＣＯＮＨＣ（ＣＨ３）２ＣＨ２ＳＯ３ −、Ｃ６Ｈ４ＣＯＯ−あるいはＣＯＯ−、
Ｒ９は水素またはＣＯＯ−、Ｙ１ ＋は水素イオンまたは陽イオンをそれぞれ表す）
Ｒ１０は水素またはメチル基、Ｈ＋Ｚ−は無機酸および／または有機酸を表し、未中和時Ｈ＋Ｚ−＝０である。
A sludge dewatering method comprising adding a coagulation treatment agent containing the following (A), the following (B), and the following (C) to sludge, mixing and stirring to agglomerate, and then dewatering.
(A): the monomer represented by the following general formula (1) or (2): 10 to 100 mol%, and the nonionic monomer consisting of 0 to 90 mol% or the monomer A cationic water-soluble polymer obtained by polymerizing a body mixture.
(B): 10 to 90 mol% of a monomer represented by the following general formula (1) or (2), 10 to 60 mol% of a monomer represented by the following general formula (3), nonionic An amphoteric water-soluble polymer obtained by polymerizing the monomer or the monomer mixture comprising 0 to 80 mol% of the polymerizable monomer.
(C): A water-soluble polymer having 10 to 90 mol% of vinylamine structural units represented by the following general formula (4).
General formula (1)
(R 1 is hydrogen or a methyl group, R 2 and R 3 are hydrogen, an alkyl or alkoxyl group having 1 to 3 carbon atoms, which may be the same or different, and R 4 is an alkyl or alkoxyl group having 1 to 3 carbon atoms, alkyl group or an aryl group of 7 to 20, a represents an oxygen atom or NH, B represents an alkylene group or an alkoxylene group having 2 to 4 carbon atoms, X 1 - represents respectively an anion)
(R 5 represents hydrogen or a methyl group, R 6 and R 7 each represent an alkyl group having 1 to 3 carbon atoms, an alkoxy group, and X 2 − represents an anion)
(R 8 is hydrogen, methyl or carboxymethyl group, Q represents SO 3 -, C 6 H 4 SO 3 -, CONHC (CH 3) 2 CH 2 SO 3 -, C 6 H 4 COO - or COO -,
R 9 represents hydrogen or COO − , and Y 1 + represents a hydrogen ion or a cation, respectively)
R 10 represents hydrogen or a methyl group, H + Z − represents an inorganic acid and / or an organic acid, and H + Z − = 0 when not neutralized.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2015150534A (en) * | 2014-02-18 | 2015-08-24 | ハイモ株式会社 | Flocculation treatment agent, and dewatering method of sludge using the same |
| JP2017154033A (en) * | 2016-02-29 | 2017-09-07 | ハイモ株式会社 | Active sludge settling method |
| WO2021112218A1 (en) | 2019-12-06 | 2021-06-10 | 栗田工業株式会社 | Sludge dehydrating agent and sludge dehydrating method |
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| JPS5927903A (en) * | 1982-08-10 | 1984-02-14 | Mitsui Saianamitsudo Kk | Water-soluble polymer, its production and its use |
| JPH06218399A (en) * | 1993-01-27 | 1994-08-09 | Mitsubishi Kasei Corp | Sludge dewatering agent |
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Cited By (3)
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| JP2015150534A (en) * | 2014-02-18 | 2015-08-24 | ハイモ株式会社 | Flocculation treatment agent, and dewatering method of sludge using the same |
| JP2017154033A (en) * | 2016-02-29 | 2017-09-07 | ハイモ株式会社 | Active sludge settling method |
| WO2021112218A1 (en) | 2019-12-06 | 2021-06-10 | 栗田工業株式会社 | Sludge dehydrating agent and sludge dehydrating method |
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