JP4177513B2 - Emulsion and flocculant compositions - 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。）
【００１８】
【化２】

（ただし、Ｒ5 ，Ｒ6 ，Ｒ7 ，Ｒ8 はＨまたはＣＨ3 、Ｘ- は対イオンをあらわす。）
【００１９】
本発明に用いられる前記式（１）で表される化合物の具体例としては、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。本発明に用いられる前記式（２）で表される化合物の具体例としては、ジ（メタ）アリルアミンの二級塩、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。 これらの中でもジメチルジアリルアンモニウムクロリドが好ましく用いられる。
【００２０】
本発明の有機高分子凝集剤のカチオン当量値は０．５ｍｅｑ／ｇ以上であることが好ましい。 カチオン性基の多い方が無機凝集剤の効果を高め、相乗効果を発揮する。 また、本発明の有機高分子凝集剤の、２重量％濃度の硫酸アンモニウム水溶液中における固有粘度は２ｄｌ／ｇ以上、好ましくは５ｄｌ／ｇ以上である。 高分子量である事が有機高分子凝集剤の凝集性能を高め、無機凝集剤と併用した場合の相乗効果を発揮し易い。
【００２１】
本発明の次ぎなる限定は、分散媒である油を容易に水中に分散させる為の親水性界面活性剤を含有するエマルジョンである事を特徴とする。本エマルジョンは原液即ち油中水型エマルジョンのままで使用する事もあり、水に溶解して使用する場合でも速やかに溶解する事が求められる。 この目的の為にＨＬＢ９〜１５の親水性のノニオン性界面活性剤を油中に添加しておく事が有効である。 特に好ましくは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、例えばポリオキシエチレンやしアルコールエーテル，ポリオキシチレンノニルフェニルエーテル等を挙げる事ができる。
【００２２】
本発明の更なる限定は、無機凝集剤を含むモノマー水溶液を、乳化剤を含む油に乳化分散させ、次いで重合操作を行う工程を経る製造方法により製造されたエマルジョンである事を特徴とする。モノマー水溶液中にはジビニル化合物の様な架橋剤を含有させ、一部あるいは大部が水不溶性の有機高分子凝集剤を製造する事もできる。モノマーに高級アルキル基等を導入して疎水性を付与する事もできる。重合開始はラジカル発生剤による。乳化時の高剪断により粒径は小さくできる。いわゆるエマルジョンタイプの高分子製造法とはモノマー水溶液があらかじめ無機凝集剤を含んでいる点で異なる。 かかる操作を経る事により無機凝集剤はポリマー粒子内に閉じ込められ安定なエマルジョンを形成する事ができる。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。例えば無機凝集剤を含まぬ重合性ビニル単量体水溶液と、ＨＬＢが３〜６であるノニオン性界面活性剤を含む油（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と共に無機凝集剤を共存させ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、凝集剤として使用する。 溶解後の添加条件等は、通常の高分子凝集剤と異なる点は無い。 またエマルジョン原液を添加して用いる事もできる。
【００２３】
本発明のエマルジョンから成る凝集剤組成物は一般的に凝集剤が用いられる全ての用途を対象とする。 本発明の凝集剤組成物は他の有機高分子凝集剤（アニオン、カチオン両性）との併用や組み合わせ使用、ベントナイトや粉末活性炭等の濾過助剤との併用や組み合わせ使用、酸や塩類との併用、高吸水性樹脂との併用等が可能であり、原液添加でも水溶液添加でも用いる事ができる。特に原液添加が容易な事は本発明品の大きな利点と言える。
【００２４】
本発明の凝集剤組成物は、汚泥、例えば砂利廃水の凝集沈殿スラリーあるいは各種有機汚泥等の凝集処理による汚泥の濃縮・脱水等に用いる事ができる。ここに言う有機汚泥とは、凝集処理汚泥の混合等による無機成分の混入を忌避するものではなく、下水やし尿の処理場から発生する汚泥、あるいは食品工業廃水の生物処理汚泥、あるいは製紙会社の汚泥等、多量の炭素成分を含有する汚泥の総称である。 汚泥濃縮には沈降・浮上等の重力利用の他にデカンターにて遠心濃縮する方法が有り、凝集剤を使用する場合も多い。 汚泥の脱水機としてはデカンター・ベルトプレス・スクリュープレス等に賞用され、フィルタープレスやベルトフィルターに使用する場合も有る。 汚泥脱水を促進する効果の発現機構は凝集によるものであるが、凝集（造粒）操作の後に一部の水分を濾過等により濃縮して脱水機に供することもできる。 また、他のカチオン性高分子凝集剤やアニオン性高分子凝集剤あるいは両性高分子凝集剤と併用あるいは混合して組み合わせて使用することもでき、活性炭，珪藻土，ベントナイト，古紙パルプの様な水不溶性物質と共に用いることもできる。 高吸水性樹脂と共に使用することが有効な場合も有る。香料や消臭剤を公知のごとく使用することも問題ない。本凝集剤組成物は、汚泥処理以外に、ラテックス廃水の凝結あるいは各種廃水の電荷の中和等に用いると卓効を示し、アオコ等藻類の除去や泥水の清澄化あるいは活性汚泥の沈降促進等に用いると良い。また、凝集剤はトンネル工事等の土木作業所から発生する含水土を、水を分離すること無く、固化あるいは粒状化する目的でも使用されている。添加方法は分散液の原液添加であり、含水土中の水に溶解して効果を発揮する。特にポリアニオン系分散剤を使用した排含水土を処理する場合にポリカチオンとしての電荷の中和と架橋吸着の相乗効果による処理効果は著しい。シールド、杭打ち、連壁等の土木工事から発生する泥水の処理にも、同様の作用効果を発揮し、水を分離する場合の泥水・泥土の処理にも有効である。本発明の凝集剤組成物による処理土はべたつかないので喜ばれる。
【００２５】
【作用】
本発明のエマルジョンは無機凝集剤の腐食性を軽減する。 その理由は油が絶縁材と成って金属表面を覆い腐食電流を防止している為である。 無機凝集剤と高分子量の有機高分子凝集剤との相乗効果が発生する理由が何故であるかは定かではない。 特にＰＡＣ等のアルミニウムの一価アニオン塩とアクリル酸エステル系の有機高分子凝集剤との相乗効果が発生する理由が何故であるかは定かではないが、縮合系等の低分子量の有機高分子凝集剤との間には見られぬ程の効果を発揮する。 アルミニウムの一価アニオン塩が存在しない場合、アクリル酸エステル系の有機高分子凝集剤の希釈水溶液は加水分解等の劣化により白濁し易い。アルミニウムの一価アニオン塩が存在すると希釈水溶液の白濁が生じないことから、アルミニウムの一価アニオン塩は加水分解等の劣化を防止する作用が有るものと考えられる。 また、効果的な面から考察すれば、凝集剤水溶液が液滴として水中に分散し架橋吸着等の凝集作用を示すことから、有機高分子凝集剤分子は液滴内でアルミニウムの一価アニオン塩の雰囲気下に有る複合物として挙動する。 またアルミニウムイオンも有機高分子凝集剤分子の雰囲気下に有るとも言える。 水酸化アルミニウムの析出粗大化は有機高分子凝集剤分子により阻害されコロイドを形成し易い。 また、アルミニウムの一価アニオン塩から供給されるところの縮合アルミニウムイオンはポリカチオンとして作用することから該液滴の電荷中和作用は大幅に高まり、有機高分子凝集剤分子の架橋吸着作用を妨害する凝集阻害物質等に対して抵抗性を持つものと考える。
【００２６】
【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。
【００２７】
（合成例−１〜８）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６５Ｋｇ、ＰＡＣ（Ａｌ2 Ｏ3 １０％、乾固形物２９％）１００Ｋｇ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）３０モル％アクリルアミド（ＡＡＭ）７０モル％の組成のモノマー１５０Ｋｇ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２０ｇ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やしアルコールエーテル７．５Ｋｇを添加混合して試験に供する試料（試料−１）（本発明の凝集剤組成物）とした。以下、同様に表１に記載の組成の無機凝集剤およびモノマー組成てエマルジョン重合を行い、試料２〜８および比較試料１〜４を得た。以上まとめて表１に記載する。
【００２８】
【表１】

【００２９】
（腐食試験）各濃度のＰＡＣ水溶液および試料１〜４原液をビーカーにとり、５００°Ｃにて１時間加熱後除冷して焼鈍したＳＵＳ−３０４のテストピース（長さ５０ｍｍ幅３０ｍｍ厚さ１ｍｍ）を表２記載の時間浸漬し重量測定を行った。結果を表２に示す。
【００３０】
【表２】

【００３１】
（有機汚泥脱水試験−１）試料および比較試料をポリマー濃度０．２％に成る様に調製した水希釈液を用いて、し尿処理場より発生するし尿膜処理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；７．２，ＳＳ；１２３００ｍｇ／ｌ，強熱減量７２．５％，Ｍアルカリ度２５００ｍｇ／ｌである。 この汚泥に表３記載量の各試料を添加攪拌しベルトプレスで脱水した結果を表３に示す。
【００３２】
【表３】

【００３３】
（有機汚泥脱水試験−２）試料および比較試料をポリマー濃度０．２％に成る様に調製した水希釈液を用いて、下水処理場より発生する下水余剰汚泥（ＰＨ；７．０，ＳＳ；２３００ｍｇ／ｌ，強熱減量７２．０％）に表４記載量の各試料を添加し造粒濃縮槽にて攪拌し、汚泥をペレット状に成形するとともに余分の水分を濾液として除去し、濃縮された凝集（造粒）汚泥をベルトプレスにより脱水した。結果を表４に示す。
【００３４】
【表４】

【００３５】
（有機汚泥脱水試験−３）都市下水汚泥の沈殿汚泥と活性汚泥法の余剰汚泥の混合汚泥に試料および比較試料の水希釈液を添加混合した後ベルトプレスにより脱水した脱水試験の結果を表ー５に示す。
【００３６】
【表５】

【００３７】
【発明の効果】
表−３〜５の記載より明らかな様に、本願発明の含水率低下効果は顕著であり焼却や埋め立て等の最終処分の経費削減に有効である。
【００４４】
次に砂利洗浄廃水の処理に使用した例を示す。
（凝集試験）砂利・砂の洗浄工程から排出される建設骨材洗浄排水をアクリルアミド・アクリル酸ソーダ共重合物から成るアニオン系高分子凝集剤にて凝集しクラリファイヤーに供給して上澄み処理水と建設骨材洗浄廃泥に分離し、この建設骨材洗浄廃泥（ＳＳ１２％）を引抜きポンプでストックタンクに移送する際、ポンプサクションに前記試料の３０倍水希釈液を注入して均一に分散させ、ストックタンクにて沈降を防止する様にゆるやかな攪拌を続け微細に造粒した廃泥を得、加圧ポンプにてフィルタープレスにチャージし脱水した。 脱水濾液はアニオン系高分子凝集剤にて凝集処理した後のクラリファイヤーへ注入する前の泥水に添加混合したところ、それまで１００ｐｐｍを越えていた処理水ＳＳがいずれも１０ｐｐｍ程度にまで減少し清澄化の効果を発揮した。フィルタープレスにチャージし脱水する１サイクルの廃泥のフィード時間を、無薬注の場合を１００％として、各試料添加時のフィード時間の割合を求めた。また最終排出ケーキの含水率を求めた。 結果を表６に示す。
【００３８】
【表６】

【００３９】
【発明の効果】
表−６の記載より明らかな様に、本願発明の脱水促進効果および処理水の清澄化効果は顕著であり砂利廃水処理の経費削減に有効である。[0001]
[Industrial application fields]
The present invention relates to a novel emulsion, which is used for use as a flocculant. The use of the flocculant is mainly wastewater treatment or sludge dewatering. Essentially, the present invention relates to a cationic or amphoteric emulsion type organic polymer flocculant containing an inorganic flocculant such as an aluminum salt.
[0002]
[Prior art]
Various flocculants have been proposed so far. For example, an amphoteric copolymer of a cationic monomer and an acrylic acid salt of an acrylic acid salt (Japanese Patent Laid-Open No. 56-118798), a cationic monomer comprising a tertiary amine salt and a quaternary ammonium salt and acrylic acid Sludge dehydrating agents such as coalesced (JP-A-3-189000), amphoteric copolymers of acrylate cationic monomer and methacrylate cationic monomer and acrylic acid (JP-A-3-293100) are known. Moreover, the sludge dehydration method (63-158200 gazette) which adds an amphoteric organic polymer flocculant with respect to the organic sludge whose sludge PH after addition of an inorganic flocculant is 5-8 is known. It is known that an inorganic flocculant and an organic polymer flocculant are used in combination as a general wastewater treatment.
[0003]
[Problems of the Invention]
Conventionally known flocculation methods using both an inorganic flocculant and an organic polymer flocculant require two additional facilities, and the apparatus is complicated. In addition, the inorganic flocculant is corrosive, and the stock tank must have corrosion resistance. In addition, when an inorganic flocculant and an organic polymer flocculant exert a synergistic effect, a flocculant having both functions has been desired.
[0004]
[Means for solving the problems]
The invention of claim 1 of the present invention is a (meth) acrylic polymer having a cationic group and / or a di (meth) allyl polymer flocculant and an inorganic flocculant, such as aluminum sulfate, aluminum chloride, polyaluminum chloride, It is an emulsion characterized by containing one kind selected from polyiron sulfate, ferric chloride and a mixture thereof in oil.
[0005]
The invention according to claim 2 of the present invention is the emulsion according to claim 1, wherein the flocculant is dispersed in oil as particles having a particle size of 10 μm or less.
[000 6 ]
The invention according to claim 3 of the present invention is the emulsion according to claim 1 , wherein the water-insoluble ignition residue in the dry solid from which oil has been removed is 0.5 to 25% by weight. .
[000 7 ]
The invention of claim 4 of the present invention is an emulsion according to claim 1, the alumina content of the removal of the oil dry solids in is characterized in that 0.5 to 20 wt%.
[000 8 ]
The invention according to claim 5 of the present invention is the emulsion according to claim 1 , wherein the cation equivalent value of the organic polymer flocculant is 0.5 meq / g or more.
[000 9 ]
The invention of claim 6 of the present invention, the organic polymer flocculant, the intrinsic viscosity in ammonium sulfate in an aqueous solution of 2% strength by weight is an emulsion according to claim 1, characterized in that it is 2 dl / g or more.
[00 10 ]
Invention of Claim 7 of this invention contains the hydrophilic surfactant for disperse | distributing the oil which is a dispersion medium in water easily, It is described in any one of Claim 1 thru | or 6 characterized by the above-mentioned. It is an emulsion.
[00 11 ]
The invention according to claim 8 of the present invention is characterized in that it is produced by a production method in which an aqueous monomer solution containing an inorganic flocculant is emulsified and dispersed in an oil containing an emulsifier, followed by a polymerization operation. The emulsion according to any one of claims 6 to 6.
[00 12 ]
A ninth aspect of the present invention is a flocculant composition comprising the emulsion according to any one of the first to eighth aspects .
[00 13 ]
DETAILED DESCRIPTION OF THE INVENTION
The first limitation of the present invention is that (meth) acrylic polymer and / or di (meth) allyl polymer flocculant having a cationic group and inorganic flocculants such as aluminum sulfate, aluminum chloride, polyaluminum chloride, poly It is characterized by being an emulsion containing one kind selected from iron sulfate, ferric chloride and mixtures thereof dispersed in oil. The inorganic flocculant is an aqueous salt solution and has a corrosive action as it is. The corrosive action of the inorganic flocculant is greatly reduced because the flocculant is sequestered in the oil. It is an object of the present invention to aim at a synergistic effect of an inorganic flocculant and an organic polymer flocculant. Specific examples of the oil used in the present invention include 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. .
[00 14 ]
A second limitation of the present invention is characterized in that in the emulsion according to claim 1, the flocculant is dispersed in oil as particles having a particle size of 10 μm or less. A small particle size contributes to the stability of the emulsion. A method of stabilizing fine particles with an emulsifier is usually taken. The surfactant used for emulsification of the emulsion of the present invention is an HLB 3-6 nonionic surfactant, and specific examples thereof include sorbitan monooleate, sorbitan monostearate, sorbitan monopalmitate and the like.
[00 15 ]
An iron salt is generally used as the inorganic flocculant, but an aluminum salt is more likely to exhibit a synergistic effect with the organic polymer flocculant. A particularly desirable inorganic flocculant is polyaluminum chloride. The mixing ratio of the inorganic flocculant is such that the water-insoluble ignition residue (content of metal oxide such as alumina) in the dry solid from which oil has been removed is in the range of 0.5 to 25% by weight. Preferably, the alumina content is in the range of 0.5 to 20% by weight, and particularly preferably the alumina content is in the range of 0.5 to 15% by weight. The ignition residue is heated and weighed in an electric furnace at 1000 ° C. until it reaches a constant weight (about 3 hours). As the mixing ratio of the inorganic flocculant, a blending ratio giving an ignition residue (ash content) or alumina content within this range is preferable in terms of synergistic effect.
[00 16 ]
The organic polymer flocculant of the present invention is a (meth) acrylic polymer and / or a di (meth) allyl polymer having a cationic group. Examples of the cationic monomer unit contained in the organic polymer include compounds represented by the following formula 1 or the following formula 2. Polymers obtained by copolymerizing nonionic or anionic monomers such as acrylamide and acrylic acid together with these cationic monomers are also organic polymer flocculants of the present invention, but if there are too many anionic monomers, the effect is adversely affected. Overuse should be avoided.
[00 17 ]
[Chemical 1]

(Wherein, A is O or NH; B is C2 H4, C3 H6, C3 H5 OH; R1 is H or CH3; R2, R3 is an alkyl group having 1 to 4 carbon atoms; R4 is hydrogen or 1 carbon atom; -4 alkyl group or benzyl group; X- represents an anionic counterion)
[00 18 ]
[Chemical 2]

(However, R5, R6, R7 and R8 represent H or CH3, and X- represents a counter ion.)
[00 19 ]
Specific examples of the compound represented by the formula (1) used in the present invention include tertiary salts and quaternary ammonium salts of dialkylaminoalkyl (meth) acrylate, tertiary salts of dialkylaminoalkyl (meth) acrylamide and Examples include quaternary ammonium salts, tertiary and quaternary ammonium salts of dialkylaminohydroxyalkyl (meth) acrylates, tertiary and quaternary ammonium salts of dialkylaminohydroxyalkyl (meth) acrylamides, or mixtures thereof. I can do things. Among these, one selected from acryloyloxyethyltrimethylammonium chloride, methacryloyloxyethyltrimethylammonium chloride, dimethylaminopropylacrylamide hydrochloride or a mixture thereof is preferably used. Specific examples of the compound represented by the formula (2) used in the present invention include one selected from di (meth) allylamine secondary salts, tertiary salts and quaternary ammonium salts, or mixtures thereof. Can do. Among these, dimethyl diallyl ammonium chloride is preferably used.
[00 20 ]
The cation equivalent value of the organic polymer flocculant of the present invention is preferably 0.5 meq / g or more. A more cationic group enhances the effect of the inorganic flocculant and exhibits a synergistic effect. The intrinsic viscosity of the organic polymer flocculant of the present invention in a 2% by weight aqueous ammonium sulfate solution is 2 dl / g or more, preferably 5 dl / g or more. The high molecular weight enhances the aggregation performance of the organic polymer flocculant, and easily exhibits a synergistic effect when used in combination with an inorganic flocculant.
[00 21 ]
The next limitation of the present invention is characterized by an emulsion containing a hydrophilic surfactant for easily dispersing oil as a dispersion medium in water. The emulsion may be used as a stock solution, that is, a water-in-oil emulsion, and it is required to dissolve quickly even when dissolved in water. For this purpose, it is effective to add a hydrophilic nonionic surfactant of HLB 9 to 15 to the oil. Particularly preferably, a nonionic surfactant having HLB of 10 to 14 is used. Typical examples of preferred nonionic surfactants include polyoxyethylene palm alcohol ether and polyoxyethylene nonylphenyl ether.
[00 22 ]
A further limitation of the present invention is that the emulsion is produced by a production method in which an aqueous monomer solution containing an inorganic flocculant is emulsified and dispersed in an oil containing an emulsifier and then subjected to a polymerization operation. A crosslinking agent such as a divinyl compound can be contained in the monomer aqueous solution to produce a partially or mostly water-insoluble organic polymer flocculant. A higher alkyl group or the like can be introduced into the monomer to impart hydrophobicity. Polymerization is initiated by a radical generator. The particle size can be reduced by high shear during emulsification. This is different from the so-called emulsion type polymer production method in that the monomer aqueous solution contains an inorganic flocculant in advance. By undergoing such an operation, the inorganic flocculant can be confined in the polymer particles to form a stable emulsion. The polymer according to the present invention can be copolymerized by a known polymerization method. For example, after mixing and emulsifying a polymerizable vinyl monomer aqueous solution not containing an inorganic flocculant and an oil (organic dispersion medium) containing a nonionic surfactant having an HLB of 3 to 6, the radical polymerization initiator A method for producing a water-in-oil cationic polymer emulsion by polymerizing at a temperature of 30 to 80 ° C. in the presence is described in JP-A-61-236250. In addition, the water-in-oil emulsion of the present invention can be synthesized by coexisting an inorganic flocculant. A hydrophilic surfactant is added to this water-in-oil emulsion, mixed with water, phase-shifted into an oil-in-water emulsion, and used as a flocculant. Addition conditions after dissolution do not differ from ordinary polymer flocculants. Further, an emulsion stock solution can be added and used.
[00 23 ]
The flocculant composition comprising the emulsion of the present invention is generally intended for all applications where flocculants are used. The flocculant composition of the present invention is used in combination with or combined with other organic polymer flocculants (anionic and cationic amphoteric), combined with or combined with filter aids such as bentonite and powdered activated carbon, combined with acids and salts In addition, it can be used in combination with a superabsorbent resin, and can be used with addition of a stock solution or an aqueous solution. In particular, the fact that the stock solution can be easily added is a great advantage of the product of the present invention.
[00 24 ]
The flocculant composition of the present invention can be used for the concentration and dehydration of sludge by agglomeration treatment of sludge, for example, agglomeration sediment slurry of gravel wastewater or various organic sludges. Organic sludge here does not avoid mixing of inorganic components due to mixing of coagulated sludge, etc., sludge generated from sewage and human waste processing plants, biological treatment sludge of food industry wastewater, or paper manufacturers A general term for sludge containing a large amount of carbon components such as sludge. Concentration of sludge includes a method of centrifugal concentration in a decanter in addition to the use of gravity such as sedimentation and levitation, and a flocculant is often used. As a sludge dewatering machine, it is used in decanters, belt presses, screw presses, etc., and sometimes used in filter presses and belt filters. The mechanism of expression of the effect of promoting sludge dehydration is due to agglomeration. However, after the agglomeration (granulation) operation, a part of water can be concentrated by filtration or the like and used in a dehydrator. It can also be used in combination with or mixed with other cationic polymer flocculants, anionic polymer flocculants or amphoteric polymer flocculants, and is insoluble in water such as activated carbon, diatomaceous earth, bentonite, and waste paper pulp. It can also be used with substances. In some cases, it is effective to use with a superabsorbent resin. It is no problem to use fragrances and deodorants as known. In addition to sludge treatment, this flocculant composition exhibits excellent effects when used for condensation of latex wastewater or neutralization of various wastewater charges, etc., for removing algae such as sea cucumbers, clarifying mud water, or promoting sedimentation of activated sludge, etc. It is good to use for. Moreover, the flocculant is used also for the purpose of solidifying or granulating the hydrous soil generated from a civil engineering work site such as tunnel construction without separating the water. The addition method is the addition of a stock solution of the dispersion, which is effective when dissolved in water in hydrous soil. In particular, when treating wastewater containing a polyanionic dispersant, the effect of treatment due to the synergistic effect of charge neutralization and crosslinking adsorption as a polycation is remarkable. The same effect is exhibited in the treatment of muddy water generated from civil engineering work such as shielding, pile driving, and continuous walls, and it is also effective in the treatment of muddy water and mud when separating water. The soil treated with the flocculant composition of the present invention is not sticky and is appreciated.
[00 25 ]
[Action]
The emulsion of the present invention reduces the corrosivity of the inorganic flocculant. The reason is that oil forms an insulating material and covers the metal surface to prevent corrosion current. It is not clear why the synergistic effect of the inorganic flocculant and the high molecular weight organic polymer flocculant occurs. In particular, it is not clear why the synergistic effect of monovalent anion salts of aluminum such as PAC and acrylate-based organic polymer flocculants occurs, but low molecular weight organic polymers such as condensation systems. An effect not seen with the flocculant is exhibited. In the absence of a monovalent anion salt of aluminum, a dilute aqueous solution of an acrylate-based organic polymer flocculant tends to become cloudy due to degradation such as hydrolysis. When the monovalent anion salt of aluminum is present, the dilute aqueous solution does not become cloudy. Therefore, the monovalent anion salt of aluminum is considered to have an action of preventing degradation such as hydrolysis. Further, from an effective viewpoint, since the aqueous flocculant solution is dispersed in water as droplets and exhibits an aggregating action such as cross-linking adsorption, the organic polymer flocculant molecules are monovalent anion salts of aluminum in the droplets. Behaves as a composite in the atmosphere of It can also be said that aluminum ions are also present in the atmosphere of organic polymer flocculant molecules. Precipitation coarsening of aluminum hydroxide is inhibited by organic polymer flocculant molecules and tends to form a colloid. In addition, the condensed aluminum ion supplied from the monovalent anion salt of aluminum acts as a polycation, so that the charge neutralization action of the droplets is greatly enhanced and the cross-linking adsorption action of organic polymer flocculant molecules is hindered. It is considered to be resistant to aggregation inhibitors and the like.
[00 26 ]
【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.
[00 27 ]
(Synthesis Examples -1 to 8) A reaction vessel equipped with a stirrer and a temperature control device 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. A mixture of 65 kg of demineralized water, 100 kg of PAC (Al2 O3 10%, dry solid 29%) and 150 kg of monomer having a composition of 30 mol% acryloylethyltrimethylammonium chloride (AMC) 30 mol% acrylamide (AAM), The mixture was stirred and emulsified with a homogenizer. After adding 20 g of isopropyl alcohol to the obtained emulsion and replacing with nitrogen, 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 palm alcohol ether Was added and mixed to obtain a sample (sample-1) (the flocculant composition of the present invention) to be used for the test. Hereinafter, similarly, emulsion polymerization was performed using the inorganic flocculant and monomer composition having the composition shown in Table 1, and Samples 2 to 8 and Comparative Samples 1 to 4 were obtained. These are summarized in Table 1.
[00 28 ]
[Table 1]

[00 29 ]
(Corrosion test) SUS-304 test piece (length: 50 mm, width: 30 mm, thickness: 1 mm) which was taken in a beaker with each concentration of PAC aqueous solution and samples 1 to 4 undiluted, heated at 500 ° C. for 1 hour, and then cooled and annealed. Was dipped for the time shown in Table 2 and weighed. The results are shown in Table 2.
[00 30 ]
[Table 2]

[00 31 ]
(Organic sludge dehydration test-1) Using a water dilution prepared so that the sample and the comparative sample had a polymer concentration of 0.2%, the urine membrane-treated sludge generated from the human waste treatment plant was dehydrated by a belt press. The properties of the sludge subjected to the test are PH: 7.2, SS: 12300 mg / l, loss on ignition 72.5%, and M alkalinity 2500 mg / l. Table 3 shows the results of adding and stirring each sample in the amount shown in Table 3 and dehydrating it with a belt press.
[00 32 ]
[Table 3]

[00 33 ]
(Organic sludge dehydration test-2) Sewage surplus sludge (PH; 7.0, SS; generated from a sewage treatment plant) using a water dilution liquid prepared so that the sample and the comparative sample had a polymer concentration of 0.2%. 2300mg / l, loss on ignition 72.0%) Add each sample of the amount listed in Table 4 and stir in the granulation concentration tank to form sludge into pellets and remove excess water as filtrate and concentrate The agglomerated (granulated) sludge was dehydrated by a belt press. The results are shown in Table 4.
[00 34 ]
[Table 4]

[00 35 ]
(Organic sludge dewatering test -3) The results of the dewatering test after dewatering with a belt press after mixing the sample sludge sludge sludge and activated sludge mixed sludge mixed with the sample and comparative sample water dilution liquid. As shown in FIG.
[00 36 ]
[Table 5]

[00 37 ]
【The invention's effect】
As is apparent from the descriptions in Tables 3 to 5, the effect of lowering the moisture content of the present invention is remarkable, and is effective in reducing the cost of final disposal such as incineration and landfill.
[0044]
Next, the example used for the treatment of gravel washing wastewater is shown.
(Coagulation test) Construction aggregate cleaning wastewater discharged from the gravel and sand washing process is agglomerated with an anionic polymer flocculant made of acrylamide / sodium acrylate copolymer and supplied to the clarifier, Separated into construction aggregate washing waste mud, and when this construction aggregate washing waste mud (SS12%) is transferred to the stock tank with a pump, it is uniformly dispersed by injecting 30 times water dilution of the sample into the pump suction. In order to prevent sedimentation in the stock tank, the slurry was gently stirred to obtain finely granulated waste mud, which was charged into a filter press with a pressure pump and dehydrated. When the dehydrated filtrate was added to and mixed with the muddy water before being injected into the clarifier after being agglomerated with the anionic polymer flocculant, the treated water SS, which had previously exceeded 100 ppm, decreased to about 10 ppm and became clear. The effect of the crystallization was demonstrated. The feed time of one cycle of waste mud that was charged into the filter press and dehydrated was defined as 100% in the case of no chemical injection, and the ratio of the feed time when each sample was added was determined. The moisture content of the final discharged cake was determined. The results are shown in Table 6.
[00 38 ]
[Table 6]

[00 39 ]
【The invention's effect】
As is clear from the description in Table-6, the dehydration promoting effect and the clarification effect of the treated water of the present invention are remarkable and effective in reducing the cost of the gravel wastewater treatment.

Claims (9)

(Meth) acrylic polymers having cationic groups and / or di (meth) allyl polymer flocculants and inorganic flocculants such as aluminum sulfate, aluminum chloride, polyaluminum chloride, polyiron sulfate, ferric chloride and these An emulsion characterized by containing a dispersion selected from the mixture of The emulsion according to claim 1 , wherein the flocculant is dispersed in oil as particles having a particle size of 10 µm or less. The emulsion according to claim 1 , wherein the water-insoluble ignition residue in the dry solid from which oil has been removed is 0.5 to 25% by weight. The emulsion according to claim 1 , wherein the content of alumina in the dry solid from which oil has been removed is 0.5 to 20% by weight. The emulsion according to claim 1 , wherein the organic polymer flocculant has a cation equivalent value of 0.5 meq / g or more. The emulsion according to claim 1 , wherein the organic polymer flocculant has an intrinsic viscosity of 2 dl / g or more in a 2 wt% ammonium sulfate aqueous solution. The emulsion according to any one of claims 1 to 6, comprising a hydrophilic surfactant for easily dispersing oil as a dispersion medium in water. The aqueous monomer solution containing an inorganic coagulant, emulsifier is emulsified and dispersed in an oil containing, then according to any one of claims 1 to 6, characterized in that is manufactured by the manufacturing method through the steps of performing a polymerization operation Emulsion. A flocculant composition comprising the emulsion according to any one of claims 1 to 8 .