200837020 九、發明說明 【發明所屬之技術領域】 本發明爲主要關於於上·下水道設施之淨化水之處理 、或蓄水池、沼澤、河川及湖等之淨化水之處理使用之凝 集劑、與使用此之淨化水之方法的改良；藉由磁力強制地 吸附回收經由攪拌混合凝集劑產生之凝集沈澱物，經由凝 集沈澱物，可爲確實的除去與除去率之提昇、淨化處理時 間之大幅縮短等之新穎的結合磁性體聚合物製之凝集劑、 與使用其淨化水之方法。 【先前技術】 近年來，地球環境污染的防止、被污染之環境的回復 係逐漸成人類社會之迫切的課題，其中亦尤其以防止大氣 暖化、水環境的回復、改善爲應優先被解決之問題。 因此，水環境之保全領域裡，爲對應此等問題，已開 發有各種之技術、系統；藉由廣大區域的污水淨化處理系 統的運用來防止經由生活排水、產業排水之河川、沼湖的 污染，廣爲推進藉由採用高效率的排水處理裝置、處理藥 劑，謀求其污染源之減量的對策。 但是，對於已污染環境的改善，有效對策的實施遲遲 不見進展，現實中係處於所謂「藉由自然的淨化來改善」 的狀態。又，因爲積極地回復已污染的環境，而使用鋁系 凝集劑、聚丙烯醯胺等之合成高分子凝集劑，亦進行淨化 蓄水池、沼湖的水’但此種以往之凝集劑係有對環境產生 200837020 2次污染的危險，於其大量使用時係留下許多問題。 一方面，本發明申請人係，爲解決於使用如上述以往 之鋁系凝集劑、合成高分子系凝集劑之水處理時的諸問題 ’開發一種不引起環境污染之凝集劑，亦即以聚麩胺酸（ polyglutamic acid，PGA)、聚麩胺酸交聯物爲主體之可自 然分解的凝集劑（PGa21、PGa21Ca)的同時，開發使用 此之河川、沼湖等之淨化水之處理技術，並公開（日本特 開 2006-142183、特開 2005-144340、特開 2005-205281、 特開-2002-2 1 03 07、特開 2004- 1 74326、特開 2004-2044 1 等）。 圖5係示使用由上述聚麩胺酸或聚麩胺酸交聯物所成 之凝集劑之沼湖的淨化處理方法之一例；使裝載凝集劑供 給裝置1 1之小型船1 2航行，混合凝集劑槽3內貯留之凝 集劑B至噴射器2中來自空氣壓縮器13的空氣流內，通 過管路1 4從噴嘴1 5朝湖水內噴出的同時，使經由螺旋槳 1 6之回轉噴出的凝集劑B與湖水攪拌混合。 經由攪拌混合凝集劑B，湖水內之污濁物質係以凝集 劑B爲核心凝集，形成所謂凝集物Η (絮凝物（fl〇c )) 的同時，藉由凝集物Η彼此附著，其形狀隨時間過去而更 大形化。 經由攪拌混合凝集劑Β而形成之凝集物Η，係以緩慢 的速度（約1〜6m/日）徐徐地沈降，到達湖底爲止，藉 由附著於所拖曳來的凝集物回收具A或經由撈取，自水中 除去。 -6- 200837020 又，殘留於水中之凝集物Η係最終堆積於湖底，堆積 之凝集劑Β、污濁物質係經過長時間由微生物被自然分解 〇 上述圖5表示蓄水池、沼湖之水質淨化處理方法，係 使用之凝集劑Β本身爲生分解性且因分解生成物爲麩胺具 安全性優異，完全不擔心會有污損其被處理溶液、且也不 會使水中生存之有益的微生物絕種。 因此，以該凝集劑Β處理的水係利用水中存在之脫氮 細菌，藉由進行生物處理，具有亦可所謂的脫氮處理之優 但是，以往的蓄水池、沼湖等之淨化水之處理方法係 留有許多應解決的問題，其中亦必需儘早解決的問題爲凝 集物之確實的除去與凝集沈降之Υ凝集物再擴散的問題。 亦即，經由攪拌混合凝集劑Β以此爲核心所凝集之凝 集物Η，係使之附著於所拖曳來的凝集物回收具A、或使 用撈取器另外來回收，但其回收效率極低、且於凝集物Η 之回收有需多費工夫與費用與時間的問題。 又，於沼湖等之水靜止時，漏於回收之凝集物係經時 間依序沈降，堆積於湖底的同時最終由微生物被自然分解 〇 然而，經發生風波等而水流動時，好不容易沈降堆積 之凝集物或沈降途中之凝集物再被擴散，有經凝集物之微 生物之自然分解慢、其S S等之凝集率降低的問題。 當然，藉由聚麩胺酸凝集劑暫時形成之凝集物，即使 200837020 經由振動等被再分散’分散物本身亦具有再凝集，生長成 大形的絮凝物之優異的特性。但是，因再凝集成大形的絮 凝物需要相當的時間，其結果淨化水之處理時間變長。 進而’於湖底等堆積之凝集物全部經由微生物被分解 係不可能，堆積之凝集物之一部份最終係成淤泥化。其結 果，要是不能提高凝集物之回收率，就有不能防止淤泥發 生的問題。 又’如上述問題，係於上水道設施之原水的凝集淨化 處理或於下水道設施之排水的沈澱淨化處理亦同樣發生的 問題，故持續開發比凝集物更有效率的回收技術。 〔專利文獻1〕日本特開2002-210307 〔專利文獻2〕日本特開2004-174326 〔專利文獻3〕日本特開2005-144340 〔專利文獻4〕日本特開2005-205281 〔專利文獻5〕日本特開2006-142183 【發明內容】 〔發明之揭示〕 〔發明所欲解決之課題〕 本發明，爲鑒於使用習知之凝集劑之淨化水之處理中 之如上述的問題，亦即欲解決（一）經由攪拌混合凝集劑 而產生之凝集物的回收率低、且回收作業時需要多費工夫 ;(二）因氣象條件等而被處理溶液流動時，於凝集物之 沈降係花時間、且一旦沈降之凝集物再被擴散，淨化水之 -8- 200837020 處理效率明顯地降低；（三）因凝集物之回收率低、沈降 之凝集物容易淤泥化等之問題，而提供以具凝集性及親水 性優異，且可以效率良好地使用磁力吸取緊固成長於水中 之凝集物的結合磁性體聚合物製之凝集劑、與使用此之淨 化水之方法爲發明之主要目的。 〔課題所欲解決之手段〕 另外，爲提高於水中生長的同時依序沈降之凝集物的 回收效率，提高藉由回收具之撈取性能或對回收具之附著 性係爲必要的條件。因此，本發明人等係構想使其凝集劑 具磁性、或使其凝集劑結合磁性材、將結合磁性材之凝集 劑粒子作成粒，其周圍吸附S S等，強制地使吸取緊固絮 凝物化之凝集物於磁石體；可於水中浮游的微小磁性材粒 子與具有s S等之吸附性的聚合物之結合體的形成方法、 或對形成之結合體的親水性等反覆各種的試驗。 又，醫療技術領域或生物化學的技術領域，例如於 DNA解析中檢驗出核酸等的領域，使表面具有官能基之微 小磁性粒子上，結合其官能基具有反應之其它的官能基的 聚合物，緊固在此微小磁性粒子的外圍面之上述聚合物中 使核酸反應而將此固定（日本特開平11-225759號等）。 本發明係藉由有機地結合本發明人等實行上述00 1 3 項記載之各種試驗的結果、與0 0 1 4項中記載之生物化學 領域中關於核酸固定的技術，可成具凝集性及親水性優異 、且使用磁力可效率良好安定地吸取緊固於水中成長之凝 -9- 200837020 集物的結合磁性體聚合物製之凝集劑、與新穎地創作出使 用此之淨化水之方法。 亦即，本發明申請項1之發明，係以由磁性材製之微 粒體、與結合於微粒體之砂院化合物或其聚合物、與結合 於微粒體之矽院化合物或結合於其聚合物之具凝集性的聚 合物形成結合磁性體聚合物製之凝集劑作爲發明之基本構 成。 申請項2之發明’係於申請項1之發明中，含有肥粒 鐵（Ferrite )之磁性材製之微粒體爲以Xn〇 · Fe203 (式 中，X 係爲選自 Fe、Mn、Ni、Zn、Co、Cu、Mg、Sn、Ca 及Cd之1種或2種以上者）表不之磁鐵礦上，使肥粒鐵 緊固含有肥粒鐵之磁鐵礦之微粒體的同時，矽烷化合物與 具凝集性之聚合物藉由共有結合而結合之構成。 申請項3之發明，係於申請項1之發明中，使具有凝 集性之聚合物爲吸附水中之懸濁物質、重金屬類或內分泌 攪亂物質之任一者的聚合物。 申請項4之發明，係於申請項1或申請項2之發明中 ，使矽烷化合物爲含有反應性官能基之矽烷或其部分水解 物。 申請項5之發明，係於申請項1或申請項2之發明中 ，使具有凝集性之聚合物爲生分解性聚合物。 申請項6之發明，係於申請項5之發明中，使生分解 性聚合物爲聚胺基酸或聚胺基酸鹽。 申請項7之發明，係於申請項5之發明中，使生分解 -10- 200837020 性聚合物爲聚胺基酸交聯體或聚胺基酸鹽交聯體。 申請項8之發明，係於申請項5之發明中，使生分解 性聚合物爲多醣類或多醣類鹽。 申請項9之發明，係於申請項1或申請項2之發明中 ’使具有凝集性之聚合物爲聚丙烯酸系聚合物。 申請項10之發明，係於申請項1或申請項2之發明 中’使具有凝集性之聚合物爲聚乙二醇系聚合物。 申請項1 1之發明，係以將於被處理溶液內投入固定 量之結合磁性體聚合物製之凝集劑，經攪拌混合之後，使 設置在被處理溶液之底部的磁石轉動，藉由磁石吸附回收 凝集沈泥物作爲發明之基本構成。 申請項1 2之發明，係於申請項1 1之發明中，使5〜 3 OOOmg/L之結合磁性體聚合物製之凝集劑攪拌混合於處 理槽內貯留之被處理溶液內，於1〜1 2 0分鐘後轉動處理 槽底部配置之電磁石，藉由電磁石來吸附回收凝集沈澱物 者。 申請項1 3之發明，係於申請項1 1之發明中，使攪拌 混合結合磁性體聚合物製凝集劑之被處理溶液流通於回收 裝置內的同時，藉由回收裝置之底部設置之磁石，吸附回 收上述流通之被處理溶液內的凝集物。 本發明中，由於將凝集劑含有磁性材製微粒體之構成 ，可使用磁力吸附回收凝集物，可使凝集物之回收率提昇 、回收時間大幅的縮短。 其結果，係可達成更高度的淨化水之處理的同時，可 200837020 謀求淨化處理需要之時間縮短，進而’被處理溶液即使因 氣象條件等變動而流動，也不會有如凝集物再被擴散的情 形，可爲安定之淨化水之處理。 〔實施發明之最佳形態〕 本發明中使用之磁性材製之微粒體，係使用磁鐵礦或 混晶肥粒鐵微粒子之外徑爲4nm〜ΙΟμιη之所謂奈米粒子 。又，磁性材製之微粒體，例如亦可爲氧化鉻、鈷等之肥 粒鐵以外的磁石材或磁性材之微粒子，從低成本、安全性 、安定性、及如後述地與朝磁性材微粒子之外表面緊固（ 或包覆）之矽烷化合物之結合性一點而言，本發明中，作 爲磁性材微粒子係選擇「肥粒鐵」。 又，於磁鐵礦之表面使用抑制氧化之耐氧化性被膜， 係因抑制磁鐵礦朝磁赤鐵礦氧化，有效於材料之安定性的 提昇。作爲耐氧化性被膜，有鋅肥粒鐵（ZnFe204 )等。 前述結合於磁鐵礦或混晶肥粒鐵微粒子之外表面的矽 烷化合物，係爲具有與磁性材製之微粒子結合之官能基的 矽烷化合物，且若爲與後述之具有SS等高凝集性之聚合 物結合之官能基的矽烷化合物爲佳而其種類等係不特別限 定。此種矽烷化合物，一般存在稱爲矽烷偶合劑之矽化合 物中。此種.矽烷化合物，有含有胺基之烷氧基矽烷、含有 環氧基之環氧矽烷等。本發明中，可使用此等之矽烷化合 物之聚合物或部分水解物。 矽烷偶合劑等之矽烷化合物，係矽烷醇基（Si-OH ) -12- 200837020 或水解後成矽烷醇基之烷氧基矽烷，因具有I 氯矽烷，氧化之金屬表面（M-OH)可與Si-O· 此，磁鐵礦之表面當然亦可與鋅肥粒鐵被覆之 共有結合。 具有與固定（結合）於前述磁性材製微粒 合物或其聚合物結合之凝集性的聚合物中，共 化合物或其聚合物的同時，具有SS等之凝集 性高、於水中容易溶解或擴散的同時具有生分 合物爲佳。 本發明中，作爲具有具備如上述特性之凝 解性聚合物，可使用聚胺基酸、聚胺基酸鹽、 醣類鹽、尤其多元胺基酸（polyacidic amino 如，聚D ·麩胺酸、聚L -麩胺酸、聚天 polyaspartic acid )、膠蛋白（C ο 11 a g e η )、 albumin )等）、聚鹼性胺基酸（例如，聚D lysine )、聚L ·離胺酸等）、多醣類（例如， 、幾丁聚醣等）。 又，前述具有凝集性之聚合物，係以使與 結合之後，以此作爲交聯體爲佳。如後述地藉 有聚胺基酸或聚胺基酸鹽等之凝集性之凝集性 爲交聯體，故其凝集性能大幅地提昇。 又，作爲結合於前述磁性材製微粒體之矽 官能基雖有胺基、硫醇基、醛基 '環氧基等各 合物’爲使與具有凝集性之聚合物共有結合， 個或複數個 • Μ結合。因 磁鐵礦形成 體之矽烷化 有結合矽烷 性，且親水 解特性的聚 集性的生分 多醣類或多 a c i d )(例 冬胺酸（ 白蛋白（ -離胺酸（ 藻酸、果膠 矽烷化合物 由以具備具 的聚合物作 烷化合物， 種的矽烷化 有必要使用 -13- 200837020 具有適合具凝集性之聚合物之官能基的矽烷化合物。具有 羧基之具凝集性的聚合物，係以於官能基具有可形成醯胺 基結合之胺基的矽烷化合物爲佳。將官能基具有胺基的矽 烷化合物，可例示3 -胺基丙基三甲氧基矽烷、3 ·( 2 -胺乙 基）胺基丙基三甲氧基矽烷、式H2N(CH2)2NH(CH2)2 NH ( CH) 2Si ( OCH3) 3所示之烷氧基矽烷等之胺基烷基 院氧基砂院。 又’藉由使結合官能基中具有胺基之矽烷化合物的磁 性材製微粒體與酸酐反應，可將末端胺基添加於羧基。將 官能基中具有羧基的磁性材製微粒體，係因可形成胺基與 醯胺基結合，故可使用於具有胺基之具凝集性的聚合物之 結合。 又’作爲具有前述水中的污濁物質（例如，s S或 BOD等）之凝集性之具凝集性的聚合物，以聚胺基酸（例 如，聚麩胺酸）、聚胺基酸鹽、（例如，聚麩胺酸鹽）或 聚胺基酸衍生物以及聚胺基酸、聚胺基酸鹽或聚胺基酸衍 生物之交聯體最適合。 更具體地，本發明中使用之胺基酸，係有甘胺酸、丙 胺酸、纈胺酸、正纈胺酸、白胺酸、正白胺酸、異白胺酸 、苯丙胺酸、酪胺酸、二碘酪胺酸（diiodotyrosine ) 、N-甲酪胺酸、蘇胺酸、絲胺酸、脯胺酸、羥基腩胺酸、色胺 酸、甲狀腺素、甲硫胺酸、胱胺酸、半胱胺酸、胺基丁 酸、天冬胺酸、麩胺酸、離胺酸、羥離胺酸、精胺酸、組 胺酸等。由此等胺基酸所成之聚胺基酸或聚胺基酸鹽於本 -14- 200837020 發明中多爲供於利用。 一般，胺基酸之構造式係以NH2 ( COOH ) -CH-R表 示。聚胺基酸中同一存在胺基酸鏈狀地聚合之均聚物與複 數種之胺基酸鏈狀地聚合之雜聚物，聚胺基酸中之氫原子 Η或氧原子Ο係因結合水與氫，所以聚胺基酸係表面具有 吸附水的保濕性。 以輻射線照射此鏈狀分子之聚胺基酸，例如，聚胺基 酸中之CH2藉由脫氫反應而成CH-，2條聚胺基酸之CH-彼此結合成CH-HC形成交聯體。多數聚胺基酸彼此以輻 射線交聯成網目構造，此網目構造的內部形成多數袋狀的 空間。 經由輻射線之交聯係因不用加熱聚胺基酸就可交聯， 故可保有胺基酸原本的性質而形成聚胺基酸輻射線交聯體 。輻射線交聯反應係爲低溫交聯反應，與經由加熱之交聯 反應不同。經由加熱，聚胺基酸係受熱力變質，但於輻射 線交聯係有不受熱力變質一點的特徵。 又，上述聚胺基酸輻射線交聯體係因內部具有多數袋 狀空間，此袋狀空間具有吸收保存水分子的能力，藉此作 用可具有比聚胺基酸還大的保水性，悉知此保水性能係爲 有吸收懸濁物質使凝集的凝集性能。 本發明中作爲聚胺基酸，使用如實施例示之曰本 P〇Iy-Glu股份有限公司製之γ-聚麩胺酸，此聚麩胺酸係 爲以（-00C-CH2-CH2-CH(C00H) ΝΗ-) η 所表示之鏈狀 分子’下標η爲給予聚合度。成爲出發原料之γ-聚麩胺酸 -15· 200837020 係分子量大者，尤其具有數十萬〜數百萬的分子量者爲合 適，此等之分子量係以前述聚合度而決定。 又’於此γ -聚魅胺酸照射輻射線，藉由脫氫反應C Η 2 成CH-，2條γ-聚麩胺酸之直鏈介由CH-HC連結，如〔（ -OOC-CH2-CH(COOH) ΝΗ-) η〕2般地進行交聯。此交聯 度更大時，生成如〔（-OOC-CH2-CH2-CH ( COOH ) ΝΗ-)n〕m般的分子量大的輻射線交聯體。其中，m係示交聯 度’爲給予被交聯連結之γ-聚麩胺酸之直鏈的條數。 又’藉由加大交聯度，γ-聚麩胺酸輻射線交聯體之分 子量係可以1 000萬以上。聚麩胺酸係爲多肽鏈，故藉 由- CH-HC-的連結於內部可形成多數個大空間之網目構造 ，如前述地，於此多數個內部空間裡吸收污濁水，於內部 積蓄污濁物質。 且，前述聚胺基酸，雖藉由種種的製造方法所生產， 但藉由微生物所生產之聚胺基酸爲天然物質，由安全性之 觀點而言也爲適合，聚胺基酸中亦有聚麩胺酸或聚天冬 胺酸也都適於本發明之實施。 又，作爲具有凝集性之聚丙烯酸系聚合物，有陰離子 性的聚丙烯酸或其鹽、非離子之聚丙烯醯胺、陽離子性的 聚（Ν，Ν，Ν，-三甲基胺基乙基甲基丙烯酸酯氯化物）等。 進而，作爲具有凝集性之聚乙二醇系聚合物，有聚乙 二醇、或聚乙二醇之一末端結合烷基或離子性官能基等之 聚乙二醇衍生物等。 具有如以上之凝集性的各聚合物，係具有吸附於水中 -16- 200837020 浮游存在之污濁物質的特性、且藉由磁力具有可吸引靠近 的特性，故合適於使用在要求有此般特性的用途上。例如 ，將本發明之結合磁性體聚合物製之凝集劑，投入於污濁 物存在之水的積存場所，例如淨化，水之處理場、蓄水池、 沼澤、河川、湖、魚之養殖場等的水中，並使其分散，於 吸附了污濁物質之後，使吸附此污濁物質之結合磁性體聚 合物製之凝集劑以磁力吸引靠近，則可容易地回收存在水 中的污濁物質。 【實施方式】 〔實施例1〕 使結合矽烷化合物之磁性材製微粒體的形成（1 ) 實施例1中，使磁性材之磁鐵礦的微粒子的外表面形 成結合（包覆）APTS的矽烷化合物。 首先，將含有肥粒鐵之磁鐵礦（Fe3 04 )的微粒體（ 平均粒徑0.2 μπι )加入乙醇中，成爲0.01 2 8M溶液。其後 ，藉由水lml +乙醇+前述溶液25ml，稀釋溶液成150ml， 將此溶液經3 0分鐘超音波後進行攪拌。其後，此溶液中 加入APTS ( 3-胺基丙基三乙氧基矽烷）35μ1，加上7小 時間激烈的攪拌。接著，將攪拌物放入蒸發器，藉由除去 所含有的乙醇，得到以APTS包覆之磁鐵礦微粒體。 亦即，磁鐵礦微粒體（磁性材製微粒體）的外表面， 可得到結合了以胺基作爲官能基之APTS (矽烷化合物） 的微粒體。 -17- 200837020 〔實施例2〕 使結合矽烷化合物之磁性材製微粒體的形成（2 ) 此實施例2中，製作使磁性材之磁鐵礦微粒子的外表 面結合以羧基作爲官能基的矽烷化合物（1 )。 首先，將APTS ·包覆磁鐵礦微粒體加入於乙酸乙酯 8 0ml中，一邊攪拌使其分散。於此再加入琥珀酸酐，使 其進行20分鐘反應。反應結束後，藉由以乙酸乙酯3次 洗淨，得到具有羧基末端之磁鐵礦微粒體。 〔實施例3〕 以具有凝集性之聚合物作成聚麩胺酸鹽之凝集劑的生 成（1 ) 生成使用前述實施例1中形成之APTS包覆磁鐵礦微 粒體，於此結合以γ-聚麩胺酸之鈉鹽作爲具有凝集性的聚 合物之凝集劑。 首先，將分子量80萬〜100萬之γ-聚麩胺酸（γ-聚麩 胺酸ΤΥΡΕ-Η、日本Poly-Glu (股）製··以下的實施例亦 相同）、APTS ·包覆磁鐵礦微粒體（9.6mm 〇1 )及4-二甲 基胺基卩比Π定（97.7mg: 0.8mmol)於80ml水中一邊攪拌使 其分散。進而，於此溶液中加入卜乙基_ 3 - ( 3 -二甲基胺 基丙基）-碳二醯亞胺鹽酸鹽（〗993.7mg: 10.4mmol), 於〇°C下攪拌2小時。其後，於室溫下攪拌一晚。在冷卻 下（〇°C )於所得溶液中，添加溶解氫氧化鈉5.5g於30ml -18- 200837020 水之NaOH水溶液，進而，於室溫下攪拌一晚。接著，於 此加入6N鹽酸溶液使該溶液成酸性（約PH5 )，再於室 溫下攪拌〗小時。其後，使用磁石分離生成物，藉由凍乾 分離出的生成物，即得本發明之凝集劑。 亦即，實施例3中所得之凝集劑，係使磁性材製微粒 體結合以胺基作爲官能基的矽烷化合物（APTS )的同時 ，此矽烷化合物中藉由醯胺基結合而結合成具有凝集性之 聚合物（聚麩胺酸之鈉鹽）而成之凝集劑。 〔實施例4〕 以具有凝集性之聚合物作成幾丁聚醣之凝集劑的生成 (2 ) 使用前述實施例2中形成之具有羧基末端之磁鐵礦微 粒體，藉由於此結合藉由以醯胺基結合幾丁聚醣使成具有 凝集性之聚合物而合成凝集劑。 首先，使具有幾丁聚醣（幾丁聚醣低分子量、Aldrich 製）、羧基末端之磁鐵礦微粒體（9.6mmol)及4 -二甲基 胺基卩比D定（9 7 · 7 m g : 0 · 8 m m ο 1 )於8 0 m I水中一邊攪拌使其 分散。進而，於此溶液中加入1-乙基- 3-(3 -二甲基胺基 丙基）-碳二醯亞胺鹽酸鹽（ 1993.7mg: 10.4mmol)，於0 °C下攪拌2小時。其後，於室溫下攪拌一晚。在冷卻下（ 〇°C )於所得溶液中，添加溶解氫氧化鈉5.5g於30ml水 之NaOH水溶液，進而，於室溫下攪拌一晚。接著，於此 加入6N鹽酸溶液使該溶液成酸性（約PH5 )，再於室溫 -19- 200837020 下攪拌1小時。其後，使用磁石分離生成物，藉由凍乾分 離出的生成物，即得本發明之凝集劑。 亦即，實施例4中所得之凝集劑爲於磁性材製微粒體 結合以胺基作爲官能基之矽烷化合物（APTS )的同時， 官能基之胺基與琥珀酸之一方面的羧基進行醯胺基結合， 其它方面之羧基爲與具凝集性之聚合物（幾丁聚醣）醯胺 基結合而成之凝集劑。 〔實施例5〕 圖1 ’係爲示使用本發明之結合磁性體型聚合物製之 凝集劑之淨化水之方法的實施例，圖1中，W爲被處理溶 液、B爲凝集劑、Μ爲電磁石、E直流電源、S爲開關、3 爲槽、1 7爲處理溶液排出口、1 7a爲閥、1 8爲凝集物排出 口、18a爲閥、19爲攪拌混合器。 對貯留於容量15 ton之槽3內之約1〇 ton的被處理 溶液W內，相對於被處理溶液W以200mg/L之比例，混 合爲凝集劑B之實施例3形成的凝集劑。 藉由攪拌混合機1 9約7分鐘攪拌混合被處理溶液W 後，使被處理溶液W靜置1 5分鐘，其後投入開關S，使 電磁石Μ轉動。又，電磁石Μ之磁通量密度設定爲0.12 〜0· 1 5 Wb/m2 〇 藉由使電磁石Μ轉動，約3 0〜60秒後槽3內漂游中 的凝集物幾乎完全地被吸附於電磁石Μ側，藉由開放排出 口 1 7而清淨之處理完畢的水，又，開放開關S，藉由開 -20» 200837020 放抽出口 1 8，被電磁石Μ吸附之凝集物各自往槽3外排 出。 以習知之聚麩胺酸爲主體之凝集劑的情形，在同一條 件下攪拌混合凝集劑之際，凝集物自然沈降到槽底部，需 要約60〜120分鐘。對此，使用本發明之凝集劑時，約20 分鐘幾乎可吸附全部的凝集物於電磁石Μ側，謀求淨化水 之處理時間大幅縮短的同時，可得更清淨之處理排水，可 比被處理溶液W更高度的淨化。 又，此實施例5中，將僅使用本發明之凝集劑，本發 明之凝集劑中加入以往之其它的凝集劑，使藉由後者之凝 集劑所形成之絮凝物結合於由前者之凝集劑所形成之絮凝 物，經由磁力可吸附兩絮凝物。 〔實施例6〕 圖2爲表示使用本發明之結合磁性體聚合物製之凝集 劑之淨化水之方法的其它實施例，於圖2中2 0爲凝集物 的回收裝置。 該實施例中，於槽3內混合固定量的凝集劑Β後，放 置於所定的時間後，槽3內之混合水通過排出口 1 7，2 1導 出至回收裝置20內，使一邊流通於回收裝置20內的同時 ，使吸附混合水內之凝集物於電磁石Μ側。 亦即，攪拌混合凝集劑Β後，於槽3內藉由短時間靜 置被處理溶液W，被處理溶液w之s S等係於某程度大地 被凝集。其後，被處理溶液W流動於回收裝置2 0內之期 -21 - 200837020 間，某程度大地被凝集之水中的凝集物係朝電磁石Μ側依 序地被吸附，其結果極高度地被處理之清淨的處理溶液從 排出口 22被排出去。 又，被吸附之凝集物係以電磁石Μ作爲非勵磁，藉由 開放抽出口 1 8朝回收裝置2 0外排出。又，被處理溶液W 於回收裝置2 0內流動時，電磁石Μ係爲於勵磁狀態，其 磁通量密度設定爲約0.1 2〜0.15 Wb/m2。 圖3之（a) 、（b)及（c)係表示朝被處理溶液（ SS30mmg/L、COD25mmg/L)內，將實施例3之結合磁性體 聚合物製之凝集劑B以200mg/L的比例混入時之凝集物之 狀態的照片，（a )係表示攪拌混合凝集劑B後不久；（b )係表示攪拌混合3 0分鐘後；（c )係表示電磁石轉動開 始之2分鐘後的狀態。 如圖3之（b )及（c )的對比也明顯地，其藉由電磁 石的轉動，凝集物被極爲迅速地幾乎完全吸附至電磁石Μ 側。亦即，經由附加磁力，分離成凝集物與磁性材製微粒 體，僅磁性材製微粒體被吸附至電磁石側，可確定完全不 產生凝集物係像在水中浮游般的情形。 〔實施例7〕 每一經由結合磁性體聚合物製之凝集劑（稱之PGM-L )之凝集處理後的經過時間之絮凝物分離性的調查 首先，製作20ppm的高嶺土懸濁液，作爲進行凝集處 理之原水，添加藉由日本Poly-Glu (股）之γ-聚麩胺酸交 -22· 200837020 聯物凝集劑（PGa21Ca )之凝集處理後的上清液、與於實 施例3形成之結合磁性體聚合物製之凝集劑（PGM-L )後 ，對添加PGoc2 1Ca進行凝集處理後的上清液、與作爲空 白試驗不進行處理下靜置者，測定每一經過時間之各別的 濁度，進行比較。 又，原水，係於水道水中添加20ppm高嶺土，均勻地 混雜般地攪拌製作。又，試樣之測定，係採取以以下的方 法製作之試樣之水深2 · 5 cm處的上清液，進行濁度的測定 〇 試樣1 :原水中添加50ppm之PGa21 Ca，進行凝集處 理。 試樣2 :原水中添加28ppm之PGM-L之後，添加 5 0ppm之PGa2 1Ca，進行凝集處理，處理後馬上投入3個 附有磁石之攪拌棒（stirrer bar)。 空白試驗：原水中什麼都不添加，進行與凝集處理一 樣的操作。 凝集處理條件係如下述。亦即，試料容器爲50OmL燒 杯、試料體積爲5 00mL。攪拌條件係進行10分鐘急速攪 拌。攪拌機使用凝集反應試驗機。又，處理時之試樣的水 溫爲 1 7.4°C、ρΗ7·6。 又，測定係使用下述表1之測定器。 -23- 200837020 〔表1〕 濁度 使用笠原理化工業之濁度計TR-55(聚苯乙烯濁度）。 測定範圍0.00〜1100mg/L pH 使用METTLER-TOLEDO公司製pH製造MP220 (玻璃電極法）。 以下示各試樣分別靜置時間之濁度。 〔表2〕 ^凝集處理後之各靜置時 間之濁度 靜置時間 (分鐘） 僅 PGcx21Ca 試樣1 (度） PGM-L+PGa21Ca 試樣2 (度） 空白試驗 (度） 2 17.0 9.30 19.5 4 14.4 8.78 19.6 6 12.0 8.46 19.9 8 11.4 8.35 20.0 10 11.0 8.01 19.3 15 9.01 7.10 18.8 20 7.16 6.57 18.7 圖4爲表示凝集處理後之各試樣的濁度的變遷，靜置 2分鐘添加PGM-L之試樣2者與試樣〗比較，濁度大爲降 低’其後兩試樣均隨時間經過濁度下降。試樣2係於凝集 處理後的2分鐘內，水中浮游之絮凝物被吸附於投入的磁 石上，大的絮凝物係幾乎被分離，但試樣1係爲尙有些許 大的絮凝物在浮游的狀態。由此可知，添加PGM-L之試 樣2的絮凝物係具有磁性，藉由可被磁石吸附，可比沒有 添加PGM-L者更能早點分離絮凝物。 -24· 200837020 又，由實施例6之試驗結果’可確認經由PGM-L被 凝集之絮凝物，經由外加磁力不會從磁性材製微粒體分離 〔產業上之可利用性〕 本發明不僅適用於上·下水道設施或河川、沼湖等之 淨化水之處理，亦可適用於工業製品之製造過程中原材料 的純化等。 【圖式簡單說明】 〔圖1〕爲表示使用本發明之凝集劑之淨化水之處理 之一側的說明圖。 〔圖2〕爲表示使用本發明之凝集劑之淨化水之處理 之其它例的說明圖。 〔圖3〕爲使用本發明之凝集劑時之水中的凝集物之 狀態的圖面（照片），各自表示（a )係表示混合攪拌凝 集劑後不久；（b )係表示停止攪拌3 0分鐘後；（c )係 表示電磁石勵磁2分鐘後之水中的狀態。 〔圖4〕表示於實施例6之各試樣的凝集處理後的濁 度之變遷的曲線。 〔圖5〕爲表示藉由以習知之聚麩胺酸爲主體之凝集 劑之池或河川的淨化處理狀態的說明圖。 【主要元件符號說明】 -25- 200837020 3 :槽 1 7 :排出口 1 7 a ··閥 1 8 :抽出口 1 8a :閥 1 9 :攪拌混合機 2 0 :回收裝置 2 1 :排水口 2 1 a :閥 W :被處理溶液 B :凝集劑 Μ :電磁石 -26-200837020 IX. INSTRUCTIONS OF THE INVENTION [Technical Field to Be Invented by the Invention] The present invention relates to a process for treating purified water in an upper and lower sewer facility, or a flocculating agent used for treatment of purified water in a reservoir, a swamp, a river, and a lake, and Improvement of the method for purifying water by using this; forcibly adsorbing and collecting the aggregated precipitate generated by stirring and mixing the aggregating agent by magnetic force, and by agglomerating the precipitate, the improvement of the removal and removal rate can be ensured, and the purification treatment time can be greatly shortened. A novel method of combining an aggregating agent made of a magnetic polymer with a method of purifying water using the same. [Prior Art] In recent years, the prevention of the pollution of the earth's environment and the response to the polluted environment have become an urgent issue in human society. In particular, prevention of atmospheric warming and restoration and improvement of the water environment should be resolved first. problem. Therefore, in the field of the preservation of the water environment, various technologies and systems have been developed to cope with such problems. The use of sewage purification treatment systems in a wide area to prevent pollution of rivers and marsh lakes through domestic drainage and industrial drainage. In order to reduce the amount of pollution sources by using a highly efficient drainage treatment device and a treatment agent. However, in the case of the improvement of the polluted environment, the implementation of effective measures has not progressed, and in reality, it is in a state of "improvement by natural purification." In addition, since the synthetic polymer aggregating agent such as an aluminum-based aggregating agent or a polyacrylamide is used to actively restore the contaminated environment, the water in the reservoir and the marsh lake is also purified, but such a conventional aggregating agent is used. There is a risk of secondary pollution to the environment of 200837020, which leaves many problems when it is used in large quantities. On the one hand, the applicant of the present invention develops a coagulant which does not cause environmental pollution, that is, agglomerates, in order to solve the problems in the water treatment using the conventional aluminum-based aggregating agent and the synthetic polymer-based aggregating agent. The glutamic acid (PGA) and polyglutamic acid cross-linking compounds are the main decomposable aggregating agents (PGa21, PGa21Ca), and the treatment technology of purified water such as rivers and lakes is developed. And it is disclosed (Japanese Laid-Open Patent Publication No. 2006-142183, JP-A-2005-144340, JP-A-2005-205281, JP-A-2002-2 1 03 07, JP-A-2004- 1 74326, JP-A-2004-2044, etc.). Fig. 5 is a view showing an example of a purification treatment method of a marsh lake using an agglutinating agent formed by the above-mentioned polyglutamic acid or polyglutamic acid cross-linking agent; the small vessel 12 loaded with the aggregating agent supply device 1 is navigated and mixed. The aggregating agent B stored in the aggregating agent tank 3 flows into the air flow from the air compressor 13 in the ejector 2, and is ejected from the nozzle 15 into the lake water through the line 14 while being ejected through the rotation of the propeller 16. Aggregate B is mixed with the lake water and stirred. By agitation and mixing of the aggregating agent B, the fouling substance in the lake water is agglomerated with the aggregating agent B as a core, and a so-called agglomerate (flocc) is formed, and the agglomerates are attached to each other, and the shape thereof is time-dependent. In the past, it has become more formalized. The agglomerate enthalpy formed by stirring and mixing the aggregating agent 徐 slowly settles at a slow speed (about 1 to 6 m/day) until reaching the bottom of the lake, by attaching to the agglomerated recovery material A or by drawing , removed from the water. -6- 200837020 In addition, the agglomerates remaining in the water are finally deposited on the bottom of the lake, and the accumulated agglomerating agents and fouling substances are naturally decomposed by microorganisms for a long time. The above-mentioned Fig. 5 shows the water purification of the reservoir and the lake. The treatment method is that the agglutinating agent itself is biodegradable and the decomposition product is glutamine which is excellent in safety, and is not worried about the beneficial microorganisms which may defile the treated solution and do not survive in the water. Extinct. Therefore, the water treated by the aggregating agent 利用 utilizes the denitrifying bacteria present in the water, and is biologically treated, and has a so-called denitrification treatment. However, the purified water of the conventional reservoir and the lake is the same. The treatment method has many problems to be solved, and the problem that must be solved as early as possible is the problem of the abundance of agglomerates and the re-diffusion of agglomerates. In other words, the agglomerate condensed by the agglutinating agent as a core is adhered to the agglomerated recovery material A that is towed, or is recovered by using a fishing device, but the recovery efficiency is extremely low. And the recovery of agglomerates 有 requires a lot of work and cost and time. In addition, when the water such as the lake is stationary, the agglomerates that have leaked out of the collection settle down in time, accumulate on the bottom of the lake, and are finally naturally decomposed by the microorganisms. However, when water flows due to wind waves or the like, it is difficult to settle. The accumulated aggregates or the agglomerates in the sedimentation are further diffused, and the natural decomposition of the microorganisms having the aggregates is slow, and the aggregation rate of the SS or the like is lowered. Of course, the agglomerates temporarily formed by the polyglutamic acid aggregating agent are redispersed even by vibration or the like in 200837020. The dispersion itself has re-aggregation and is excellent in the growth of large-sized flocs. However, it takes a considerable amount of time to recondense the large-sized flocs, and as a result, the treatment time for purifying the water becomes long. Further, all of the aggregates deposited on the bottom of the lake are not decomposed by microorganisms, and one part of the accumulated aggregates is eventually sludged. As a result, if the recovery rate of aggregates cannot be increased, there is a problem that sludge cannot be prevented. Further, as described above, the same problem occurs in the agglomeration purification treatment of the raw water in the sewer facility or the sediment purification treatment in the drainage of the sewer facility, so that a more efficient recovery technique than the aggregate is continuously developed. [Patent Document 1] JP-A-2002-210307 [Patent Document 2] JP-A-2004-174326 [Patent Document 3] JP-A-2005-144340 [Patent Document 4] JP-A-2005-205281 [Patent Document 5] Japan JP-A-2006-142183 [Disclosure of the Invention] [Problem to be Solved by the Invention] The present invention is to solve the above problems in the treatment of purified water using a conventional aggregating agent. The recovery rate of the aggregate generated by stirring and mixing the aggregating agent is low, and it takes much time to recover the operation; (2) When the treated solution flows due to meteorological conditions or the like, the sedimentation of the aggregate takes time, and once The settled agglomerates are further diffused, the treatment efficiency of the purified water is significantly reduced -8-200837020; (3) the agglutination and the agglutination are provided due to the problem that the recovery rate of the aggregate is low and the agglomerated sediment is easily sludged. An agglomerating agent made of a bonded magnetic polymer which is excellent in hydrophilicity and which can efficiently extract agglomerates which are grown in water by magnetic attraction, and a method of using the purified water. The main purpose. [Means to be Solved by the Problem] In addition, in order to improve the recovery efficiency of the aggregates which are sequentially settled while growing in water, it is necessary to improve the fishing performance by the recovery tool or the adhesion to the recovery tool. Therefore, the inventors of the present invention have conceived that the aggregating agent is magnetic, or that the coagulating agent is bonded to the magnetic material, the agglomerating agent particles of the bonded magnetic material are granulated, and SS or the like is adsorbed around the coagulating agent, and the suction flocculation is forcibly caused. The aggregate is in a magnet body; a method of forming a combination of a fine magnetic material particle floating in water and a polymer having an adsorption property such as s S, or a hydrophilicity test of the formed combination is repeated. Further, in the field of medical technology or biochemistry, for example, in the field of DNA analysis, a nucleic acid or the like is examined, and a small magnetic particle having a functional group on its surface is bonded to a polymer having a functional group having another functional group. The nucleic acid is immobilized in the above-mentioned polymer which is fastened to the outer surface of the micromagnetic particles to fix the nucleic acid (Japanese Patent Laid-Open No. Hei 11-225759, etc.). The present invention is capable of forming agglutination by organically combining the results of various tests described in the above-mentioned 00 1 3, and the technique of nucleic acid immobilization in the field of biochemistry described in WO 01. An aggregating agent made of a bonded magnetic polymer which is excellent in hydrophilicity and which is capable of efficiently and stably aspirating the aggregate of the condensed -9-200837020 which is fastened in water, and a method of artificially using the purified water. That is, the invention of claim 1 of the present invention is a microsomal body made of a magnetic material, a sand compound compound or a polymer thereof bonded to the microsome, a broth compound combined with the microsome, or a polymer thereof The agglomerated polymer forms a coagulant made of a magnetic polymer as a basic constitution of the invention. The invention of claim 2 is the invention of claim 1, wherein the microparticles of the ferrite-containing magnetic material are Xn〇·Fe203 (wherein X is selected from the group consisting of Fe, Mn, and Ni, In the magnetite ore, which is one or more of Zn, Co, Cu, Mg, Sn, Ca, and Cd, the ferrite is fixed to the magnetite containing the ferrite and iron. The decane compound and the agglutinating polymer are combined by mutual bonding. The invention of claim 3 is the invention of claim 1, wherein the polymer having aggregability is a polymer which adsorbs any of a suspended substance, a heavy metal or an endocrine disrupting substance in water. The invention of claim 4 is the invention of claim 1 or 2, wherein the decane compound is a decane containing a reactive functional group or a partial hydrolyzate thereof. The invention of claim 5 is the invention of claim 1 or 2, wherein the polymer having aggregability is a biodegradable polymer. The invention of claim 6 is the invention of claim 5, wherein the biodegradable polymer is a polyamino acid or a polyamino acid salt. The invention of claim 7 is in the invention of claim 5, and the biodegradable -10- 200837020 polymer is a polyamino acid crosslinked body or a polyamino acid salt crosslinked body. The invention of claim 8 is the invention of claim 5, wherein the biodegradable polymer is a polysaccharide or a polysaccharide salt. The invention of claim 9 is the invention of claim 1 or 2, wherein the polymer having aggregability is a polyacrylic polymer. The invention of claim 10 is the invention of claim 1 or 2, wherein the polymer having aggregability is a polyethylene glycol-based polymer. According to the invention of claim 11, the agglomerating agent of the bonded magnetic polymer is put into a fixed amount in the solution to be treated, and after stirring and mixing, the magnet disposed at the bottom of the solution to be processed is rotated, and the magnet is adsorbed by the magnet. The recovery of agglomerated sediments is a basic component of the invention. The invention of claim 1 is the invention of claim 1, wherein the agglomerating agent of the bonded magnetic polymer of 5 to 3 mg mg/L is stirred and mixed in the treated solution stored in the treatment tank, in 1~ After 120 minutes, the electromagnet disposed at the bottom of the treatment tank was rotated, and the agglomerated sediment was adsorbed and recovered by the electromagnet. The invention of claim 1 is the invention of claim 1, wherein the solution to be mixed and combined with the magnetic polymer aggregating agent is passed through the recovery device while the magnet is disposed at the bottom of the recovery device. The aggregates in the above-mentioned treated solution are adsorbed and recovered. In the present invention, since the aggregating agent contains a magnetic material-made fine particle structure, the aggregate can be recovered by magnetic adsorption, and the recovery rate of the aggregate can be improved, and the recovery time can be greatly shortened. As a result, it is possible to achieve a higher level of treatment of purified water, and the time required for the purification treatment can be shortened in 200837020, and the 'processed solution will flow even if it flows due to changes in meteorological conditions, and there will be no diffusion of aggregates. In case, it can be the treatment of stable purified water. [Best Mode for Carrying Out the Invention] The microparticles produced by the magnetic material used in the present invention are so-called nanoparticles having an outer diameter of 4 nm to ΙΟμηη of magnetite or mixed crystallite iron fine particles. Further, the fine particles made of a magnetic material may be, for example, a magnetic stone such as chrome oxide or cobalt, or a fine particle of a magnetic material, which is low in cost, safety, stability, and magnetic material as will be described later. In the present invention, in the present invention, "fertilizer iron" is selected as the magnetic material fine particle system in the point of bonding of the decane compound which is fastened (or coated) on the outer surface of the microparticle. Further, the use of an oxidation-resistant coating for suppressing oxidation on the surface of magnetite is effective in suppressing the oxidation of magnetite to maghemite and improving the stability of the material. Examples of the oxidation resistant coating include zinc ferrite (ZnFe204). The decane compound bonded to the outer surface of the magnetite or the mixed crystal iron fine particles is a decane compound having a functional group bonded to the fine particles of the magnetic material, and has a high agglutination property such as SS as described later. The decane compound having a polymer-bonded functional group is preferred, and the kind thereof is not particularly limited. Such a decane compound is generally present in a ruthenium compound called a decane coupling agent. Such a decane compound includes an alkoxy decane having an amino group, an epoxy decane containing an epoxy group, and the like. In the present invention, polymers or partial hydrolyzates of such decane compounds can be used. a decane compound such as a decane coupling agent, which is a stanol group (Si-OH) -12-200837020 or an alkoxy decane which is hydrolyzed to a stanol group, and has an oxidized metal surface (M-OH) because of I chlorodecane. With Si-O·, the surface of magnetite can of course also be combined with the coating of zinc-coated iron. It has a cohesive polymer which is bonded (bonded) to the above-mentioned magnetic material-made microparticles or a polymer thereof, and has a high aggregability of SS or the like and is easily dissolved or diffused in water. It is better to have a raw fraction at the same time. In the present invention, as the condensable polymer having the above characteristics, a polyamino acid, a polyamino acid salt, a saccharide salt, particularly a polyamino acid (such as poly D glutamic acid) can be used. , poly-L-glutamic acid, polyaspartic acid), gelatin (C ο 11 age η ), albumin), polybasic amino acids (eg, poly D lysine ), poly L · lysine, etc. ), polysaccharides (eg, chitosan, etc.). Further, the above-mentioned polymer having agglomerability is preferably used as a crosslinked body after bonding. As described later, the agglutinating aggregability of the polyamino acid or the polyamino acid salt is a crosslinked body, so that the aggregation property is greatly improved. Further, the oxime functional group bonded to the magnetic material-made microparticles has an amine group, a thiol group, or an aldehyde group 'epoxy group, etc., in order to share the polymer with the agglutinating polymer, or plural • Μ combined. Because of the crystallization of magnetite forming bodies, there are saccharin-like and polyhydric-characteristic aggregation of polysaccharides or polyacids (such as aspartic acid (alginic acid (alginic acid, alginic acid, pectin) It is necessary to use a decane compound having a polymer having a polymer as an alkyl compound, and it is necessary to use a decane compound having a functional group suitable for a polymer having agglomerability. A polymer having a carboxyl group is agglomerating. The decane compound having a functional group having an amine group capable of forming a mercapto group is preferred. A decane compound having an amine group as a functional group is exemplified by 3-aminopropyltrimethoxydecane, 3 ·(2-amine B Aminoalkyl trimethoxy decane, an alkoxy decane such as alkoxy decane represented by the formula H2N(CH2)2NH(CH2)2 NH(CH) 2Si(OCH3)3. 'The terminal amine group can be added to a carboxyl group by reacting a microparticle of a magnetic material having a decane compound having an amine group in a functional group with an acid anhydride. A magnetic material having a carboxyl group in a functional group can be formed into a microparticle. The amine group is combined with the guanamine group, so it can be used a combination of an agglomerated polymer having an amine group. Also as a polymerizable agglomerating polymer having a turbid substance (for example, s S or BOD or the like) in the above water, a polyamino acid (for example, Polysorbate, polyamine acid salt, (for example, polyglutamate) or polyamino acid derivative, and crosslinked body of polyamino acid, polyamino acid salt or polyamino acid derivative More specifically, the amino acid used in the present invention is glycine, alanine, valine, n-proline, leucine, orthraenic acid, isoleucine, phenylalanine , tyrosine, diiodotyrosine, N-methyltyramine, threonine, serine, valine, hydroxyproline, tryptophan, thyroxine, methionine, Cystamine, cysteine, aminobutyric acid, aspartic acid, glutamic acid, lysine, hydroxy lysine, arginine, histidine, etc. Polyamino acids or polyamino acid salts are mostly used in the invention of the present invention. In general, the structural formula of the amino acid is represented by NH2(COOH)-CH-R. a polyglycol in which a homopolymer of a chain-like polymerization of an amino acid is present and a chain polymerized heteropolymer of a plurality of amino acids, a hydrogen atom of a polyamino acid or a ruthenium of an oxygen atom Water and hydrogen, so the surface of the polyamino acid has the moisture retention property of adsorbing water. The polyamino acid which irradiates the chain molecule with radiation, for example, CH2 in the polyamino acid is converted into CH- by dehydrogenation reaction. CH-HC of two polyamino acids are combined with each other to form a crosslinked body. Most of the polyamino acids are ray-crosslinked to each other in a mesh structure, and the inside of the mesh structure forms a space of a plurality of pockets. The intersection of the wires can be cross-linked without heating the polyamino acid, so that the original nature of the amino acid can be retained to form a radioactive crosslinked body of the polyamino acid. The radiation crosslinking reaction is a low temperature crosslinking reaction, which is different from the crosslinking reaction via heating. Upon heating, the polyamic acid is degraded by heat, but it is characterized by the fact that it is not affected by thermal deterioration. Moreover, the above-mentioned polyamino acid radiation crosslinking system has a plurality of pocket spaces inside, and the pocket space has the ability to absorb and retain water molecules, thereby having a larger water retention than the polyamino acid, and it is known. This water retention property is an agglutination property in which a suspended substance is absorbed to agglomerate. In the present invention, as the polyamino acid, γ-poly glutamic acid manufactured by 〇本P〇Iy-Glu Co., Ltd. as shown in the examples, which is (-00C-CH2-CH2-CH) is used. (C00H) ΝΗ-) The chain molecule 'subscript η' represented by η is the degree of polymerization. Γ-polyglycolic acid -15·200837020 which is a starting material is suitable for those having a large molecular weight, especially having a molecular weight of several hundred thousand to several millions, and these molecular weights are determined by the degree of polymerization. In addition, the gamma-polyamic acid illuminates the radiation, and the dehydrogenation reaction C Η 2 becomes CH-, and the two linear chains of γ-poly glutamic acid are linked by CH-HC, such as [(-OOC- CH2-CH(COOH) ΝΗ-) η] is crosslinked in the same manner as in the above. When the degree of crosslinking is larger, a radiation crosslinked body having a large molecular weight like [(-OOC-CH2-CH2-CH(COOH) ΝΗ-)n]m is formed. Here, m indicates that the degree of crosslinking 'is the number of linear chains to which the γ-poly glutamic acid to be crosslinked is administered. Further, by increasing the degree of crosslinking, the molecular weight of the γ-polyglycine radiation crosslinker can be more than 10 million. Since polyglutamic acid is a polypeptide chain, a mesh structure in which a large number of large spaces are formed by the connection of -CH-HC-, as described above, absorbs dirty water in many internal spaces, and accumulates internal pollution. substance. Further, although the polyamino acid is produced by various production methods, the polyamino acid produced by the microorganism is a natural substance, and is also suitable from the viewpoint of safety, and the polyamino acid is also suitable. Polyglutamic acid or polyaspartic acid is also suitable for the practice of the present invention. Further, as the polyacrylic polymer having aggregability, there are anionic polyacrylic acid or a salt thereof, nonionic polyacrylamide, and cationic poly(fluorene, fluorene, fluorene, -trimethylaminoethyl) Methacrylate chloride) and the like. Further, the polyethylene glycol-based polymer having agglomerability may be polyethylene glycol or a polyethylene glycol derivative in which one end of a polyethylene glycol is bonded to an alkyl group or an ionic functional group. Each of the polymers having the above-mentioned aggregability has the characteristics of being adsorbed in the water--16-200837020 floating matter, and has a property of being attracted by the magnetic force, so that it is suitable for use in such a property. Use. For example, the agglomerating agent of the magnetic polymer of the present invention is placed in a storage place of water in which the dirt is present, such as purification, water treatment sites, reservoirs, swamps, rivers, lakes, fish farms, etc. In the water, it is dispersed, and after the contaminated substance is adsorbed, the agglomerating agent made of the bonded magnetic polymer adsorbing the contaminated substance is attracted by magnetic attraction, and the contaminated substance in the water can be easily recovered. [Embodiment 1] [Example 1] Formation of fine particles of a magnetic material in which a decane compound is bonded (1) In Example 1, the outer surface of the fine particles of magnetite of the magnetic material is formed into a decane which binds (coats) APTS. Compound. First, microsomes (average particle diameter 0.2 μm) containing ferrite iron (Fe3 04 ) were added to ethanol to obtain a 0.01 2 8 M solution. Thereafter, the solution was diluted to 150 ml with water 1 ml + ethanol + 25 ml of the above solution, and the solution was ultrasonicated over 30 minutes and stirred. Thereafter, APTS (3-aminopropyltriethoxydecane) 35 μl was added to the solution, followed by vigorous stirring for 7 hours. Next, the agitated material was placed in an evaporator, and by removing the contained ethanol, magnetite fine particles coated with APTS were obtained. In other words, the outer surface of the magnetite microparticles (microparticles made of a magnetic material) can be obtained as a microparticle of APTS (decane compound) having an amine group as a functional group. -17- 200837020 [Example 2] Formation of fine particles of a magnetic material in which a decane compound is bonded (2) In Example 2, a decane in which an outer surface of a magnetite fine particle of a magnetic material is bonded with a carboxyl group as a functional group is prepared. Compound (1). First, the APTS-coated magnetite fine particles were added to 80 ml of ethyl acetate, and the mixture was stirred and dispersed. Further, succinic anhydride was added thereto and allowed to react for 20 minutes. After completion of the reaction, the mixture was washed three times with ethyl acetate to obtain a magnetite microparticle having a carboxyl terminal. [Example 3] Formation of agglomerating agent of polyglutamate using a polymer having aggregability (1) Formation of the APTS-coated magnetite microparticles formed in the above Example 1 was used, and γ- The sodium salt of polyglutamic acid acts as a coagulant for the aggregating polymer. First, γ-poly glutamic acid having a molecular weight of 800,000 to 1,000,000 (the same applies to the following examples of γ-polyuryl glutamate, 日本, Japan Poly-Glu), and APTS coated magnetic The iron ore fines (9.6 mm 〇1) and the 4-dimethylamino hydrazine oxime (97.7 mg: 0.8 mmol) were stirred and dispersed in 80 ml of water. Further, to this solution was added ethyl ethyl-3-(3-dimethylaminopropyl)-carbodiimide hydrochloride (〗: 993.7 mg: 10.4 mmol), and stirred at 〇 ° C for 2 hr. Thereafter, it was stirred at room temperature for one night. Under cooling (〇 ° C), 5.5 g of dissolved sodium hydroxide in 30 ml of -18-200837020 aqueous NaOH was added to the resulting solution, and the mixture was stirred at room temperature overnight. Next, a 6 N hydrochloric acid solution was added thereto to make the solution acidic (about pH 5), and stirred at room temperature for an hour. Thereafter, the product is separated by using a magnet, and the product obtained by lyophilization is used to obtain the aggregating agent of the present invention. That is, the aggregating agent obtained in Example 3 is such that the magnetic material-made microparticles are combined with a decane compound (APTS) having an amine group as a functional group, and the decane compound is combined to form agglomerated by amidino group-bonding. Agglomerating agent made of a polymer (sodium salt of polyglutamic acid). [Example 4] Formation of agglomerating agent of chitosan by a polymer having agglutination (2) The magnetite microsome having a carboxyl terminal formed in the above Example 2 was used, whereby The guanamine group binds chitosan to form a coagulating polymer to synthesize an aggregating agent. First, a magnetite microsome (9.6 mmol) having a chitosan (low molecular weight of chitosan, manufactured by Aldrich), a carboxy terminal, and a 4-dimethylamino group ruthenium D (9 7 · 7 mg) : 0 · 8 mm ο 1 ) Disperse in 80 μm of water while stirring. Further, 1-ethyl-3-(3-dimethylaminopropyl)-carbodiimide hydrochloride (1993.7 mg: 10.4 mmol) was added to the solution, and the mixture was stirred at 0 ° C for 2 hours. . Thereafter, it was stirred at room temperature for one night. Under cooling ((°C), 5.5 g of sodium hydroxide dissolved in 30 ml of water was added to the resulting solution, and the mixture was stirred at room temperature overnight. Next, a 6 N hydrochloric acid solution was added thereto to make the solution acidic (about pH 5), and then stirred at room temperature -19-200837020 for 1 hour. Thereafter, the product is separated using a magnet, and the product obtained by lyophilization is used to obtain the aggregating agent of the present invention. That is, the aggregating agent obtained in Example 4 is a sulfonium compound (APTS) in which a microparticle of a magnetic material is bonded with an amine group as a functional group, and an amine group of a functional group and a carboxyl group of one of succinic acid are subjected to a decylamine. The carboxyl group in other aspects is an aggregating agent which is combined with the agglutinating polymer (chitosan) guanamine group. [Embodiment 5] Fig. 1 is an embodiment showing a method of purifying water using an agglomerating agent made of a magnetic material-type polymer of the present invention. In Fig. 1, W is a solution to be treated, B is a coagulant, and Μ is Electromagnet, E DC power supply, S is a switch, 3 is a tank, 17 is a treatment solution discharge port, 17 7a is a valve, 18 is an aggregate discharge port, 18a is a valve, and 19 is a stirring mixer. The coagulant formed in Example 3 which was agglomerating agent B in a ratio of 200 mg/L to the solution W to be treated was stored in a solution W of about 1 ton in a tank 3 having a capacity of 15 ton. After the mixture solution W was stirred and stirred for about 7 minutes by stirring the mixer, the solution W to be treated was allowed to stand for 15 minutes, and then the switch S was turned on to rotate the electrode. Further, the magnetic flux density of the electromagnetic stone is set to 0.12 to 0·15 Wb/m2. By rotating the electromagnetic stone, the agglomerates in the floating in the groove 3 are almost completely adsorbed to the side of the electromagnetic stone after about 30 to 60 seconds. The water that has been cleaned by opening the discharge port 17 is opened, and the switch S is opened, and the agglomerates adsorbed by the electromagnetic stone are discharged to the outside of the tank 3 by the outlet -20»200837020. In the case of a conventional agglomerating agent which is mainly composed of polyglutamic acid, when the aggregating agent is stirred and mixed under the same conditions, the agglomerates naturally settle to the bottom of the tank, and it takes about 60 to 120 minutes. On the other hand, when the aggregating agent of the present invention is used, almost all of the aggregates can be adsorbed on the side of the electromagnetic stone in about 20 minutes, and the treatment time for purifying the water can be greatly shortened, and the treated wastewater can be obtained more cleanly than the treated solution W. More highly purified. Further, in the fifth embodiment, only the aggregating agent of the present invention is used, and the other aggregating agent of the present invention is added to the aggregating agent of the present invention, so that the floc formed by the latter aggregating agent is bonded to the aggregating agent of the former. The formed flocs can adsorb two flocs via magnetic force. [Embodiment 6] Fig. 2 is a view showing another embodiment of a method for purifying water using the agglomerating agent of the magnetic polymer of the present invention. In Fig. 2, 20 is a collecting device for agglomerates. In this embodiment, after a fixed amount of aggregating agent enthalpy is mixed in the tank 3, after being left for a predetermined period of time, the mixed water in the tank 3 is led to the recovery device 20 through the discharge port 127, and is circulated to the side. While collecting the inside of the apparatus 20, the aggregate in the adsorbed mixed water is adsorbed on the side of the electromagnetic stone. Namely, after the aggregating agent is stirred and mixed, the treated solution W is allowed to stand in the tank 3 for a short period of time, and the s S of the treated solution w is agglomerated to some extent. Thereafter, the treated solution W flows between the periods 21 - 200837020 in the recovery device 20, and the agglomerates in the agglomerated water are adsorbed to the side of the electromagnetic stone in a certain degree, and the result is extremely highly processed. The cleaned treatment solution is discharged from the discharge port 22. Further, the adsorbed aggregate is non-excited by electromagnetic gangue, and is discharged to the outside of the recovery device 20 by the open suction port 18. Further, when the solution W to be treated flows in the recovery device 20, the electromagnetism is in an excited state, and the magnetic flux density is set to be about 0.1 2 to 0.15 Wb/m2. Fig. 3 (a), (b) and (c) show that the agglomerating agent B made of the bonded magnetic polymer of Example 3 is 200 mg/L in the solution to be treated (SS 30 mmg/L, COD 25 mmg/L). A photograph of the state of the agglomerate when the ratio is mixed, (a) indicates that the agitation agent B is stirred and mixed; (b) indicates that the mixture is stirred for 30 minutes; (c) indicates that the electrode is rotated 2 minutes after the start of rotation. status. As is apparent from the comparison of (b) and (c) of Fig. 3, the aggregate is extremely rapidly and almost completely adsorbed to the side of the electromagnetic stone by the rotation of the electromagnet. In other words, the agglomerates and the magnetic material-made fine particles are separated by the additional magnetic force, and only the magnetic material-made fine particles are adsorbed to the electromagnet side, and it is confirmed that the aggregate-like image does not float in the water at all. [Example 7] Investigation of the flocculation separation property of the elapsed time after the aggregation treatment of the aggregating agent (referred to as PGM-L) made of a magnetic polymer was first prepared by first preparing a 20 ppm kaolin suspension. The agglutination-treated raw water was added to the supernatant obtained by agglutination treatment of γ-poly glutamic acid -22-200837020 conjugated agglutinating agent (PGa21Ca) of Japan Poly-Glu (share), and formed in Example 3. After the agglutinating agent (PGM-L) made of a magnetic polymer was added, the supernatant after the agglutination treatment with the addition of PGoc2 1Ca and the standing without the treatment as a blank test were carried out, and each elapsed time was measured. Turbidity, for comparison. Further, in the raw water, 20 ppm of kaolin was added to the water of the channel, and the mixture was uniformly stirred and mixed. In the measurement of the sample, the supernatant of the sample prepared by the following method at a depth of 2 · 5 cm was used to measure the turbidity. Sample 1 : 50 ppm of PGa21 Ca was added to the raw water to perform agglutination treatment. . Sample 2: After adding 28 ppm of PGM-L to the raw water, 50 ppm of PGa2 1Ca was added to carry out agglutination treatment, and immediately after the treatment, three stirrrer bars with magnets were charged. Blank test: Nothing is added to the raw water, and the same operation as the agglutination treatment is performed. The agglutination treatment conditions are as follows. That is, the sample container was a 50 mL flask and the sample volume was 500 mL. The stirring conditions were stirred rapidly for 10 minutes. The agitator uses an agglutination reaction tester. Further, the water temperature of the sample at the time of the treatment was 1 7.4 ° C and ρ Η 7 · 6. Further, the measurement apparatus used in the following Table 1 was used for the measurement. -23- 200837020 [Table 1] Turbidity The turbidity meter TR-55 (polystyrene turbidity) of the industrial principle was used. Measurement range: 0.001 to 1100 mg/L pH MP220 (glass electrode method) was produced using a pH manufactured by METTLER-TOLEDO. The turbidity of each sample at rest time is shown below. [Table 2] ^ Turbidity standing time after each agglutination treatment (minutes) Only PGCx21Ca Sample 1 (degrees) PGM-L+PGa21Ca Sample 2 (degrees) Blank test (degrees) 2 17.0 9.30 19.5 4 14.4 8.78 19.6 6 12.0 8.46 19.9 8 11.4 8.35 20.0 10 11.0 8.01 19.3 15 9.01 7.10 18.8 20 7.16 6.57 18.7 Figure 4 shows the change of turbidity of each sample after agglutination treatment, and PGM-L is added for 2 minutes. In the case of sample 2, the turbidity was greatly reduced as compared with the sample, and both turbidity decreased with time. Sample 2 is within 2 minutes after the agglutination treatment. The flocculent floating in the water is adsorbed on the input magnet, and the large floc system is almost separated, but the sample 1 is a large floc floating in the float. status. From this, it was found that the floc of the sample 2 to which PGM-L was added had magnetic properties, and it was possible to separate the flocs earlier than those without PGM-L by being adsorbed by the magnet. -24·200837020 Further, it is confirmed from the test result of the example 6 that the floc aggregated by the PGM-L is not separated from the magnetic material microparticles by the applied magnetic force. [Industrial Applicability] The present invention is applicable not only to the present invention The treatment of purified water in the upper and lower sewer facilities or in rivers and lakes can also be applied to the purification of raw materials in the manufacturing process of industrial products. [Brief Description of the Drawings] Fig. 1 is an explanatory view showing one side of the treatment of purified water using the aggregating agent of the present invention. Fig. 2 is an explanatory view showing another example of the treatment of purified water using the aggregating agent of the present invention. [Fig. 3] is a drawing (photograph) showing the state of agglomerates in water when the aggregating agent of the present invention is used, and each of (a) indicates that the mixing and aggregating agent is shortly followed; (b) indicates that the stirring is stopped for 30 minutes. After that; (c) shows the state of the water after the electromagnet is excited for 2 minutes. Fig. 4 is a graph showing the transition of turbidity after the aggregation treatment of each sample of Example 6. [Fig. 5] is an explanatory view showing a state of purification treatment by a pool or a river of a flocculant mainly composed of a conventional polyglutamic acid. [Description of main component symbols] -25- 200837020 3 : Slot 1 7 : Discharge port 1 7 a ··Valve 1 8 : Sump 1 8a : Valve 1 9 : Mixing mixer 2 0 : Recovery unit 2 1 : Drain 2 1 a : Valve W : treated solution B : aggregating agent Μ : electromagnetic stone -26-