JP3729973B2 - Method for producing dewatering agent for sewage mixed raw sludge and dewatering agent for sewage mixed raw sludge - Google Patents

Description

（但し、式中、ＡはＯまたはＮＨ；ＢはＣ₂ Ｈ₄ 、Ｃ₃ Ｈ₆ 、Ｃ₃ Ｈ₅ ＯＨ；Ｒ₁ はＨまたはＣＨ₃ ；Ｒ₂ 、Ｒ₃ は炭素数１〜４のアルキル基；Ｒ₄ は水素または炭素数１〜４のアルキル基あるいはベンジル基；Ｘ^- はアニオン性対イオンを表す。）
【０００７】
本発明の請求項２の発明は、（Ａ）全単量体中５〜９９．９９９９モル％の下記式（１）で表される水溶性カチオン性ビニル単量体またはその混合物、（Ｂ）全単量体中０．０００１〜０．０１モル％の２官能性単量体、（Ｃ）全単量体中０〜３０モル％の水溶性アニオン性ビニル単量体またはその混合物、（Ｄ）ノニオン性水溶性単量体、（Ｅ）連鎖移動剤、（Ｆ）水、（Ｇ）少なくとも１種類の炭化水素から成る油状物および（Ｈ）逆相エマルジョンすなわち油中水型エマルジョンを生成するに有効な量とＨＬＢである少なくとも１種類の界面活性剤を用意し、上記（Ａ）〜（Ｈ）成分を適時混合強攪拌し、油相中に微細単量体相液滴を形成させた後に重合操作を行い、親水性界面活性剤を混合し、水により希釈して使用することを特徴とする下水混合生汚泥の脱水剤の製造方法である。
【化５】

（但し、式中、ＡはＯまたはＮＨ；ＢはＣ₂ Ｈ₄ 、Ｃ₃ Ｈ₆ 、Ｃ₃ Ｈ₅ ＯＨ；Ｒ₁ はＨまたはＣＨ₃ ；Ｒ₂ 、Ｒ₃ は炭素数１〜４のアルキル基；Ｒ₄ は水素または炭素数１〜４のアルキル基あるいはベンジル基；Ｘ^- はアニオン性対イオンを表す。）
【０００８】
本発明の請求項３の発明は、（Ａ）全単量体中５〜９７．９９９９モル％の下記式（１）で表される水溶性カチオン性ビニル単量体またはその混合物、（Ｂ）全単量体中０．０００１〜０．０１モル％の２官能性単量体、（Ｃ）全単量体中２〜３０モル％の水溶性アニオン性ビニル単量体またはその混合物、（Ｄ）ノニオン性水溶性単量体、（Ｅ）連鎖移動剤、（Ｆ）水、（Ｇ）少なくとも１種類の炭化水素から成る油状物および（Ｈ）逆相エマルジョンすなわち油中水型エマルジョンを生成するに有効な量とＨＬＢである少なくとも１種類の界面活性剤を用意し、上記（Ａ）〜（Ｈ）成分を適時混合強攪拌し、油相中に微細単量体相液滴を形成させた後に重合操作を行い、親水性界面活性剤を混合し、水により希釈して使用することを特徴とする請求項２に記載の下水混合生汚泥の脱水剤の製造方法である。
【化６】

（但し、式中、ＡはＯまたはＮＨ；ＢはＣ₂ Ｈ₄ 、Ｃ₃ Ｈ₆ 、Ｃ₃ Ｈ₅ ＯＨ；Ｒ₁ はＨまたはＣＨ₃ ；Ｒ₂ 、Ｒ₃ は炭素数１〜４のアルキル基；Ｒ₄ は水素または炭素数１〜４のアルキル基あるいはベンジル基；Ｘ^- はアニオン性対イオンを表す。）
【０００９】
本発明の請求項４の発明は、ノニオン性水溶性単量体が（メタ）アクリルアミドであることを特徴とする請求項２ないし請求項３のいずれか１項に記載の下水混合生汚泥の脱水剤の製造方法である。
【００１０】
本発明の請求項５の発明は、水溶性アニオン性ビニル単量体が（メタ）アクリル酸であることを特徴とする請求項２ないし請求項３のいずれか１項に記載の下水混合生汚泥の脱水剤の製造方法である。
【００１１】
本発明の請求項６の発明は、２官能性単量体がＮ，Ｎ’−メチレンビスアクリルアミドあるいは２ヒドロキシプロピリデン１，３ビス〔（Ｎアクリロイルアミノプロピル）Ｎ，Ｎジメチルアンモニウムクロリド〕であることを特徴とする請求項２ないし請求項３のいずれか１項に記載の下水混合生汚泥の脱水剤の製造方法である。
【００１２】
本発明の請求項７の発明は、 親水性界面活性剤がＨＬＢ９〜１５のノニオン性界面活性剤であることを特徴とする請求項２ないし請求項３のいずれか１項に記載の下水混合生汚泥の脱水剤の製造方法である。
【００１３】
【発明の実施の形態】
本発明に用いられる前記式（１）で表される（Ａ）成分の水溶性カチオン性ビニル単量体の具体例としては、ジアルキルアミノアルキル（メタ）アクリレートの三級塩および四級アンモニウム塩、ジアルキルアミノアルキル（メタ）アクリルアミドの三級塩および四級アンモニウム塩、ジアルキルアミノヒドロキシアルキル（メタ）アクリレートの三級塩および四級アンモニウム塩、ジアルキルアミノヒドロキシアルキル（メタ）アクリルアミドの三級塩および四級アンモニウム塩あるいはこれらの混合物から選ばれる一種を挙げる事ができる。 これらの中でもアクリロイロキシエチルトリメチルアンモニウムクロリド、メタクリロイロキシエチルトリメチルアンモニウムクロリド、ジメチルアミノプロピルアクリルアミド塩酸塩あるいはこれらの混合物から選ばれる一種が好ましく用いられる。
【００１４】
本発明に用いられる（Ｂ）成分の２官能性単量体の具体例としては２ヒドロキシプロピリデン１，３ビス〔（Ｎアクリロイルアミノプロピル）Ｎ，Ｎジメチルアンモニウムクロリド〕、Ｎ，Ｎ’−メチレンビスアクリルアミド、Ｎ，Ｎ’−メチレンビスメタクリルアミド、ジビニルベンゼンなどのジビニル化合物、メチロールアクリルアミド、メチロールメタクリルアミドなどのビニル系メチロール化合物、アクロレインなどのビニル系アルデヒド化合物あるいはこれらの混合物が挙げられるが、これらの中でも２ヒドロキシプロピリデン１，３ビス〔（Ｎアクリロイルアミノプロピル）Ｎ，Ｎジメチルアンモニウムクロリド〕が好ましく使用でき、Ｎ，Ｎ’−メチレンビスアクリルアミドはこれに次ぐ。
【００１５】
本発明に用いられる（Ｃ）成分の水溶性アニオン性ビニル単量体の具体例としては、（メタ）アクリル酸、２−アクリルアミド−２−メチルプロパンスルホン酸、ビニルスルホン酸、スチレンスルホン酸、イタコン酸、マレイン酸、フマール酸、アリールスルホン酸およびその塩あるいはこれらの混合物が挙げられるが、これらの中でもアクリル酸が最も好ましく使用できる。
【００１６】
本発明に用いられる（Ｄ）成分の水溶性ノニオン性ビニル単量体の具体例としては、（メタ）アクリルアミド、ビニルメチルエーテル、ビニルエチルエーテルあるいはこれらの混合物が挙げられるが、これらの中でもアクリルアミドが最も好ましく使用できる。
【００１７】
本発明に用いられる（Ｅ）成分の連鎖移動剤の具体例としては、アルコール、メルカプタン、ホスファイト、サルファイトあるいはこれらの混合物が挙げられ。 これら連鎖移動剤の添加量は、有機高分子凝集剤を汚泥に添加する濃度まで水で希釈した状態で、粒系３０μｍ以下の粒子が顕微鏡にて観察され、該希釈液をガラス板に塗布して１０５°Ｃにて加熱乾燥したときに連続状の乾燥膜を形成する性質を有する様に選ばれる。
【００１８】
本発明に用いられる（Ｇ）成分である少なくとも１種類の炭化水素から成る油状物の具体例としては、灯油、軽油、中油などの鉱油、あるいはこれらと実質的に同じ範囲の沸点や粘度など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挙げられる。
【００１９】
本発明に用いられる（Ｈ）成分である界面活性剤はＨＬＢ３〜６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などを挙げる事ができる。
【００２０】
本発明において油中水型エマルジョン重合により得られた重合物と混合される親水性界面活性剤としてはカチオン性界面活性剤あるいはＨＬＢ９〜１５のノニオン性界面活性剤が用いられ、好ましくはＨＬＢ１０〜１４のノニオン性界面活性剤が用いられる。 好ましいノニオン性界面活性剤の代表例としては例えばポリオキシエチレンノニルフェニルエーテルを挙げる事ができる。
【００２１】
本発明に用いられる（Ｂ）成分の２官能性単量体の重合性単量体全量に対する割合は０．０００１〜０．０１モル％、好ましくは０．０００２〜０．００３モル％の範囲で共重合する事が望ましい。 ０．０００１モル％未満では十分な網目構造が得られず優れた脱水性能が得られない。 また０．０１モル％を超えた量では水不溶性の重合体と成り、汚泥に添加混合しても脱水性良好なフロックが得られない。
【００２２】
本発明に係る高分子は本質的に公知の重合法により共重合する事ができる。
例えば重合性ビニル単量体と連鎖移動剤を含む水溶液と、ＨＬＢが３〜６であるノニオン性界面活性剤を含む有機分散媒とを混合し乳化させた後、ラジカル重合開始剤の存在下、温度３０〜８０°Ｃで重合させ油中水型カチオン性重合体エマルジョンを製造する方法が特開昭６１−２３６２５０号公報に記載されているが、この方法を適用して単量体組成を代える事により本発明の油中水型エマルジョンを合成する事ができる。 この油中水型エマルジョンに親水性界面活性剤を添加して水に混合し、水中油型エマルジョンに転相し、脱水剤として使用する。
溶解後の汚泥への添加条件は、通常の高分子凝集剤と異なる点は無い。
【００２３】
本発明の汚泥の処理方法は、下水の混合生汚泥の前処理として無機凝集剤を添加混合した後に、請求項１に記載の汚泥脱水剤の水による希釈液を添加し、攪拌を加えて下水混合生汚泥を凝集させ、脱水機にて凝集汚泥を脱水することもできる。 ここに言う無機凝集剤とは硫酸アルミニウム、塩化アルミニウム、ポリ塩化アルミニウム、ポリ硫酸鉄、塩化第二鉄およびこれらの混合物から選ばれる一種である。 無機凝集剤の添加量は汚泥ＳＳ（懸濁物）あたり１０〜１００重量％添加し、必要によりＰＨ調整を行う。 本発明における脱水機はベルトプレス・フィルタープレス・デカンター等の公知の汚泥脱水機を選定することができる。
【００２４】
【実施例】
次に実施例によって、本発明を具体的に説明するが、本発明はその要旨を超えない限り、以下の実施例に制約されるものではない。
【００２５】
（合成例−１）
攪拌機および温度制御装置を備えた反応槽に沸点１９０°Ｃないし２３０°Ｃのイソパラフィン１２０．０Ｋｇおよびソルビタンモノオレート７．５Ｋｇを仕込んだ。 脱塩水１６５Ｋｇおよびアクリロイロキシエチルトリメチルアンモニウムクロリド（ＡＭＣ）２７．９９９７モル％（表１中に約２８と表す）、アクリル酸（ＡＡＣ）２モル％、２ヒドロキシプロピリデン１，３ビス〔（Ｎアクリロイルアミノプロピル）Ｎ，Ｎジメチルアンモニウムクロリド〕（ＨＰＡＤ）３×１０^-4モル％、アクリルアミド（ＡＡＭ）７０モル％の組成のモノマー２００Ｋｇの混合物を添加し、ホモジナイザーにて攪拌乳化した。 得られたエマルジョンにイソプロピルアルコール２００ｇを加え窒素置換の後、ジメチルアゾビスイソブチレート４０ｇを加え、温度５０°Ｃに制御しながら重合反応を完結させ、その後ポリオキシエチレンノニルフェニルエーテル７．５Ｋｇを添加混合して試験に供する試料（試料−１）（本発明の凝集剤）とした。
【００２６】
（合成例−２）
アクリロイロキシエチルトリメチルアンモニウムクロリド（ＡＭＣ）２７．９９８モル％（表１中に約２８と表す）、アクリル酸（ＡＡＣ）２モル％、２ヒドロキシプロピリデン１，３ビス〔（Ｎアクリロイルアミノプロピル）Ｎ，Ｎジメチルアンモニウムクロリド〕（ＨＰＡＤ）２×１０^-3モル％、アクリルアミド（ＡＡＭ）７０モル％の組成のモノマー２００Ｋｇのの混合物を用いた以外は合成例−１と同様にして試験に供する試料（試料−２）（本発明の凝集剤）を作った。
【００２７】
（合成例−３）
アクリロイロキシエチルトリメチルアンモニウムクロリド（ＡＭＣ）４９．９９９７モル％（表１中に約５０と表す）、アクリル酸（ＡＡＣ）１０モル％、２ヒドロキシプロピリデン１，３ビス〔（Ｎアクリロイルアミノプロピル）Ｎ，Ｎジメチルアンモニウムクロリド〕（ＨＰＡＤ）３×１０^-4モル％、アクリルアミド（ＡＡＭ）４０モル％の組成のモノマー２００Ｋｇの混合物を用いた以外は合成例−１と同様にして試験に供する試料（試料−３）（本発明の凝集剤）を作った。
【００２８】
（合成例−４）
アクリロイロキシエチルトリメチルアンモニウムクロリド（ＡＭＣ）４９．９９８モル％（表１中に約５０と表す）、アクリル酸（ＡＡＣ）１０モル％、２ヒドロキシプロピリデン１，３ビス〔（Ｎアクリロイルアミノプロピル）Ｎ，Ｎジメチルアンモニウムクロリド〕（ＨＰＡＤ）２×１０^-3モル％、アクリルアミド（ＡＡＭ）４０モル％の組成のモノマー２００Ｋｇの混合物を用いた以外は合成例−１と同様にして試験に供する試料（試料−４）（本発明の凝集剤）を作った。
【００２９】
（合成例−５）
アクリロイロキシエチルトリメチルアンモニウムクロリド（ＡＭＣ）４９．９９９７モル％（表１中に約９０と表す）、２ヒドロキシプロピリデン１，３ビス〔（Ｎアクリロイルアミノプロピル）Ｎ，Ｎジメチルアンモニウムクロリド〕（ＨＰＡＤ）３×１０^−４モル％、アクリルアミド（ＡＡＭ）５０モル％の組成のモノマー２００Ｋｇの混合物を用いた以外は合成例−１と同様にして試験に供する試料（試料−５）（本発明の凝集剤）を作った。
【００３０】
（合成例−６）
アクリロイロキシエチルトリメチルアンモニウムクロリド（ＡＭＣ）４９．９９８モル％（表１中に約５０と表す）、２ヒドロキシプロピリデン１，３ビス〔（Ｎアクリロイルアミノプロピル）Ｎ，Ｎジメチルアンモニウムクロリド〕（ＨＰＡＤ）３×１０^−４モル％、アクリルアミド（ＡＡＭ）５０モル％の組成のモノマー２００Ｋｇの混合物を用いた以外は合成例−１と同様にして試験に供する試料（試料−６）（本発明の凝集剤）を作った。
【００３１】
（比較合成例−１）
架橋剤である２ヒドロキシプロピリデン１，３ビス〔（Ｎアクリロイルアミノプロピル）Ｎ，Ｎジメチルアンモニウムクロリド〕（ＨＰＡＤ）を添加することなくアクリロイロキシエチルトリメチルアンモニウムクロリド（ＡＭＣ）２８モル％、アクリル酸（ＡＡＣ）２モル％、アクリルアミド（ＡＡＭ）７０モル％のみの組成のモノマー２００Ｋｇの混合物を用いた以外は合成例−１と同様にして試験に供する試料（試料−７）を作った。
【００３２】
（比較合成例−２）
架橋剤である２ヒドロキシプロピリデン１，３ビス〔（Ｎアクリロイルアミノプロピル）Ｎ，Ｎジメチルアンモニウムクロリド〕（ＨＰＡＤ）を添加することなくアクリロイロキシエチルトリメチルアンモニウムクロリド（ＡＭＣ）５０モル％、アクリル酸（ＡＡＣ）１０モル％、アクリルアミド（ＡＡＭ）４０モル％のみの組成のモノマー２００Ｋｇの混合物を用いた以外は合成例−１と同様にして試験に供する試料（試料−８）を作った。
【００３３】
（比較合成例−３）
架橋剤である２ヒドロキシプロピリデン１，３ビス〔（Ｎアクリロイルアミノプロピル）Ｎ，Ｎジメチルアンモニウムクロリド〕（ＨＰＡＤ）を添加することなくアクリロイロキシエチルトリメチルアンモニウムクロリド（ＡＭＣ）５０モル％、アクリルアミド（ＡＡＭ）５０モル％のみの組成のモノマー２００Ｋｇの混合物を用いた以外は合成例−１と同様にして試験に供する試料（試料−９）を作った。
【００３４】
（比較合成例−４）
連鎖移動剤としてのイソプロピルアルールを添加することなく重合を行った以外は合成例−２と同様に、アクリロイロキシエチルトリメチルアンモニウムクロリド（ＡＭＣ）２７．９９８モル％（表１中に約２８と表す）、アクリル酸（ＡＡＣ）２モル％、２ヒドロキシプロピリデン１，３ビス〔（Ｎアクリロイルアミノプロピル）Ｎ，Ｎジメチルアンモニウムクロリド〕（ＨＰＡＤ）２×１０^-3モル％、アクリルアミド（ＡＡＭ）７０モル％の組成のモノマー２００Ｋｇの混合物をもちいて試験に供する試料（試料−１０）を作った。
【００３５】
（比較合成例−５）
連鎖移動剤としてのイソプロピルアルールを添加することなく重合を行った以外は合成例−４と同様に、アクリロイロキシエチルトリメチルアンモニウムクロリド（ＡＭＣ）４９．９９８モル％（表１中に約５０と表す）、アクリル酸（ＡＡＣ）１０モル％、２ヒドロキシプロピリデン１，３ビス〔（Ｎアクリロイルアミノプロピル）Ｎ，Ｎジメチルアンモニウムクロリド〕（ＨＰＡＤ）２×１０^-3モル％、アクリルアミド（ＡＡＭ）４０モル％の組成のモノマー２００Ｋｇの混合物を用いて試験に供する試料（試料−１１）を作った。
【００３６】
（比較合成例−６）
連鎖移動剤としてのイソプロピルアルールを添加することなく重合を行った以外は合成例−６と同様に、アクリロイロキシエチルトリメチルアンモニウムクロリド（ＡＭＣ）４９．９９８モル％（表１中に約５０と表す）、２ヒドロキシプロピリデン１，３ビス〔（Ｎアクリロイルアミノプロピル）Ｎ，Ｎジメチルアンモニウムクロリド〕（ＨＰＡＤ）２×１０^-3モル％、アクリルアミド（ＡＡＭ）５０モル％の組成のモノマー２００Ｋｇの混合物を用いて試験に供する試料（試料−１２）を作った。
【００３７】
（比較合成例−７）
連鎖移動剤の共存下、アクリロイロキシエチルトリメチルアンモニウムクロリド（ＡＭＣ）２７．９９８モル％（表１中に約２８と表す）、アクリル酸（ＡＡＣ）２モル％、２ヒドロキシプロピリデン１，３ビス〔（Ｎアクリロイルアミノプロピル）Ｎ，Ｎジメチルアンモニウムクロリド〕（ＨＰＡＤ）２×１０^-3モル％、アクリルアミド（ＡＡＭ）７０モル％の組成のモノマー２００Ｋｇの混合物を用いて合成例２におけると同様の逆相乳化重合物を合成し、転相剤であるポリオキシエチレンノニルフェニルエーテルを重合物に後添加することなく、試験に供する試料（試料−１３）を作った。
【００３８】
（比較合成例−８）
連鎖移動剤の共存下、アクリロイロキシエチルトリメチルアンモニウムクロリド（ＡＭＣ）４９．９９８モル％（表１中に約５０と表す）、アクリル酸（ＡＡＣ）１０モル％、２ヒドロキシプロピリデン１，３ビス〔（Ｎアクリロイルアミノプロピル）Ｎ，Ｎジメチルアンモニウムクロリド〕（ＨＰＡＤ）２×１０^-3モル％、アクリルアミド（ＡＡＭ）４０モル％の組成のモノマー２００Ｋｇの混合物を用いて合成例２におけると同様の逆相乳化重合物を合成し、転相剤であるポリオキシエチレンノニルフェニルエーテルを重合物に後添加することなく、試験に供する試料（試料−１４）を作った。
【００３９】
（比較合成例−９）
連鎖移動剤の共存下、アクリロイロキシエチルトリメチルアンモニウムクロリド（ＡＭＣ）４９．９９８モル％（表１中に約５０と表す）、２ヒドロキシプロピリデン１，３ビス〔（Ｎアクリロイルアミノプロピル）Ｎ，Ｎジメチルアンモニウムクロリド〕（ＨＰＡＤ）２×１０^-3モル％、アクリルアミド（ＡＡＭ）５０モル％の組成のモノマー２００Ｋｇの混合物を用いて合成例２におけると同様の逆相乳化重合物を合成し、転相剤であるポリオキシエチレンノニルフェニルエーテルを重合物に後添加することなく、試験に供する試料（試料−１５）を作った。
以上まとめて表１に記載する。
【００４０】
【表１】
【００４１】
（観察結果−１）
エマルジョン状態の試料−１〜試料−６を水道水にて実機スクリュウ式攪拌装置（３００ｒｐｍ）により攪拌下ポリマー濃度０．２重量％になるように希釈し、１時間経過し増粘した液を採取し、顕微鏡にて観察したところ、全て一面に粒径３０μｍ以下（約３μｍ）の粒子が観察され、該希釈液をガラス板に塗布して１０５°Ｃにて加熱乾燥したところ連続状の乾燥膜を形成した。 また、この希釈液をコロイド適定によりイオン当量値を測定したところ、全て理論値の８５％以上のイオン当量値であった。
【００４２】
（観察結果−２）
観察結果−１と同様にエマルジョン状態の試料−７〜試料−９を水道水にて実機攪拌装置により攪拌下ポリマー濃度０．２重量％になるように希釈し１時間経過し増粘した液を採取し、顕微鏡にて観察したところ、全て均一溶液であり粒子は観察されなかった。 該希釈液をガラス板に塗布して１０５°Ｃにて加熱乾燥したところ連続状の乾燥膜を形成した。 また、この希釈液をコロイド適定によりイオン当量値を測定したところ、全て理論値の１００％のイオン当量値であった。
【００４３】
（観察結果−３）
観察結果−１と同様にエマルジョン状態の試料−１０〜試料−１２を水道水にて実機攪拌装置により攪拌下ポリマー濃度０．２重量％になるように希釈し１時間経過し増粘した液を採取し、顕微鏡にて観察したところ、すべて一面に粒径３０μｍ以下（約３μｍ）の粒子が観察され、該希釈液をガラス板に塗布して１０５°Ｃにて加熱乾燥したところ粒状の不連続乾燥膜を形成した。 また、この希釈液をコロイド適定によりイオン当量値を測定したところ、全て理論値の６０％以下のイオン当量値であった。
【００４４】
（観察結果−４）
観察結果−１と同様にエマルジョン状態の試料−１３〜試料−１５を水道水にて実機攪拌装置により攪拌下ポリマー濃度０．２重量％になるように希釈した結果、エマルジョンは水中に分散せず、ゲル状の塊が浮遊し、均一なポリマー希釈液は得られなかった。 これに対しビーカースケールでマグネティックスターラーにより強攪拌をした場合はエマルジョンは水中に分散し、ゲル状の塊が浮遊することなく、均一なポリマー希釈液が得られた。
溶解性不良の為に試料−１３〜試料−１５の効果試験は実施しなかった。
【００４５】
（効果試験）
観察結果−１〜３で調製した希釈液を用いて、下水処理場より発生する下水混合生汚泥をベルトプレスにより脱水した。 試験に供した汚泥の性状はＰＨ；６．７，ＳＳ；１４３００ｍｇ／ｌ，強熱減量７２．５％，Ｍアルカリ度１５００ｍｇ／ｌである。 この汚泥に、対ＳＳ３０％のポリ硫酸鉄を加え十分混合したのち、対ＳＳ１．２％のポリマーを添加攪拌しベルトプレスで脱水した結果を表２に示す。
【００４６】
【表２】

【００４７】
【発明の効果】
重合時の連鎖移動剤および架橋剤を欠くと本願発明品よりも脱水効果が劣ることは上記効果試験より明白であり、逆相乳化重合物に転相剤を加えない場合は、凝集剤の現場溶解が不能であるため実用に耐えない。 本願発明の従来品に対する優位性は明らかである。
【表−１】

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a sludge dewatering agent comprising a crosslinked polymer, and the sludge dewatering agent of the present invention is effective for dewatering raw sewage mixed sludge.
[0002]
[Prior art]
Various sludge dewatering agents and sludge dewatering methods have been known so far. For example, a sludge dewatering method (Japanese Patent Laid-Open No. 63-158200) is known in which an amphoteric polymer flocculant is added to organic sludge having a sludge pH of 5 to 8 after addition of an inorganic flocculant.
In addition, in order to improve the drawbacks of conventional polymer flocculants, cross-linked cationic / anionic / nonionic organic polymer compositions (European Patent No. 0,202,780, JP-A JP-A-61-293510, JP-A-64-85199, JP-A-2-2-29877, JP-A-4-226102, etc.) have been proposed to be effective for various solid-liquid separations.
[0003]
There is an activated sludge method as a method for treating sewage. Excess sludge is generated from the activated sludge process. In order to reduce the load of the activated sludge method, sludge in which suspended solids in sewage are settled without chemicals is called primary sedimentation sludge, and the mixture of both is called mixed raw sludge.
[0004]
With recent changes in the quality of sewage, dewatering treatment of sewage mixed raw sludge is becoming very difficult, and the conventional addition of cationic polymer flocculants is unsatisfactory. That is, when filter dewatering such as a belt filter or a filter press is performed, the cake does not peel easily and adheres to the filter cloth. When centrifugal dewatering is performed with a decanter, a cake with a high moisture content is discharged and the flammability is poor.
[0005]
[Problems to be solved by the invention]
Conventionally known amphoteric polymers or cationic polymers are unsatisfactory in performance. In particular, with recent changes in the quality of sewage, a method for efficiently dewatering raw sewage mixed sludge has not been known.
[0006]
The invention according to claim 1 of the present invention performs reverse phase emulsion polymerization of a monomer containing a water-soluble cationic vinyl monomer represented by the following formula (1) or a mixture thereof in the presence of a chain transfer agent. In the state diluted with water to the concentration to be added to the sludge, particles having a particle size of 30 μm or less are observed with a microscope, and the diluted solution is applied to a glass plate. A sewage-mixed raw sludge characterized by forming a continuous dry film when heated and dried at 105 ° C., and having an ion equivalent value measured by colloid titration of 85% or more of the theoretical value It is a dehydrating agent.
[Chemical 1]

(Wherein, A is O or NH; B is C ₂ H ₄ , C ₃ H ₆ , C ₃ H ₅ OH; R ₁ is H or CH ₃ ; R ₂ and R ₃ are each having 1 to 4 carbon atoms. R ₄ is hydrogen, an alkyl group having 1 to 4 carbon atoms or a benzyl group; X ⁻ represents an anionic counter ion.)
[0007]
The invention of claim 2 of the present invention is (A) 5 to 99.9999 mol% of a water-soluble cationic vinyl monomer represented by the following formula (1) or a mixture thereof, (B) 0.0001 to 0.01 mol% of bifunctional monomer in all monomers, (C) 0 to 30 mol% of water-soluble anionic vinyl monomer in all monomers or a mixture thereof (D A nonionic water-soluble monomer, (E) a chain transfer agent, (F) water, (G) an oil consisting of at least one hydrocarbon, and (H) a reverse phase emulsion, ie a water-in-oil emulsion. An effective amount and at least one surfactant which is HLB were prepared, and the above components (A) to (H) were mixed and agitated in a timely manner to form fine monomer phase droplets in the oil phase. The polymerization operation is performed later, and a hydrophilic surfactant is mixed and diluted with water for use. It is a manufacturing method of sewage mixed raw sludge dehydrating agent.
[Chemical formula 5]

(Wherein, A is O or NH; B is C ₂ H ₄ , C ₃ H ₆ , C ₃ H ₅ OH; R ₁ is H or CH ₃ ; R ₂ and R ₃ are each having 1 to 4 carbon atoms. R ₄ is hydrogen, an alkyl group having 1 to 4 carbon atoms or a benzyl group; X ⁻ represents an anionic counter ion.)
[0008]
Invention of Claim 3 of this invention is (A) The water-soluble cationic vinyl monomer represented by following formula (1) of 5-97.9999 mol% in all the monomers, or its mixture, (B) 0.0001 to 0.01 mol% of bifunctional monomer in all monomers, (C) 2 to 30 mol% of water-soluble anionic vinyl monomer in all monomers, or a mixture thereof (D A nonionic water-soluble monomer, (E) a chain transfer agent, (F) water, (G) an oil consisting of at least one hydrocarbon, and (H) a reverse phase emulsion, ie a water-in-oil emulsion. An effective amount and at least one surfactant which is HLB were prepared, and the above components (A) to (H) were mixed and agitated in a timely manner to form fine monomer phase droplets in the oil phase. The polymerization operation is performed later, and a hydrophilic surfactant is mixed and diluted with water for use. It is a manufacturing method of sewage mixed raw sludge dehydrating agent according to claim 2.
[Chemical 6]

(Wherein, A is O or NH; B is C ₂ H ₄ , C ₃ H ₆ , C ₃ H ₅ OH; R ₁ is H or CH ₃ ; R ₂ and R ₃ are each having 1 to 4 carbon atoms. R ₄ is hydrogen, an alkyl group having 1 to 4 carbon atoms or a benzyl group; X ⁻ represents an anionic counter ion.)
[0009]
The invention according to claim 4 of the present invention is characterized in that the nonionic water-soluble monomer is (meth) acrylamide, and the dewatered raw sludge mixed with sewage according to any one of claims 2 to 3 It is a manufacturing method of an agent.
[0010]
The invention according to claim 5 of the present invention is the sewage mixed raw sludge according to any one of claims 2 to 3 , wherein the water-soluble anionic vinyl monomer is (meth) acrylic acid. This is a method for producing a dehydrating agent.
[0011]
According to a sixth aspect of the present invention, the bifunctional monomer is N, N′-methylenebisacrylamide or 2hydroxypropylidene 1,3 bis [(N acryloylaminopropyl) N, N dimethylammonium chloride]. It is a manufacturing method of the dehydrating agent of the sewage mixing raw sludge of any one of Claim 2 thru | or 3 characterized by the above-mentioned.
[0012]
The invention according to claim 7 of the present invention is the sewage mixture according to any one of claims 2 to 3 , wherein the hydrophilic surfactant is a nonionic surfactant having an HLB of 9 to 15. This is a method for producing a sludge dehydrating agent.
[0013]
DETAILED DESCRIPTION OF THE INVENTION
Specific examples of the water-soluble cationic vinyl monomer of the component (A) represented by the formula (1) used in the present invention include tertiary salts and quaternary ammonium salts of dialkylaminoalkyl (meth) acrylates, Tertiary and quaternary ammonium salts of dialkylaminoalkyl (meth) acrylamide, tertiary and quaternary ammonium salts of dialkylaminohydroxyalkyl (meth) acrylate, tertiary and quaternary salts of dialkylaminohydroxyalkyl (meth) acrylamide One kind selected from ammonium salts or mixtures thereof can be mentioned. Among these, one selected from acryloyloxyethyltrimethylammonium chloride, methacryloyloxyethyltrimethylammonium chloride, dimethylaminopropylacrylamide hydrochloride or a mixture thereof is preferably used.
[0014]
Specific examples of the bifunctional monomer of the component (B) used in the present invention include 2-hydroxypropylidene 1,3 bis [(N acryloylaminopropyl) N, N dimethylammonium chloride], N, N′-methylene. Examples thereof include divinyl compounds such as bisacrylamide, N, N′-methylenebismethacrylamide, and divinylbenzene, vinyl methylol compounds such as methylolacrylamide and methylolmethacrylamide, vinyl aldehyde compounds such as acrolein, and mixtures thereof. Among them, 2-hydroxypropylidene 1,3bis [(N acryloylaminopropyl) N, N dimethylammonium chloride] can be preferably used, followed by N, N′-methylenebisacrylamide.
[0015]
Specific examples of the water-soluble anionic vinyl monomer (C) used in the present invention include (meth) acrylic acid, 2-acrylamido-2-methylpropanesulfonic acid, vinylsulfonic acid, styrenesulfonic acid, and itacon. Examples of the acid include maleic acid, fumaric acid, arylsulfonic acid and salts thereof, and mixtures thereof. Among these, acrylic acid is most preferably used.
[0016]
Specific examples of the water-soluble nonionic vinyl monomer of the component (D) used in the present invention include (meth) acrylamide, vinyl methyl ether, vinyl ethyl ether or a mixture thereof. Among these, acrylamide is used. Most preferably used.
[0017]
Specific examples of the component (E) chain transfer agent used in the present invention include alcohols, mercaptans, phosphites, sulfites, and mixtures thereof. The addition amount of these chain transfer agents is such that particles having a particle size of 30 μm or less are observed with a microscope in a state diluted with water to a concentration at which the organic polymer flocculant is added to sludge, and the diluted solution is applied to a glass plate. The film is selected so as to have a property of forming a continuous dry film when heated and dried at 105 ° C.
[0018]
Specific examples of the oily substance composed of at least one kind of hydrocarbon as the component (G) used in the present invention include mineral oils such as kerosene, light oil, and middle oil, or boiling points and viscosities in substantially the same range as these. Examples thereof include hydrocarbon-based synthetic oils having characteristics and mixtures thereof.
[0019]
The surfactant (H) used in the present invention is an HLB 3-6 nonionic surfactant, and specific examples thereof include sorbitan monooleate, sorbitan monostearate, sorbitan monopalmitate and the like. it can.
[0020]
As the hydrophilic surfactant mixed with the polymer obtained by water-in-oil emulsion polymerization in the present invention, a cationic surfactant or a nonionic surfactant of HLB 9-15 is used, preferably HLB 10-14. Nonionic surfactants are used. Typical examples of preferred nonionic surfactants include polyoxyethylene nonylphenyl ether.
[0021]
The ratio of the bifunctional monomer of the component (B) used in the present invention to the total amount of the polymerizable monomer is in the range of 0.0001 to 0.01 mol%, preferably 0.0002 to 0.003 mol%. It is desirable to copolymerize. If it is less than 0.0001 mol%, a sufficient network structure cannot be obtained, and excellent dewatering performance cannot be obtained. Further, if it exceeds 0.01 mol%, it becomes a water-insoluble polymer, and even if added to and mixed with sludge, flocs with good dewaterability cannot be obtained.
[0022]
The polymer according to the present invention can be copolymerized by a known polymerization method.
For example, after mixing and emulsifying an aqueous solution containing a polymerizable vinyl monomer and a chain transfer agent and an organic dispersion medium containing a nonionic surfactant having an HLB of 3 to 6, in the presence of a radical polymerization initiator, A method for producing a water-in-oil cationic polymer emulsion by polymerization at a temperature of 30 to 80 ° C. is described in JP-A-61-236250, and this method is applied to change the monomer composition. Thus, the water-in-oil emulsion of the present invention can be synthesized. A hydrophilic surfactant is added to this water-in-oil emulsion, mixed with water, phase-inverted to an oil-in-water emulsion, and used as a dehydrating agent.
Addition conditions to the sludge after dissolution do not differ from ordinary polymer flocculants.
[0023]
In the sludge treatment method of the present invention, the inorganic flocculant is added and mixed as a pretreatment of the mixed raw sludge of sewage, and then the sludge dewatering agent according to claim 1 is added with a water-diluted solution and stirred to add sewage. The mixed raw sludge can be agglomerated, and the agglomerated sludge can be dehydrated with a dehydrator. The inorganic flocculant mentioned here is a kind selected from aluminum sulfate, aluminum chloride, polyaluminum chloride, polyiron sulfate, ferric chloride, and mixtures thereof. The amount of the inorganic flocculant added is 10 to 100% by weight per sludge SS (suspension), and the pH is adjusted if necessary. As the dehydrator in the present invention, a known sludge dehydrator such as a belt press, a filter press, or a decanter can be selected.
[0024]
【Example】
EXAMPLES Next, although an Example demonstrates this invention concretely, this invention is not restrict | limited to a following example, unless the summary is exceeded.
[0025]
(Synthesis Example-1)
A reaction vessel equipped with a stirrer and a temperature controller was charged with 120.0 kg of isoparaffin having a boiling point of 190 ° C. to 230 ° C. and 7.5 kg of sorbitan monooleate. 165 kg of demineralized water and acryloyloxyethyltrimethylammonium chloride (AMC) 27.9997 mol% (represented as about 28 in Table 1), acrylic acid (AAC) 2 mol%, 2 hydroxypropylidene 1,3 bis [(N A mixture of 200 kg of monomer having a composition of (acryloylaminopropyl) N, N dimethylammonium chloride] (HPAD) 3 × 10 ⁻⁴ mol% and acrylamide (AAM) 70 mol% was added and emulsified with stirring by a homogenizer. 200 g of isopropyl alcohol was added to the obtained emulsion, and after nitrogen substitution, 40 g of dimethylazobisisobutyrate was added to complete the polymerization reaction while controlling the temperature at 50 ° C., and then 7.5 kg of polyoxyethylene nonylphenyl ether was added. A sample (sample-1) (the flocculant of the present invention) to be added and mixed for the test was used.
[0026]
(Synthesis Example-2)
27.998 mol% of acryloyloxyethyltrimethylammonium chloride (AMC) (represented as about 28 in Table 1), 2 mol% of acrylic acid (AAC), 2 hydroxypropylidene 1,3 bis [(N acryloylaminopropyl) N, N-dimethylammonium chloride] (HPAD) 2 × 10 ⁻³ mol% and acrylamide (AAM) 70 mol% A mixture of 200 kg of monomer was used in the same manner as in Synthesis Example 1 except that a sample was used for the test. (Sample-2) (flocculating agent of the present invention) was prepared.
[0027]
(Synthesis Example-3)
49.9997 mol% of acryloyloxyethyltrimethylammonium chloride (AMC) (represented as about 50 in Table 1), 10 mol% of acrylic acid (AAC), 2 hydroxypropylidene 1,3 bis [(N acryloylaminopropyl) N, N-dimethylammonium chloride] (HPAD) 3 × 10 ⁻⁴ mol% and acrylamide (AAM) 40 mol% in a composition similar to Synthesis Example 1 except that a mixture of 200 kg of monomer was used ( Sample 3) (flocculating agent of the present invention) was prepared.
[0028]
(Synthesis Example-4)
49.998 mol% of acryloyloxyethyltrimethylammonium chloride (AMC) (represented as about 50 in Table 1), 10 mol% of acrylic acid (AAC), 2 hydroxypropylidene 1,3 bis [(N acryloylaminopropyl) N, N-dimethylammonium chloride] (HPAD) 2 × 10 ⁻³ mol% and acrylamide (AAM) 40 mol% in a composition similar to Synthesis Example 1 except that a mixture of 200 kg monomer was used ( Sample-4) (flocculating agent of the present invention) was prepared.
[0029]
(Synthesis Example-5)
49.9997 mol% of acryloyloxyethyltrimethylammonium chloride (AMC) (represented as about 90 in Table 1), 2 hydroxypropylidene 1,3 bis [(N acryloylaminopropyl) N, N dimethylammonium chloride] (HPAD ) Sample used for test (Sample-5) (Aggregation of the present invention) in the same manner as in Synthesis Example-1 except that a mixture of 200 kg monomer having a composition of 3 × 10 ⁻⁴ mol% and acrylamide (AAM) 50 mol% was used. Agent).
[0030]
(Synthesis Example-6)
49.998 mol% of acryloyloxyethyltrimethylammonium chloride (AMC) (represented as about 50 in Table 1), 2 hydroxypropylidene 1,3 bis [(N acryloylaminopropyl) N, N dimethylammonium chloride] (HPAD ) Sample (Sample-6) to be used for the test in the same manner as in Synthesis Example 1 except that a mixture of 200 kg monomer having a composition of 3 × 10 ⁻⁴ mol% and acrylamide (AAM) 50 mol% was used (aggregation of the present invention) Agent).
[0031]
(Comparative Synthesis Example-1)
Acryloyloxyethyltrimethylammonium chloride (AMC) 28 mol%, acrylic acid without adding the crosslinking agent 2hydroxypropylidene 1,3bis [(N acryloylaminopropyl) N, N dimethylammonium chloride] (HPAD) A sample (Sample-7) to be used for the test was prepared in the same manner as in Synthesis Example-1, except that a mixture of 200 kg monomer having a composition of 2 mol% (AAC) and 70 mol% acrylamide (AAM) was used.
[0032]
(Comparative Synthesis Example-2)
50 mol% acryloyloxyethyltrimethylammonium chloride (AMC), acrylic acid, without the addition of the crosslinking agent 2hydroxypropylidene 1,3 bis [(N acryloylaminopropyl) N, N dimethylammonium chloride] (HPAD) A sample (sample-8) to be used for the test was prepared in the same manner as in Synthesis Example-1 except that a mixture of 200 kg monomer having a composition of only 10 mol% (AAC) and 40 mol% acrylamide (AAM) was used.
[0033]
(Comparative Synthesis Example-3)
Acryloyloxyethyltrimethylammonium chloride (AMC) 50 mol%, acrylamide (2) without addition of the crosslinking agent 2hydroxypropylidene 1,3 bis [(N acryloylaminopropyl) N, N dimethylammonium chloride] (HPAD) AAM) A sample (sample-9) to be used for the test was prepared in the same manner as in Synthesis Example-1, except that a mixture of 200 kg monomer having a composition of only 50 mol% was used.
[0034]
(Comparative Synthesis Example-4)
27.998 mol% acryloyloxyethyltrimethylammonium chloride (AMC) (represented as about 28 in Table 1) as in Synthesis Example-2 except that the polymerization was carried out without adding isopropyl aryl as a chain transfer agent. ), Acrylic acid (AAC) 2 mol%, 2-hydroxypropylidene 1,3 bis [(N acryloylaminopropyl) N, N dimethylammonium chloride] (HPAD) 2 × 10 ⁻³ mol%, acrylamide (AAM) 70 mol A sample (Sample-10) to be used for the test was prepared using a mixture of 200 kg of monomer having a% composition.
[0035]
(Comparative Synthesis Example-5)
49.998 mol% of acryloyloxyethyltrimethylammonium chloride (AMC) (represented as about 50 in Table 1) as in Synthesis Example-4 except that the polymerization was performed without adding isopropyl aryl as a chain transfer agent. ), Acrylic acid (AAC) 10 mol%, 2-hydroxypropylidene 1,3 bis [(N acryloylaminopropyl) N, N dimethyl ammonium chloride] (HPAD) 2 × 10 ⁻³ mol%, acrylamide (AAM) 40 mol A sample (Sample-11) to be tested was prepared using a mixture of 200 kg of monomer having a% composition.
[0036]
(Comparative Synthesis Example-6)
49.998 mol% of acryloyloxyethyltrimethylammonium chloride (AMC) (represented as about 50 in Table 1) in the same manner as in Synthesis Example-6 except that the polymerization was carried out without adding isopropyl aryl as a chain transfer agent. ) 2 hydroxypropylidene 1,3 bis [(N acryloylaminopropyl) N, N dimethylammonium chloride] (HPAD) 2 × 10 ⁻³ mol%, acrylamide (AAM) 50 mol% composition of 200 kg monomer A sample (Sample-12) was prepared for use in the test.
[0037]
(Comparative Synthesis Example-7)
In the presence of a chain transfer agent, acryloyloxyethyltrimethylammonium chloride (AMC) 27.998 mol% (represented as about 28 in Table 1), acrylic acid (AAC) 2 mol%, 2 hydroxypropylidene 1,3 bis [(N acryloylaminopropyl) N, N dimethylammonium chloride] (HPAD) 2 × 10 ⁻³ mol%, acrylamide (AAM) 70 mol% A mixture similar to that in Synthesis Example 2 using a mixture of 200 kg of monomer A phase emulsion polymer was synthesized, and a sample (sample-13) to be used for the test was prepared without post-adding polyoxyethylene nonylphenyl ether as a phase inversion agent to the polymer.
[0038]
(Comparative Synthesis Example-8)
In the presence of a chain transfer agent, acryloyloxyethyltrimethylammonium chloride (AMC) 49.998 mol% (represented as about 50 in Table 1), acrylic acid (AAC) 10 mol%, 2 hydroxypropylidene 1,3 bis [(N acryloylaminopropyl) N, N dimethylammonium chloride] (HPAD) 2 × 10 ⁻³ mol%, acrylamide (AAM) 40 mol% A mixture similar to that in Synthesis Example 2 using a mixture of 200 kg of monomer A phase emulsion polymer was synthesized, and a sample (sample -14) to be used for the test was prepared without post-adding polyoxyethylene nonylphenyl ether as a phase inversion agent to the polymer.
[0039]
(Comparative Synthesis Example-9)
In the presence of a chain transfer agent, acryloyloxyethyltrimethylammonium chloride (AMC) 49.998 mol% (represented as about 50 in Table 1), 2 hydroxypropylidene 1,3 bis [(N acryloylaminopropyl) N, N-dimethylammonium chloride] (HPAD) 2 × 10 ⁻³ mol% and acrylamide (AAM) 50 mol% in a mixture of 200 kg of monomer was used to synthesize a reversed phase emulsion polymer similar to that in Synthesis Example 2, A sample (Sample-15) to be used for the test was prepared without post-adding polyoxyethylene nonylphenyl ether as a compatibilizer to the polymer.
These are summarized in Table 1.
[0040]
[Table 1]
[0041]
(Observation result-1)
Emulsified Sample-1 to Sample-6 were diluted with tap water with an actual screw-type stirrer (300 rpm) to a polymer concentration of 0.2% by weight while stirring, and a liquid with increased viscosity after 1 hour was collected. When observed with a microscope, all particles with a particle size of 30 μm or less (about 3 μm) were observed on one surface, and the diluted solution was applied to a glass plate and heated and dried at 105 ° C. to form a continuous dry film. Formed. Moreover, when the ion equivalent value of this diluted solution was measured by colloid determination, all of the ion equivalent values were 85% or more of the theoretical values.
[0042]
(Observation result-2)
As in observation result-1, samples 7 to 9 in the emulsion state were diluted with tap water with an actual stirrer to a polymer concentration of 0.2% by weight, and the liquid thickened after 1 hour. The sample was collected and observed with a microscope. As a result, all were homogeneous solutions and no particles were observed. The diluted solution was applied to a glass plate and heated and dried at 105 ° C. to form a continuous dry film. Further, when the ion equivalent value of this diluted solution was measured by colloidal titration, the ion equivalent value was 100% of the theoretical value.
[0043]
(Observation result-3)
As in observation result-1, emulsion samples -10 to -12 were diluted with tap water with an actual stirring device to a polymer concentration of 0.2% by weight with stirring, and a liquid that had been thickened after 1 hour was obtained. When collected and observed with a microscope, all particles with a particle size of 30 μm or less (about 3 μm) were observed on one side. The diluted solution was applied to a glass plate and dried at 105 ° C. to form a granular discontinuity. A dry film was formed. Moreover, when the ion equivalent value of this diluted solution was measured by colloid determination, all of the ion equivalent values were 60% or less of the theoretical value.
[0044]
(Observation result-4)
As in observation result-1, samples 13 to 15 in the emulsion state were diluted with tap water with an actual stirring device to a polymer concentration of 0.2% by weight with stirring. As a result, the emulsion was not dispersed in water. The gel-like lump floated and a uniform polymer dilution was not obtained. In contrast, when the magnetic stirrer was vigorously stirred at the beaker scale, the emulsion was dispersed in water, and a uniform polymer dilution was obtained without the gel-like lump floating.
Due to poor solubility, the effect tests of Sample-13 to Sample-15 were not performed.
[0045]
(Effectiveness test)
Sewage mixed raw sludge generated from the sewage treatment plant was dehydrated by a belt press using the diluent prepared in Observation Results -1 to 3. The properties of the sludge subjected to the test are PH: 6.7, SS: 14300 mg / l, loss on ignition 72.5%, and M alkalinity 1500 mg / l. Table 2 shows the results obtained by adding and mixing the SS30% polysulfate to the sludge, adding the SS1.2% polymer, stirring and dewatering with a belt press.
[0046]
[Table 2]

[0047]
【The invention's effect】
It is clear from the above effect test that the dehydration effect is inferior to the product of the present invention when the chain transfer agent and the crosslinking agent at the time of polymerization are absent. It cannot be practically used because it cannot be dissolved. The superiority of the present invention over the conventional product is clear.
[Table-1]

Claims (7)

A polymer obtained by subjecting a monomer containing a water-soluble cationic vinyl monomer represented by the following formula (1) or a mixture thereof to reverse phase emulsion polymerization in the presence of a chain transfer agent and a hydrophilic surfactant In a state diluted with water to a concentration to be added to sludge, particles having a particle size of 30 μm or less were observed with a microscope, and the diluted solution was applied to a glass plate and dried at 105 ° C. by heating. A dewatering agent for sewage mixed raw sludge, characterized in that it sometimes forms a continuous dry film and has an ion equivalent value measured by colloid determination of 85% or more of the theoretical value .

(Wherein, A is O or NH; B is C ₂ H ₄ , C ₃ H ₆ , C ₃ H ₅ OH; R ₁ is H or CH ₃ ; R ₂ and R ₃ are each having 1 to 4 carbon atoms. R ₄ is hydrogen, an alkyl group having 1 to 4 carbon atoms or a benzyl group; X ⁻ represents an anionic counter ion.) (A) 5 to 99.9999 mol% of the water-soluble cationic vinyl monomer represented by the following formula (1) or a mixture thereof, (B) 0.0001 to 0 in all monomers 0.01 mol% of a bifunctional monomer, (C) 0-30 mol% of a water-soluble anionic vinyl monomer or a mixture thereof in all monomers, (D) a nonionic water-soluble monomer, ( E) an amount effective to produce a chain transfer agent, (F) water, (G) an oil consisting of at least one hydrocarbon and (H) a reverse phase emulsion, ie a water-in-oil emulsion, and at least one HLB. Prepare a variety of surfactants, mix and stir the above components (A) to (H) in a timely manner, form fine monomer phase droplets in the oil phase, and perform a polymerization operation to obtain hydrophilic surfactant Of raw sludge mixed with sewage, characterized by mixing the agent and diluting with water The method of production.

(Wherein, A is O or NH; B is C ₂ H ₄ , C ₃ H ₆ , C ₃ H ₅ OH; R ₁ is H or CH ₃ ; R ₂ and R ₃ are each having 1 to 4 carbon atoms. R ₄ is hydrogen, an alkyl group having 1 to 4 carbon atoms or a benzyl group; X ⁻ represents an anionic counter ion.) (A) 5 to 97.9999 mol% of all monomers in water-soluble cationic vinyl monomer represented by the following formula (1) or a mixture thereof, (B) 0.0001 to 0 in all monomers 0.01 mol% of a bifunctional monomer, (C) 2 to 30 mol% of a water-soluble anionic vinyl monomer or a mixture thereof in all monomers, (D) a nonionic water-soluble monomer, ( E) an amount effective to produce a chain transfer agent, (F) water, (G) an oil consisting of at least one hydrocarbon and (H) a reverse phase emulsion, ie a water-in-oil emulsion, and at least one HLB. Prepare a variety of surfactants, mix and stir the above components (A) to (H) in a timely manner, form fine monomer phase droplets in the oil phase, and perform a polymerization operation to obtain hydrophilic surfactant The sewage according to claim 2, wherein the agent is mixed and diluted with water. Gosei manufacturing method of sludge dewatering agent.

(Wherein, A is O or NH; B is C ₂ H ₄ , C ₃ H ₆ , C ₃ H ₅ OH; R ₁ is H or CH ₃ ; R ₂ and R ₃ are each having 1 to 4 carbon atoms. R ₄ is hydrogen, an alkyl group having 1 to 4 carbon atoms or a benzyl group; X ⁻ represents an anionic counter ion.) The method for producing a dewatering agent for sewage mixed raw sludge according to any one of claims 2 to 3 , wherein the nonionic water-soluble monomer is (meth) acrylamide. The method for producing a dewatering agent for sewage mixed raw sludge according to any one of claims 2 to 3, wherein the water-soluble anionic vinyl monomer is (meth) acrylic acid. The bifunctional monomer is N, N-methylenebisacrylamide or 2hydroxypropylidene 1,3bis [(N acryloylaminopropyl) N, N dimethylammonium chloride]. 4. The method for producing a dewatering agent for sewage mixed raw sludge according to any one of 3 above. The method for producing a dewatering agent for sewage mixed raw sludge according to any one of claims 2 to 3, wherein the hydrophilic surfactant is a nonionic surfactant having an HLB of 9 to 15.