JP2017159193A - Wastewater treatment method by water-soluble polymer dispersion liquid - Google Patents
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Abstract
Description
本発明は排水の処理方法に関する。更に詳しくは塩化物イオン及び多価アニオンを含有する塩水溶液中で、特定の単量体及び構成単位としてジアリルジメチルアンモニウム塩化物を含有する高分子分散剤を共存させ、攪拌下、分散重合して得られる水溶性重合体分散液であり、該水溶性重合体分散液総量に対して、無機塩の総量が１５質量％未満である水溶性重合体分散液を添加することからなる排水処理方法に関する。 The present invention relates to a method for treating waste water. More specifically, in a salt aqueous solution containing chloride ions and polyvalent anions, a specific monomer and a polymer dispersant containing diallyldimethylammonium chloride as a structural unit are allowed to coexist, and dispersion polymerization is performed under stirring. It is a water-soluble polymer dispersion obtained, and relates to a wastewater treatment method comprising adding a water-soluble polymer dispersion whose total amount of inorganic salt is less than 15% by mass with respect to the total amount of the water-soluble polymer dispersion. .
放流水質の規制強化に伴い、排水の処理において排水中の懸濁物質の凝集処理効率の向上だけでなく処理水の水質、ＣＯＤやアンモニウム態窒素やノルマルヘキサン抽出物等の低減も強く要望される様になっている。一般的に凝集処理として、硫酸バンド、ポリ塩化アルミニウム、ポリ硫酸鉄、ポリ塩化鉄等の無機凝集剤を添加した後に高分子凝集剤を添加して凝集フロックを生成させ、次いで、凝集沈殿処理あるいは凝集浮上処理する方法が適用されている。処理効果を上げるには無機凝集剤の添加量を増やすことになり、スラッジ量が増加し、処理コストが掛かるだけではなくアルミニウムの様に環境系に有害な物質を放出する等の問題点が指摘されている。そのため、一般的に高分子凝集剤として汎用されているポリアクリルアミド（ＰＡＭ）系水溶性高分子の種々の改良や提案が行なわれている。一般的にその形態は、水溶液、粉末、油中水型エマルジョン等があるが、水溶液、粉末タイプは溶解効率が低く、油中水型エマルジョンは溶剤と乳化剤が配合されているため環境への影響が懸念される。そこで、これら問題点を解消するためには溶解性が良く、溶剤、乳化剤を使用しない塩水溶液中でイオン性高分子分散剤を共存させ、攪拌下、分散重合して得られる水溶性重合体分散液が使用される（特許文献１、２）。
塩水溶液中でイオン性高分子分散剤を共存させ、攪拌下、分散重合して得られる水溶性重合体分散液の技術については、種々の特許公報により開示されている。一般的に分散重合時において無機塩として硫酸アンモニウムが汎用されているが、平成２６年の水質汚濁防止法改正に伴いアンモニウム化合物が有害物質に指定されていることから硫酸アンモニウムを含有する水溶性重合体分散液は好ましくはない。特許文献３では、硫酸アンモニウムを使用しない水溶性重合体分散液の製造方法が開示されているが、具体的な凝集処理効果や処理水質に対する効果については記載がない。
Along with stricter regulations on the quality of discharged water, there is a strong demand not only for improving the efficiency of flocculation of suspended solids in wastewater but also for reducing the quality of treated water, COD, ammonium nitrogen, normal hexane extract, etc. It is like. In general, as an agglomeration treatment, an inorganic flocculant such as sulfate band, polyaluminum chloride, polyiron sulfate, or polyiron chloride is added, and then a polymer flocculant is added to produce an agglomerate floc. A method of coagulating levitation is applied. In order to increase the treatment effect, the amount of inorganic flocculant added must be increased, the amount of sludge increases, processing costs increase, and problems such as the release of substances harmful to the environment such as aluminum are pointed out. Has been. For this reason, various improvements and proposals have been made on polyacrylamide (PAM) water-soluble polymers that are generally used as polymer flocculants. In general, there are aqueous solutions, powders, water-in-oil emulsions, etc., but aqueous solutions and powder types have low dissolution efficiency. Is concerned. Therefore, in order to solve these problems, the water-soluble polymer dispersion obtained by dissolving with good solubility and coexisting an ionic polymer dispersant in an aqueous salt solution that does not use a solvent and an emulsifier, and dispersion polymerization under stirring. A liquid is used (Patent Documents 1 and 2).
Various patent publications disclose techniques for water-soluble polymer dispersions obtained by coexisting an ionic polymer dispersant in an aqueous salt solution and performing dispersion polymerization under stirring. In general, ammonium sulfate is widely used as an inorganic salt during dispersion polymerization. Ammonium compounds are designated as hazardous substances in accordance with the 2014 revision of the Water Pollution Control Law, so water-soluble polymer dispersions containing ammonium sulfate The liquid is not preferred. Patent Document 3 discloses a method for producing a water-soluble polymer dispersion that does not use ammonium sulfate, but does not describe a specific coagulation treatment effect or treatment water quality.
本発明の目的は、排水の凝集沈殿処理あるいは凝集浮上処理において、高分子凝集剤を添加し、凝集処理により処理効率を高めると共に処理水質の改善を図ることができる排水の処理方法を提供することである。 An object of the present invention is to provide a wastewater treatment method capable of increasing the treatment efficiency and improving the quality of treated water by adding a polymer flocculant in the coagulation sedimentation treatment or coagulation flotation treatment of wastewater. It is.
本発明者は、鋭意検討の結果、以下に述べる発明に達した。即ち、塩化物イオン及び多価アニオンを含有する塩水溶液中で、下記一般式（１）で表される単量体を必須として含有する単量体あるいは単量体混合物水溶液を、該塩水溶液中に構成単位としてジアリルジメチルアンモニウム塩化物を含有する高分子分散剤を共存させ、攪拌下、分散重合して得られる水溶性重合体分散液であり、該水溶性重合体分散液総量に対して、無機塩の総量が１５質量％未満である水溶性重合体分散液を添加することを特徴とする排水の処理方法である。
一般式（１）
Ｒ１は水素又はメチル基、Ｒ２、Ｒ３は炭素数１〜３のアルキル基、アルコキシ基、Ｒ４は炭素数７〜２０のアルキル基あるいはアリール基である。Ａは酸素またはＮＨ、Ｂは炭素数２〜４のアルキレン基またはアルコキシレン基、Ｘ１は陰イオンをそれぞれ表わす。
As a result of intensive studies, the present inventor has reached the invention described below. That is, in a salt aqueous solution containing a chloride ion and a polyvalent anion, a monomer or monomer mixture aqueous solution containing the monomer represented by the following general formula (1) as an essential component in the salt aqueous solution. Is a water-soluble polymer dispersion obtained by coexisting with a polymer dispersant containing diallyldimethylammonium chloride as a structural unit and stirring and dispersing, with respect to the total amount of the water-soluble polymer dispersion, A wastewater treatment method comprising adding a water-soluble polymer dispersion having a total amount of inorganic salt of less than 15% by mass.
General formula (1)
R 1 is hydrogen or a methyl group, R 2 and R 3 are alkyl groups having 1 to 3 carbon atoms, alkoxy groups, and R 4 is an alkyl group or aryl group having 7 to 20 carbon atoms. A represents oxygen or NH, B represents an alkylene group or alkoxylene group having 2 to 4 carbon atoms, and X 1 represents an anion.
本発明における水溶性重合体分散液は、高分子凝集剤として凝集沈殿処理あるいは凝集浮上処理に適用することができる。 The water-soluble polymer dispersion in the present invention can be applied to a coagulation-precipitation treatment or a coagulation flotation treatment as a polymer flocculant.
本発明における排水の処理方法は、本発明における水溶性重合体分散液を排水に添加、混合し凝集させた後、固液分離することを特徴とする。一般的に使用されている高分子凝集剤に比べて、特定の組成を有し、特定の製法により製造されるため、溶解効率が良く、排水に添加すると優れた凝集処理効果を発揮し処理水質も改善することができる。 The method for treating waste water in the present invention is characterized in that the water-soluble polymer dispersion in the present invention is added to the waste water, mixed and agglomerated, followed by solid-liquid separation. Compared to commonly used polymer flocculants, it has a specific composition and is manufactured by a specific manufacturing method, so it has good dissolution efficiency and exhibits excellent flocculation effect when added to wastewater. Can also be improved.
本発明における水溶性重合体分散液は、塩水溶液中で、下記一般式（１）で表される単量体を必須として含有する単量体あるいは単量体混合物水溶液を、該塩水溶液中に可溶な高分子分散剤を共存させ、攪拌下、分散重合して得られる水溶性重合体分散液である。
一般式（１）
Ｒ１は水素又はメチル基、Ｒ２、Ｒ３は炭素数１〜３のアルキル基、アルコキシ基、Ｒ４は炭素数７〜２０のアルキル基あるいはアリール基である。Ａは酸素またはＮＨ、Ｂは炭素数２〜４のアルキレン基またはアルコキシレン基、Ｘ１は陰イオンをそれぞれ表わす。
The water-soluble polymer dispersion in the present invention contains a monomer or a monomer mixture aqueous solution containing a monomer represented by the following general formula (1) as an essential component in a salt aqueous solution. This is a water-soluble polymer dispersion obtained by coexisting a soluble polymer dispersant and dispersing polymerization with stirring.
General formula (1)
R 1 is hydrogen or a methyl group, R 2 and R 3 are alkyl groups having 1 to 3 carbon atoms, alkoxy groups, and R 4 is an alkyl group or aryl group having 7 to 20 carbon atoms. A represents oxygen or NH, B represents an alkylene group or alkoxylene group having 2 to 4 carbon atoms, and X 1 represents an anion.
本発明における水溶性重合体分散液を製造する際に使用する一般式（１）で表されるカチオン性単量体は、ジメチルアミノエチル（メタ）アクリレートあるいはジメチルアミノプロピルアクリルアミドの塩化ベンジル等のハロゲン化アリール化合物や炭素数が７〜２０のハロゲン化アルキルによる４級化物等が挙げられ、これらのカチオン性ビニル系単量体は１種を単独で用いることができ、２種以上を組み合わせて用いることもできる。具体的な例としては、（メタ）アクリロイルオキシエチルジメチルベンジルアンモニウム塩化物、（メタ）アクリロイルオキシ−２−ヒドロキシプロピルベンジルジメチルアンモニウム塩化物、（メタ）アクリロイルアミノプロピルジメチルベンジルアンモニウム塩化物等である。一般式（１）で表されるカチオン性単量体は１０〜７０モル％の範囲が好ましく、１０〜６０モル％が更に好ましい。 The cationic monomer represented by the general formula (1) used for producing the water-soluble polymer dispersion in the present invention is a halogen such as dimethyl chloride of dimethylaminoethyl (meth) acrylate or dimethylaminopropylacrylamide. Cationized aryl compounds and quaternized products of alkyl halides having 7 to 20 carbon atoms. These cationic vinyl monomers can be used alone or in combination of two or more. You can also. Specific examples include (meth) acryloyloxyethyldimethylbenzylammonium chloride, (meth) acryloyloxy-2-hydroxypropylbenzyldimethylammonium chloride, (meth) acryloylaminopropyldimethylbenzylammonium chloride, and the like. The cationic monomer represented by the general formula (1) is preferably in the range of 10 to 70 mol%, more preferably 10 to 60 mol%.
本発明における水溶性重合体分散液を製造する際に使用する一般式（１）で表されるカチオン性単量体と下記一般式（２）で表されるカチオン性単量体を共重合して使用することができる。
一般式（２）
Ｒ５は水素又はメチル基、Ｒ６、Ｒ７は炭素数１〜３のアルキルあるいはヒドロキシアルキル基、Ｒ８は水素、炭素数１〜３のアルキル基であり、Ａは酸素またはＮＨ、Ｂは炭素数２〜４のアルキレン基を表わす、Ｘ２ −は陰イオンをそれぞれ表わす。
A cationic monomer represented by the general formula (1) and a cationic monomer represented by the following general formula (2) used for producing the water-soluble polymer dispersion in the present invention are copolymerized. Can be used.
General formula (2)
R 5 is hydrogen or a methyl group, R 6 and R 7 are alkyl or hydroxyalkyl groups having 1 to 3 carbon atoms, R 8 is hydrogen and an alkyl group having 1 to 3 carbon atoms, A is oxygen or NH, B is represents an alkylene group having 2 to 4 carbon atoms, X 2 - represents respectively an anion.
一般式（２）で表されるカチオン性単量体として、ジメチルアミノエチル（メタ）アクリレート等、塩化メチル等のハロゲン化アルキル等が挙げられ、これらのカチオン性単量体は１種を単独で用いることができ、２種以上を組み合わせて用いることもできる。具体的な例としては、ジメチルアミノエチル（メタ）アクリレートあるいはジメチルアミノプロピルアクリルアミドの塩化メチルや塩化エチルなど低級アルキル基のハロゲン化物による四級化物である。例えば（メタ）アクリロイルオキシエチルトリメチルアンモニウム塩化物、（メタ）アクリロイルオキシ−２−ヒドロキシプロピルトリメチルアンモニウム塩化物、（メタ）アクリロイルアミノプロピルトリメチルアンモニウム塩化物等である。 Examples of the cationic monomer represented by the general formula (2) include dimethylaminoethyl (meth) acrylate, alkyl halides such as methyl chloride, and the like. It can also be used and it can also be used in combination of 2 or more types. Specific examples include quaternized products of dimethylaminoethyl (meth) acrylate or dimethylaminopropylacrylamide with a halide of a lower alkyl group such as methyl chloride or ethyl chloride. For example, (meth) acryloyloxyethyltrimethylammonium chloride, (meth) acryloyloxy-2-hydroxypropyltrimethylammonium chloride, (meth) acryloylaminopropyltrimethylammonium chloride, and the like.
一般式（１）で表されるカチオン性単量体と非イオン性単量体を共重合させる場合に使用する非イオン性単量体としては、（メタ）アクリルアミド、Ｎ,Ｎ−ジメチルアクリルアミド、アクリロニトリル、（メタ）アクリル酸−２−ヒドロキシエチル、ジアセトンアクリルアミド、Ｎ−ビニルピロリドン、Ｎ−ビニルホルムアミド、Ｎ−ビニルアセトアミド、アクリロイルモルホリン等が挙げられる。これらを二種以上組み合わせて使用しても良い。又、一般式（１）で表されるカチオン性単量体と一般式（２）で表されるカチオン性単量体と非イオン性単量体を共重合させても良い。本発明における水溶性重合体分散液を構成するカチオン性単量体の総量は３０〜７０モル％が好ましく、３０〜６０モル％が更に好ましく適用できる。これはカチオン度がこの範囲にあると分子量もある程度上げることができ、排水中の懸濁粒子のアニオン電荷を中和させる中和作用と、架橋吸着による凝集効果がバランス良く発揮できるためである。 Examples of the nonionic monomer used when the cationic monomer represented by the general formula (1) and the nonionic monomer are copolymerized include (meth) acrylamide, N, N-dimethylacrylamide, Examples include acrylonitrile, 2-hydroxyethyl (meth) acrylate, diacetone acrylamide, N-vinylpyrrolidone, N-vinylformamide, N-vinylacetamide, acryloylmorpholine, and the like. Two or more of these may be used in combination. Moreover, you may copolymerize the cationic monomer represented by General formula (1), the cationic monomer represented by General formula (2), and a nonionic monomer. The total amount of the cationic monomer constituting the water-soluble polymer dispersion in the present invention is preferably from 30 to 70 mol%, more preferably from 30 to 60 mol%. This is because when the cation degree is within this range, the molecular weight can be increased to some extent, and the neutralizing action for neutralizing the anionic charge of the suspended particles in the waste water and the aggregation effect by cross-linking adsorption can be exhibited in a well-balanced manner.
本発明における水溶性重合体分散液は、イオン性が両性であっても良く、その場合は製造時に、下記一般式（３）で表されるアニオン性単量体が使用される。
一般式（３）
Ｒ９は水素、メチル基又はカルボキシメチル基、ＱはＳＯ３、Ｃ６Ｈ４ＳＯ３、ＣＯＮＨＣ（ＣＨ３）２ＣＨ２ＳＯ３、Ｃ６Ｈ４ＣＯＯあるいはＣＯＯ、Ｒ１０は水素又はＣＯＯＹ２、Ｙ１あるいはＹ２は水素又は陽イオンをそれぞれ表わす。
The water-soluble polymer dispersion in the present invention may be amphoteric in ionicity. In that case, an anionic monomer represented by the following general formula (3) is used at the time of production.
General formula (3)
R 9 is hydrogen, methyl group or carboxymethyl group, Q is SO 3 , C 6 H 4 SO 3 , CONHC (CH 3 ) 2 CH 2 SO 3 , C 6 H 4 COO or COO, R 10 is hydrogen or COOY 2 , Y 1 or Y 2 each represents hydrogen or a cation.
本発明における両性水溶性重合体分散液を製造する際に使用する前記一般式（３）で表されるアニオン性単量体は０〜２０モル％の範囲である。アニオン性単量体の例としては、ビニルスルホン酸、ビニルベンゼンスルホン酸あるいは２−アクリルアミド−２−メチルプロパンスルホン酸、メタクリル酸、アクリル酸、イタコン酸、マレイン酸、フタル酸あるいはｐ−カルボキシスチレン酸等が挙げられる。これらを二種以上組み合わせて使用しても良い。又、一般式（３）で表されるアニオン性単量体と非イオン性単量体を使用しても良く、一般式（３）で表されるアニオン性単量体と一般式（２）で表されるカチオン性単量体と非イオン性単量体を使用しても良い。 The anionic monomer represented by the general formula (3) used when producing the amphoteric water-soluble polymer dispersion in the present invention is in the range of 0 to 20 mol%. Examples of anionic monomers include vinyl sulfonic acid, vinyl benzene sulfonic acid or 2-acrylamido-2-methylpropane sulfonic acid, methacrylic acid, acrylic acid, itaconic acid, maleic acid, phthalic acid or p-carboxystyrene acid Etc. Two or more of these may be used in combination. An anionic monomer and a nonionic monomer represented by the general formula (3) may be used, and an anionic monomer represented by the general formula (3) and the general formula (2) A cationic monomer and a nonionic monomer represented by
本発明における塩水中分散重合は、特開昭６２−１５２５１号公報、特開昭６２−２０５１１号公報、特開２００７−１６０８６号公報、特開２０１６−００３２５５号公報等で開示されている製法により製造することができる。塩水溶液中において、該塩水溶液中に構成単位としてジアリルジメチルアンモニウム塩化物を含有する高分子分散剤を共存させ、一般式（１）で表される単量体を必須として含有する単量体あるいは単量体混合物水溶液を分散重合する。一般式（１）で表される単量体を必須として含有して得られた水溶性重合体は、一般式（１）中のベンジル基等の疎水性基の存在により塩水溶液に溶解し難くなっており分散重合する際に適している。分散重合する際に、重合遅延性物質を全単量体に対し０．５〜５モル％添加することにより、増粘の抑制効果があり、適宜に添加して製造することができる。重合遅延性物質としては、イタコン酸、マレイン酸、フタル酸等が挙げられる。 The salt water dispersion polymerization in the present invention is carried out by a method disclosed in JP-A-62-215251, JP-A-62-25111, JP-A-2007-16086, JP-A-2006-003255, and the like. Can be manufactured. In the salt aqueous solution, a polymer dispersant containing diallyldimethylammonium chloride as a structural unit is coexisted in the salt aqueous solution, and a monomer containing the monomer represented by the general formula (1) as an essential component or The aqueous monomer mixture solution is subjected to dispersion polymerization. The water-soluble polymer obtained by containing the monomer represented by the general formula (1) as an essential component is difficult to dissolve in an aqueous salt solution due to the presence of a hydrophobic group such as a benzyl group in the general formula (1). It is suitable for dispersion polymerization. At the time of dispersion polymerization, by adding 0.5 to 5 mol% of a polymerization retarding substance with respect to all monomers, there is an effect of suppressing thickening, and it can be produced by appropriately adding. Examples of the polymerization retarding substance include itaconic acid, maleic acid, and phthalic acid.
塩水中分散重合に使用する高分子分散剤は、本発明においては、構成単位としてジアリルジメチルアンモニウム塩化物を含有するものを使用する。ポリジアリルジメチルアンモニウム塩化物でも良いが、ジアリルジメチルアンモニウム塩化物と非イオン性単量体との共重合体も使用可能である。非イオン性単量体の例としては、アクリルアミド、Ｎ−ビニルホルムアミド、Ｎ−ビニルアセトアミド、Ｎ−ビニルピロリドン、Ｎ、Ｎ−ジメチルアクリルアミド、アクリロニトリル、ジアセトンアクリルアミド、２−ヒドロキシエチル（メタ）アクリレート等であるが、アクリルアミドとの共重合体が好ましい。又、その他のカチオン性単量体、例えば、（メタ）アクリロイルオキシエチルトリメチルアンモニウム塩化物などを高分子分散剤組成中に含有していても差し支えない。 In the present invention, the polymer dispersant used for the salt water dispersion polymerization is one containing diallyldimethylammonium chloride as a structural unit. Polydiallyldimethylammonium chloride may be used, but a copolymer of diallyldimethylammonium chloride and a nonionic monomer can also be used. Examples of nonionic monomers include acrylamide, N-vinylformamide, N-vinylacetamide, N-vinylpyrrolidone, N, N-dimethylacrylamide, acrylonitrile, diacetone acrylamide, 2-hydroxyethyl (meth) acrylate, etc. However, a copolymer with acrylamide is preferred. In addition, other cationic monomers such as (meth) acryloyloxyethyltrimethylammonium chloride may be contained in the polymer dispersant composition.
前記高分子分散剤の分子量としては、高いと分散液の粘性が高くなり好ましくない。従って５，０００〜２００万、好ましくは５万〜１００万である。高分子分散剤の添加率は、単量体に対して１〜２０質量％であり、好ましくは５〜２０質量％である。分散液に対して５質量％未満が好ましい。これは５質量％以上含有すると経済的に不利であり、高分子の機能を阻害する可能性が有るためである。 When the molecular weight of the polymer dispersant is high, the viscosity of the dispersion becomes high, which is not preferable. Therefore, it is 5,000 to 2,000,000, preferably 50,000 to 1,000,000. The addition rate of a polymer dispersing agent is 1-20 mass% with respect to a monomer, Preferably it is 5-20 mass%. The amount is preferably less than 5% by mass with respect to the dispersion. This is because containing 5% by mass or more is economically disadvantageous and may inhibit the function of the polymer.
重合時に使用する無機塩としては、塩化物イオンと多価アニオンを含有する塩を使用する。この二種類の塩を必須として使用することで大きな増粘を抑制し、且つ無機塩総量を減少させた水溶性重合体分散液を製造することができる。塩化物イオンを含有する塩として、塩化ナトリウム、塩化カリウム、塩化カルシウム、等が挙げられる。多価アニオンを含有する塩として、硫酸ナトリウム、硫酸マグネシウムが好ましい。塩化物イオン含有塩と多価アニオン含有塩の比率は、質量比で１：９〜９：１の範囲であり、好ましくは３：７〜７：３である。これら以外のアルカリ金属イオン、ハロゲン化物イオン、硝酸イオン、リン酸イオン、アンモニウムイオン等も含まれていても良い。これら無機塩水溶液中に前記単量体類を溶解させ、更に高分子分散剤を共存させ、ｐＨを２〜５に調製した後、窒素置換後、重合開始剤によって重合を開始させる。 As the inorganic salt used at the time of polymerization, a salt containing a chloride ion and a polyvalent anion is used. By using these two types of salts as essential, it is possible to produce a water-soluble polymer dispersion in which a large viscosity is suppressed and the total amount of inorganic salts is reduced. Examples of the salt containing chloride ions include sodium chloride, potassium chloride, calcium chloride and the like. As a salt containing a polyvalent anion, sodium sulfate and magnesium sulfate are preferable. The ratio of the chloride ion-containing salt to the polyvalent anion-containing salt is in the range of 1: 9 to 9: 1 by mass ratio, preferably 3: 7 to 7: 3. Alkali metal ions, halide ions, nitrate ions, phosphate ions, ammonium ions and the like other than these may also be included. The monomers are dissolved in these inorganic salt aqueous solutions, a polymer dispersant is further allowed to coexist, the pH is adjusted to 2 to 5, and after substitution with nitrogen, polymerization is initiated by a polymerization initiator.
塩化物イオンと多価アニオンを併用すると無機塩の総量を減らすことができ、水溶性重合体分散液総量に対して、１５質量％未満にすることができる。通常は２０質量％以上存在しないと安定した分散液は製造できない。これは製造時に大きな増粘が生じるためである。しかし、本発明における水溶性重合体分散液では、構成単位としてジアリルジメチルアンモニウム塩化物を含有する高分子分散剤を使用し、塩化物イオンと多価アニオンを併用することで増粘を抑制できる。 When chloride ions and polyvalent anions are used in combination, the total amount of inorganic salts can be reduced, and the total amount of water-soluble polymer dispersion can be reduced to less than 15% by mass. Usually, a stable dispersion cannot be produced unless it is present in an amount of 20% by mass or more. This is because large thickening occurs during production. However, in the water-soluble polymer dispersion in the present invention, thickening can be suppressed by using a polymer dispersant containing diallyldimethylammonium chloride as a structural unit and using chloride ions and polyvalent anions in combination.
構成単位としてジアリルジメチルアンモニウム塩化物を含有する高分子分散剤と、塩化物イオンと多価アニオンを併用すると増粘を抑制する効果があることについては、理論的には不明な部分が多く解明できないが、現象面から推定すると以下の様になる。即ち、塩水溶液中で重合が進行していくと、生成高分子濃度は、溶解度以上となり高分子粒子の析出が始まるが、その手前では溶解している高分子のため重合物自体（重合系）の粘性も増加し、溶解高分子と析出粒子が共存した状態になる。この後、析出した高分子の割合は増加していき、重合物は徐々に粘性が低下し、分散状態に相変化する。この共存状態時に、析出粒子とゲル状の溶解高分子間における滑りを向上させ、相変化前の増粘状態から分散状態への相変化をスムーズに移行させるのが、相移行期における分散剤の主な役目と考えられる。重合の初期段階では、分散剤の構成単位であるジアリルジメチルアンモニウム塩化物と塩化物イオンの作用により、生成高分子の比較的低分子量の相分離に関与し、相変化を円滑に進行させ、重合の後半では塩析力の強い多価アニオンの作用により生成高分子の比較的高分子量のものとの塩析効果を促進する結果、高分子分散液が安定して製造できると考えられる。 Theoretically, there are many unclear points about the fact that the use of a polymeric dispersant containing diallyldimethylammonium chloride as a structural unit and the combined use of chloride ions and polyvalent anions has the effect of suppressing thickening. However, it is as follows when estimated from the phenomenon side. That is, as polymerization proceeds in an aqueous salt solution, the concentration of the produced polymer becomes higher than the solubility, and precipitation of polymer particles begins, but the polymer itself (polymerization system) because of the dissolved polymer before that. The viscosity of the polymer also increases, and the dissolved polymer and precipitated particles coexist. Thereafter, the ratio of the precipitated polymer increases, the viscosity of the polymer gradually decreases, and changes into a dispersed state. In this coexisting state, the slip between the precipitated particles and the gel-like dissolved polymer is improved, and the phase transition from the thickened state before the phase change to the dispersed state smoothly shifts. It is considered the main role. In the initial stage of polymerization, due to the action of diallyldimethylammonium chloride, which is a constituent unit of the dispersant, and chloride ions, it participates in the phase separation of the resulting polymer with a relatively low molecular weight, allowing the phase change to proceed smoothly. In the latter half of the process, it is considered that the polymer dispersion can be stably produced as a result of promoting the salting out effect of the produced polymer with a relatively high molecular weight by the action of the polyvalent anion having a strong salting out power.
本発明において、有効成分として作用せず、又、高分子の機能を阻害する場合がある無機塩を抑制することができる。特に水溶性重合体分散液の無機塩として、一般的に硫酸アンモニウムが好適に使用されているが、硫酸アンモニウム塩由来の全窒素含有量は、５００００ｐｐｍ（対水溶性重合体分散液製品）程度は含まれている。この硫酸アンモニウム塩由来の窒素を無くすことで、全窒素含有量を３００００ｐｐｍ（対水溶性重合体分散液製品）未満にまで低減することができる。平成２６年の水質汚濁防止法改正に伴いアンモニウム化合物が有害物質に指定されていることから環境に与える影響が懸念されており、本発明における水溶性重合体分散液は、無機塩総量を１５質量％未満に抑制できるので環境に与える影響を減少させることができると共に凝集処理効果及び処理水質を改善できるものである。又、油中水型エマルジョンとは異なり、溶剤と乳化剤を使用しないためノルマルヘキサン抽出物の量も低減することが可能となり、総合的に判断して従来の高分子凝集剤を使用するよりも水質改善効果が達成できる。このため、し尿処理場の脱離液の膜処理施設等、濾液を直接河川水等に放流するため高分子凝集剤の形態が粉末品しか使用できなかった現場においても使用が見込める。 In the present invention, an inorganic salt that does not act as an active ingredient and may inhibit the function of the polymer can be suppressed. In particular, ammonium sulfate is preferably used as the inorganic salt of the water-soluble polymer dispersion, but the total nitrogen content derived from the ammonium sulfate salt is about 50,000 ppm (for water-soluble polymer dispersion products). ing. By eliminating the nitrogen derived from the ammonium sulfate salt, the total nitrogen content can be reduced to less than 30000 ppm (for a water-soluble polymer dispersion product). With the amendment of the Water Pollution Control Act of 2014, the ammonium compound is designated as a hazardous substance, so there is concern about the impact on the environment. The water-soluble polymer dispersion in the present invention has a total inorganic salt content of 15 mass. Since it can suppress to less than%, the influence which it has on an environment can be reduced, and the agglomeration effect and the quality of treated water can be improved. In addition, unlike water-in-oil emulsions, the amount of normal hexane extract can be reduced because no solvent and emulsifier are used, and water quality is better than using conventional polymer flocculants. Improvement effect can be achieved. For this reason, since the filtrate is directly discharged into river water or the like, such as a membrane treatment facility for the effluent of a human waste treatment plant, it can be used even in the field where the polymer flocculant can only be used in the form of powder.
重合濃度としては、単量体濃度として１０質量％〜３５質量％であるが、好ましくは１５質量％〜３０質量％である。これは単量体濃度が高い程、輸送コストの問題で経済的に有利であるが、単量体濃度が３５質量％を超えると製造時に増粘が大きくなり分散液が得られ難くなるためである。単量体供給方法としては、重合開始時、一括して仕込んでも良いし、適宜分割して仕込んでも良い。 The polymerization concentration is 10% by mass to 35% by mass as the monomer concentration, and preferably 15% by mass to 30% by mass. This is because the higher the monomer concentration, the more economically advantageous due to the problem of transportation costs. However, if the monomer concentration exceeds 35% by mass, the viscosity increases during production and it becomes difficult to obtain a dispersion. is there. As a monomer supply method, it may be charged all at once at the start of polymerization, or may be charged in an appropriate manner.
重合条件は通常、使用する単量体や共重合モル％によって適宜決定し、温度としては０〜１００℃の範囲で行う。重合開始はラジカル重合開始剤を使用する。これら開始剤は油溶性あるいは水溶性のどちらでも良く、アゾ系、過酸化物系、レドックス系の何れでも重合することが可能である。油溶性アゾ系開始剤の例としては、２、２’−アゾビスイソブチロニトリル、１、１’−アゾビス（シクロヘキサンカルボニトリル）、２、２’−アゾビス（２−メチルブチロニトリル）、２、２’−アゾビス（２−メチルプロピオネート）、４、４−アゾビス（４−メトキシ−２、４ジメチル）バレロニトリル等が挙げられ、水混溶性溶剤に溶解し添加する。 The polymerization conditions are usually determined appropriately depending on the monomers used and the copolymerization mol%, and the temperature is in the range of 0 to 100 ° C. For the initiation of polymerization, a radical polymerization initiator is used. These initiators may be either oil-soluble or water-soluble, and can be polymerized by any of azo, peroxide, and redox systems. Examples of oil-soluble azo initiators are 2,2′-azobisisobutyronitrile, 1,1′-azobis (cyclohexanecarbonitrile), 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobis (2-methylpropionate), 4,4-azobis (4-methoxy-2,4dimethyl) valeronitrile, and the like are mentioned, which are dissolved in a water-miscible solvent and added.
水溶性アゾ系開始剤の例としては、２，２’−アゾビス［２−（２−イミダゾリン−２−イル）プロパン］二塩酸塩、２、２’−アゾビス［２−（２−アミジノプロパン）二塩酸塩、４、４’−アゾビス（４−シアノ吉草酸）等が挙げられる。又、レドックス系の例としては、ペルオクソ二硫酸アンモニウムと亜硫酸ナトリウム、亜硫酸水素ナトリウム、トリメチルアミン、テトラメチルエチレンジアミン等との組み合わせが挙げられる。更に過酸化物の例としては、ペルオクソ二硫酸アンモニウム或いはカリウム、過酸化水素、ベンゾイルペルオキサイド、ラウロイルペルオキサイド、オクタノイルペルオキサイド、サクシニックペルオキサイド、ｔ−ブチルペルオキシ２−エチルヘキサノエート等を挙げることができる。これら開始剤の中で最も好ましいのは、水溶性アゾ開始剤の２，２’−アゾビス［２−（２−イミダゾリン−２−イル）プロパン］二塩酸塩、２、２’−アゾビス［２−（２−アミジノプロパン）二塩酸塩である。アゾ系開始剤の添加量は、重合開始時、単量体当たり５０〜５００ｐｐｍ、好ましくは７０〜２００ｐｐｍ添加する。しかし、一回の添加では重合率が低くなるので、数回に分けて添加することが好ましい。 Examples of water-soluble azo initiators include 2,2′-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride, 2,2′-azobis [2- (2-amidinopropane) And dihydrochloride, 4,4′-azobis (4-cyanovaleric acid), and the like. Examples of the redox system include a combination of ammonium peroxodisulfate and sodium sulfite, sodium bisulfite, trimethylamine, tetramethylethylenediamine and the like. Further examples of peroxides include ammonium or potassium peroxodisulfate, hydrogen peroxide, benzoyl peroxide, lauroyl peroxide, octanoyl peroxide, succinic peroxide, t-butylperoxy 2-ethylhexanoate, and the like. be able to. Most preferred among these initiators is the water-soluble azo initiator 2,2′-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride, 2,2′-azobis [2- (2-Amidinopropane) dihydrochloride. The addition amount of the azo initiator is 50 to 500 ppm, preferably 70 to 200 ppm per monomer at the start of polymerization. However, since the polymerization rate is lowered by a single addition, it is preferable to add in several portions.
又、レドックス系開始剤で共重合する場合、４０℃以上の条件で重合を開始させると重合の制御は難しく、急激な温度上昇や重合液の塊状化などが起きて、高重合度で安定な分散液が得られないため、１５〜３５℃が好ましい。この開始剤の添加率は、重合開始時、単量体当たり５〜１００ｐｐｍ、好ましくは１０〜５０ｐｐｍ添加する。しかし、一回の添加では重合率が低くなるので、数回添加することが好ましい。添加回数としては、２〜５回、好ましくは２〜３回である。これらイオン性高分子からなる高分子分散剤の添加量としては、対単量体１〜３０質量％であり、好ましくは２〜２０質量％である。１質量％以下では、分散剤としての効果がなく、３０質量％以上では、分散液の粘性が高くなる上、コスト的に不利になる。 In addition, when copolymerizing with a redox initiator, it is difficult to control the polymerization when the polymerization is started at a temperature of 40 ° C. or more, and a rapid temperature rise or agglomeration of the polymerization solution occurs, resulting in a high degree of polymerization and stability. Since a dispersion liquid cannot be obtained, 15-35 degreeC is preferable. The initiator is added at a rate of 5 to 100 ppm, preferably 10 to 50 ppm per monomer at the start of polymerization. However, since the polymerization rate is lowered by a single addition, it is preferably added several times. As addition frequency, it is 2-5 times, Preferably it is 2-3 times. The addition amount of the polymer dispersant composed of these ionic polymers is 1 to 30% by mass, preferably 2 to 20% by mass with respect to the monomer. If it is 1% by mass or less, there is no effect as a dispersing agent, and if it is 30% by mass or more, the viscosity of the dispersion becomes high and it is disadvantageous in terms of cost.
本発明における水溶性重合体分散液は、高分子凝集剤として排水に添加、混合し凝集させた後、固液分離することを特徴とする排水の処理方法であるが、排水の懸濁物質の種類によって凝集沈殿処理あるいは凝集浮上処理が可能である。食品排水や古紙排水の様にＳＳ濃度が比較的低い場合、ＳＳ３０００ｐｐｍ以下の場合は浮上処理が適し、砂利洗浄排水の様にＳＳ濃度が比較的高い場合、３０００ｐｐｍを超える場合は、沈殿処理が適している。 The water-soluble polymer dispersion in the present invention is a wastewater treatment method characterized in that it is added to the wastewater as a polymer flocculant, mixed and agglomerated, and then solid-liquid separated. Depending on the type, coagulation sedimentation treatment or coagulation flotation treatment is possible. When SS concentration is relatively low, such as food wastewater and waste paper wastewater, floating treatment is suitable when SS is 3000ppm or less, and when SS concentration is relatively high such as gravel washing wastewater, precipitation treatment is suitable when it exceeds 3000ppm. ing.
本発明における水溶性重合体分散液は、従来の塩水溶液中でイオン性高分子分散剤を共存させ、撹拌下、分散重合して得られる水溶性重合体分散液に比べて、無機塩を低減させることができるので、高い分子量の重合体を得ることができる。凝集沈殿処理あるいは凝集浮上処理として機能を発揮するためには、本発明における水溶性重合体分散液の分子量の指標となる０．５質量％塩水溶液粘度、即ち、分散液を構成する水溶性重合体の２５℃で測定した０．５質量％における、２質量％硫酸アンモニウム水溶液中の水溶液粘度が３０〜１００ｍＰａ・ｓの範囲であり、５０〜１００ｍＰａ・ｓが好ましく、６０〜１００ｍＰａ・ｓがより一層、好ましい。特に凝集処理効果に加えてＣＯＤ成分、アンモニア態窒素を抑制することができるため、本発明における水溶性重合体分散液を適用する処理方法として凝集浮上処理はより好適である。これは、水溶性重合体分散液に含有される無機塩の総量が少なく硫酸アンモニウムを使用しないことに加えて、分子量、カチオン量、親水性・疎水性のバランス、溶解液粘性が低いこと等が影響していることが考えられるが、加圧水と混合されるときに微細気泡を取り込みながら効率的に凝集フロックが生じる結果、ＣＯＤ成分をより吸着しやすいことによるものと推測される。そのため、無機凝集剤の添加量を抑制、あるいは無添加でも処理することが可能である。 The water-soluble polymer dispersion in the present invention reduces inorganic salts compared to a water-soluble polymer dispersion obtained by coexisting an ionic polymer dispersant in a conventional aqueous salt solution and dispersion polymerization under stirring. Therefore, a high molecular weight polymer can be obtained. In order to exert the function as the coagulation sedimentation treatment or the coagulation flotation treatment, the 0.5 mass% salt aqueous solution viscosity, which is an index of the molecular weight of the water-soluble polymer dispersion in the present invention, that is, the water-soluble weight constituting the dispersion is used. The aqueous solution viscosity in a 2% by mass ammonium sulfate aqueous solution at 0.5% by mass measured at 25 ° C. of the coalescence is in the range of 30 to 100 mPa · s, preferably 50 to 100 mPa · s, and more preferably 60 to 100 mPa · s. ,preferable. In particular, since the COD component and ammonia nitrogen can be suppressed in addition to the aggregation treatment effect, the aggregation levitation treatment is more suitable as a treatment method to which the water-soluble polymer dispersion in the present invention is applied. This is due to the fact that the total amount of inorganic salts contained in the water-soluble polymer dispersion is small and ammonium sulfate is not used, as well as the molecular weight, cation content, hydrophilic / hydrophobic balance, and low viscosity of the solution. However, it is presumed that the COD component is more easily adsorbed as a result of efficient aggregation flocs occurring while taking in fine bubbles when mixed with pressurized water. For this reason, it is possible to suppress the addition amount of the inorganic flocculant or to perform the treatment without addition.
本発明における水溶性重合体分散液は、溶解性が優れるため製品のままの状態で添加することもできるし、任意の濃度に水で溶解、希釈して排水に添加できる。溶解する場合は、一般的に溶解濃度０．０５〜０．３質量％を適用する。又、排水に対する添加率は、排水に対して通常１〜１００ｐｐｍ、好ましくは２〜５０ｐｐｍである。又、塩化第二鉄、硫酸第二鉄、ＰＡＣ、硫酸バンド等の無機系凝集剤と併用しても差し支えないが、処理水質の改善と同時に薬品使用量やＳＳ処分費コスト等の削減改善の観点から添加量を抑制あるいは無添加が好ましい。 Since the water-soluble polymer dispersion in the present invention has excellent solubility, it can be added as it is, or can be added to waste water after being dissolved and diluted with water to an arbitrary concentration. In the case of dissolution, a dissolution concentration of 0.05 to 0.3% by mass is generally applied. Moreover, the addition rate with respect to a waste_water | drain is 1-100 ppm normally with respect to a waste_water | drain, Preferably it is 2-50 ppm. Also, it can be used in combination with inorganic flocculants such as ferric chloride, ferric sulfate, PAC, and sulfuric acid bands. From the viewpoint, it is preferable to suppress the addition amount or to add no addition.
以下、実施例によって本発明を更に詳しく説明するが、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。 EXAMPLES Hereinafter, although an Example demonstrates this invention in more detail, this invention is not restrict | limited to a following example, unless the summary is exceeded.
先ず、特開２０１６−００３２５５号公報等で開示されている製法により本発明で使用する水溶性重合体分散液を得た。以下に製造例を示す。 First, the water-soluble polymer dispersion used by this invention was obtained by the manufacturing method currently disclosed by Unexamined-Japanese-Patent No. 2006-003255 etc. Production examples are shown below.
（製造例１）アンカー翼撹拌機、冷却管及び窒素導入管を備えた０．５Ｌのセパラブルフラスコに脱塩水１５４．２ｇ、３５質量％ポリジアリルジメチルアンモニウム塩化物２０．５ｇ、更に塩化ナトリウム１１．１ｇ、硫酸ナトリウム４．５ｇを加え、撹拌下４０℃に昇温し均一に溶解した。次に、５０質量％アクリルアミド４１．７ｇ、８０質量％アクリロイルオキシエチルトリメチルアンモニウム塩化物１０．９ｇ、８０質量％アクリロイルオキシエチルジメチルベンジルアンモニウム塩化物３８ｇを加え均一溶液とし、４０℃の湯浴に浸し温度を安定化させた。次に、窒素雰囲気下、１０質量％の２，２’−アゾビス［２−（２−イミダゾリン−２−イル）プロパン］二塩酸塩水溶液を重合開始剤として対単量体あたり２００ｐｐｍ添加し、撹拌下４０℃で１８時間重合した。反応終了後、得られた分散液に硫酸ナトリウム１８ｇを加え硫酸ナトリウムの溶け残りがなくなるまで、撹拌し水溶性重合体分散液を得た。この水溶性重合体のモル組成比は、アクリルアミド／アクリロイルオキシエチルトリメチルアンモニウム塩化物／アクリロイルオキシエチルジメチルベンジルアンモニウム塩化物＝６５／１０／２５モル％となる。この分散液の粘度は５２６ｍＰａ・ｓで、２質量％硫酸アンモニウム水溶液に水溶性重合体分散液を０．５質量％濃度に溶かした時の粘度は８５ｍＰａ・ｓであった。これを試料１として表１に示す。 (Production Example 1) In a 0.5 L separable flask equipped with an anchor blade stirrer, a cooling tube and a nitrogen introduction tube, 154.2 g of demineralized water, 20.5 g of 35 mass% polydiallyldimethylammonium chloride, and sodium chloride 11 0.1 g and sodium sulfate 4.5 g were added, and the mixture was heated to 40 ° C. with stirring and dissolved uniformly. Next, 41.7 g of 50% by mass acrylamide, 10.9 g of 80% by mass acryloyloxyethyltrimethylammonium chloride, and 38 g of 80% by mass acryloyloxyethyldimethylbenzylammonium chloride were added to make a homogeneous solution, and immersed in a 40 ° C. hot water bath. The temperature was stabilized. Next, in a nitrogen atmosphere, 10 ppm by mass of 2,2′-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride aqueous solution as a polymerization initiator was added at 200 ppm per monomer and stirred. Polymerization was carried out at 40 ° C. for 18 hours. After completion of the reaction, 18 g of sodium sulfate was added to the obtained dispersion, and the mixture was stirred until the remaining sodium sulfate was not dissolved to obtain a water-soluble polymer dispersion. The molar composition ratio of this water-soluble polymer is acrylamide / acryloyloxyethyltrimethylammonium chloride / acryloyloxyethyldimethylbenzylammonium chloride = 65/10/25 mol%. The dispersion had a viscosity of 526 mPa · s, and the viscosity when the water-soluble polymer dispersion was dissolved in a 2% by mass aqueous ammonium sulfate solution at a concentration of 0.5% by mass was 85 mPa · s. This is shown in Table 1 as Sample 1.
（製造例２）アンカー翼撹拌機、冷却管及び窒素導入管を備えた０．５Ｌのセパラブルフラスコに脱塩水１３９．２ｇ、３５質量％ポリジアリルジメチルアンモニウム塩化物３２．４ｇ、更に塩化ナトリウム６．３ｇ、硫酸ナトリウム４．２ｇを加え、撹拌下４０℃に昇温し均一に溶解した。次に、５０質量％アクリルアミド２４．６ｇ、８０質量％アクリロイルオキシエチルトリメチルアンモニウム塩化物２０．９ｇ、８０質量％アクリロイルオキシエチルジメチルベンジルアンモニウム塩化物５８．２ｇを加え均一溶液とし、４０℃の湯浴に浸し温度を安定化させた。次に、窒素雰囲気下、１０質量％の２，２’−アゾビス［２−（２−イミダゾリン−２−イル）プロパン］二塩酸塩水溶液を重合開始剤として対単量体あたり２００ｐｐｍ添加し、撹拌下４０℃で１８時間重合した。反応終了後、得られた分散液に硫酸ナトリウム１４ｇを加え硫酸ナトリウムの溶け残りがなくなるまで、撹拌し水溶性重合体分散液を得た。この水溶性重合体のモル組成比は、アクリルアミド／アクリロイルオキシエチルトリメチルアンモニウム塩化物／アクリロイルオキシエチルジメチルベンジルアンモニウム塩化物＝４０／２０／４０モル％となる。この分散液は５４６０ｍＰａ・ｓで、２質量％硫酸アンモニウム水溶液に分散液を０．５質量％濃度に溶かした時の粘度は７１ｍＰａ・ｓであった。これを試料２として表１に示す。 (Production Example 2) In a 0.5 L separable flask equipped with an anchor blade stirrer, a cooling pipe and a nitrogen introducing pipe, 139.2 g of demineralized water, 32.4 g of 35% by mass polydiallyldimethylammonium chloride, and further sodium chloride 6 .3 g and sodium sulfate 4.2 g were added, and the mixture was heated to 40 ° C. with stirring and dissolved uniformly. Next, 24.6 g of 50% by mass acrylamide, 20.9 g of 80% by mass acryloyloxyethyltrimethylammonium chloride, and 58.2 g of 80% by mass acryloyloxyethyldimethylbenzylammonium chloride were added to obtain a homogeneous solution, and a hot bath at 40 ° C. So as to stabilize the temperature. Next, in a nitrogen atmosphere, 10 ppm by mass of 2,2′-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride aqueous solution as a polymerization initiator was added at 200 ppm per monomer and stirred. Polymerization was carried out at 40 ° C. for 18 hours. After the completion of the reaction, 14 g of sodium sulfate was added to the obtained dispersion, and the mixture was stirred until there was no undissolved sodium sulfate to obtain a water-soluble polymer dispersion. The molar composition ratio of this water-soluble polymer is acrylamide / acryloyloxyethyltrimethylammonium chloride / acryloyloxyethyldimethylbenzylammonium chloride = 40/20/40 mol%. This dispersion was 5460 mPa · s, and the viscosity when the dispersion was dissolved in a 2% by mass ammonium sulfate aqueous solution to a concentration of 0.5% by mass was 71 mPa · s. This is shown in Table 1 as Sample 2.
（製造例３）アンカー翼撹拌機、冷却管及び窒素導入管を備えた０．５Ｌのセパラブルフラスコに脱塩水１９３．６ｇ、３５質量％ポリジアリルジメチルアンモニウム塩化物１２．３ｇ、更に塩化ナトリウム１２．４ｇ、硫酸マグネシウム４．９ｇを加え、撹拌下３６℃に昇温し均一に溶解した。次に、５０質量％アクリルアミド２５．０ｇ、８０質量％アクリロイルオキシエチルトリメチルアンモニウム塩化物６．６ｇ、８０質量％アクリロイルオキシエチルジメチルベンジルアンモニウム塩化物２２．８ｇを加え均一溶液とし、３６℃の湯浴に浸し温度を安定化させた。次に、窒素雰囲気下、１０質量％の２，２’−アゾビス［２−（２−イミダゾリン−２−イル）プロパン］二塩酸塩水溶液を重合開始剤として対単量体あたり８０ｐｐｍ添加し、撹拌下３６℃で１８時間重合した。反応終了後、得られた分散液に硫酸マグネシウム１７．０ｇを加え硫酸マグネシウムの溶け残りがなくなるまで、撹拌し水溶性重合体分散液を得た。この水溶性重合体のモル組成比は、アクリルアミド／アクリロイルオキシエチルトリメチルアンモニウム塩化物／アクリロイルオキシエチルジメチルベンジルアンモニウム塩化物＝６５／１０／２５モル％となる。この分散液は４２５ｍＰａ・ｓで、２質量％硫酸アンモニウム水溶液に分散液を０．５質量％濃度に溶かした時の粘度は６１ｍＰａ・ｓであった。これを試料３として表１に示す。 (Production Example 3) In a 0.5 L separable flask equipped with an anchor blade stirrer, a cooling pipe and a nitrogen introduction pipe, 193.6 g of demineralized water, 12.3 g of 35% by mass polydiallyldimethylammonium chloride, and 12% of sodium chloride 0.4 g and magnesium sulfate 4.9 g were added, and the mixture was heated to 36 ° C. with stirring and dissolved uniformly. Next, 25.0 g of 50% by mass acrylamide, 6.6 g of 80% by mass acryloyloxyethyltrimethylammonium chloride, and 22.8 g of 80% by mass acryloyloxyethyldimethylbenzylammonium chloride were added to form a homogeneous solution, and a 36 ° C. water bath So as to stabilize the temperature. Next, in a nitrogen atmosphere, 10 ppm by mass of 2,2′-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride aqueous solution as a polymerization initiator was added at 80 ppm per monomer and stirred. Polymerization was carried out at 36 ° C. for 18 hours. After the completion of the reaction, 17.0 g of magnesium sulfate was added to the obtained dispersion, and the mixture was stirred until the magnesium sulfate was not dissolved to obtain a water-soluble polymer dispersion. The molar composition ratio of this water-soluble polymer is acrylamide / acryloyloxyethyltrimethylammonium chloride / acryloyloxyethyldimethylbenzylammonium chloride = 65/10/25 mol%. This dispersion was 425 mPa · s, and the viscosity when the dispersion was dissolved in a 2% by mass ammonium sulfate aqueous solution to a concentration of 0.5% by mass was 61 mPa · s. This is shown in Table 1 as Sample 3.
尚、製造例１と同様に同じ単量体組成、重合条件で、それ以外の高分子分散剤質量、重合時塩、単量体濃度、あるいは無機塩濃度を変更したものを製造した。比較試料１〜４として表１に示す。尚、比較試料３、４は反応途中、反応液の粘度が上昇し撹拌困難となり固化した。 In the same manner as in Production Example 1, with the same monomer composition and polymerization conditions, other polymer dispersant masses, salt during polymerization, monomer concentration, or inorganic salt concentration were changed. It shows in Table 1 as comparative samples 1-4. In Comparative Samples 3 and 4, during the reaction, the viscosity of the reaction solution increased, making stirring difficult and solidifying.
（表１）
ＡＡＭ：アクリルアミド
ＤＭＱ：アクリロイルオキシエチルトリメチルアンモニウム塩化物
ＤＭＢＺ：アクリロイルオキシエチルジメチルベンジルアンモニウム塩化物
高分子分散剤ｐ−ＤＤ：ポリジアリルジメチルアンモニウム塩化物
高分子分散剤ｐ−ＤＭＱ：ポリアクリロイルオキシエチルトリメチルアンモニウム塩化物
重合時塩：（ａ）塩化ナトリウム、（ｂ）硫酸ナトリウム、（ｃ）硫酸マグネシウム、（ｄ）硫酸アンモニウム
単量体濃度：水溶性重合体分散液に対する単量体の質量割合
無機塩濃度：水溶性重合体分散液に対する無機塩の質量割合
分散液粘度：水溶性重合体分散液の２５℃において測定した粘度
０．５質量％塩水溶液粘度：２質量％硫酸アンモニウム水中に高分子濃度が０．５質量％になるように溶解したときの２５℃において測定した粘度。
(Table 1)
AAM: acrylamide DMQ: acryloyloxyethyltrimethylammonium chloride DMBZ: acryloyloxyethyldimethylbenzylammonium chloride polymer dispersant p-DD: polydiallyldimethylammonium chloride polymer dispersant p-DMQ: polyacryloyloxyethyltrimethylammonium Salt during chloride polymerization: (a) sodium chloride, (b) sodium sulfate, (c) magnesium sulfate, (d) ammonium sulfate monomer concentration: mass ratio of monomer to water-soluble polymer dispersion inorganic salt concentration: Weight ratio of inorganic salt to water-soluble polymer dispersion Dispersion viscosity: 0.5% by weight of water-soluble polymer dispersion measured at 25 ° C. Viscosity of salt aqueous solution: 2% by weight The polymer concentration is 0. 25 when dissolved to 5% by mass The viscosity measured in.
排水処理に高分子凝集剤として汎用されている市販品の水溶性高分子試料Ａ、〜Ｄを用意した。組成、物性を表２に示す。 Commercially available water-soluble polymer samples A to D that are widely used as polymer flocculants for wastewater treatment were prepared. The composition and physical properties are shown in Table 2.
（表２）
０．５質量％塩水溶液粘度；４質量％食塩水中に高分子濃度が０．５質量％になるように溶解したときの２５℃において測定した粘度（ｍＰａ・ｓ）。
０．２質量％水溶液粘度；高分子濃度が０．２質量％になるように水で溶解したときの２５℃において測定した粘度（ｍＰａ・ｓ）
(Table 2)
0.5 mass% salt aqueous solution viscosity; viscosity (mPa · s) measured at 25 ° C. when dissolved in 4 mass% saline so that the polymer concentration becomes 0.5 mass%.
0.2 mass% aqueous solution viscosity; viscosity (mPa · s) measured at 25 ° C. when dissolved in water so that the polymer concentration becomes 0.2 mass%
（実施例１）
本発明における水溶性重合体分散液の凝集性能を評価した。凝集性能評価には、沈降性が不良で沈殿槽で流出が発生している活性汚泥、ｐＨ７．６、ＭＬＳＳ濃度５１９０ｐｐｍ、ＳＶＩが１９０（ｍＬ／ｇ）を曝気槽からメスシリンダーに２００ｍＬ採取し試験に用いた。当該活性汚泥は、高カチオンであるＰＡＭ系水溶性高分子が使用されていたが、処理効果が不安定な状況であった。表１の本発明における水溶性重合体分散液試料１の０．２質量％溶解液を、対処理液１０ｐｐｍあるいは１５ｐｐｍ添加後、上下転倒強攪拌５回、弱撹拌５回行い静置し、対処理液の沈降性を比較するため３０分後の沈降界面容積、フロック径、沈降速度を測定した。その結果を表３に示す。
Example 1
The aggregation performance of the water-soluble polymer dispersion in the present invention was evaluated. For the coagulation performance evaluation, 200 ml of activated sludge, pH 7.6, MLSS concentration of 5190 ppm, SVI of 190 (mL / g) with poor sedimentation and outflow in the sedimentation tank was sampled from the aeration tank to the measuring cylinder and tested. Used for. The activated sludge used a PAM water-soluble polymer having a high cation, but the treatment effect was unstable. After adding 0.2 ppm by weight of the water-soluble polymer dispersion sample 1 in Table 1 of the present invention in Table 1 to the treatment solution 10 ppm or 15 ppm, the mixture was allowed to stand 5 times with strong stirring up and down 5 times and 5 times with weak stirring. In order to compare the sedimentation properties of the treatment liquids, the sedimentation interface volume, floc diameter, and sedimentation speed after 30 minutes were measured. The results are shown in Table 3.
（比較例１）
比較試験として実施例１と同様な試験を比較試料１あるいは表２の市販品水溶性高分子試料０．２質量％溶解液を対処理液１５ｐｐｍ添加後、上下転倒強攪拌５回、弱撹拌５回行い静置し、対処理液の沈降性を比較するため３０分後の沈降界面容積、フロック径、沈降速度を測定した。その結果を表３に示す。
(Comparative Example 1)
As a comparative test, the same test as in Example 1 was conducted. After adding 15 ppm of a commercially available water-soluble polymer sample 0.2% by weight of Comparative Sample 1 or Table 2, the solution was stirred up and down 5 times with weak stirring 5 times. In order to compare the sedimentation properties of the treatment liquid, the sedimentation interface volume, floc diameter, and sedimentation rate after 30 minutes were measured. The results are shown in Table 3.
（表３）
(Table 3)
本発明における水溶性重合体分散液試料１を添加時、比較例よりも大きいフロックを形成し、沈降速度が速く凝集性能が高いことが確認できた。同様に試料２、３についても実施例１と同様な試験を実施した結果、同様な効果が得られた。 When the water-soluble polymer dispersion sample 1 in the present invention was added, a floc larger than the comparative example was formed, and it was confirmed that the sedimentation rate was high and the aggregation performance was high. Similarly, as for the samples 2 and 3, the same test as in Example 1 was performed. As a result, the same effect was obtained.
（実施例２）
畜産排水（ｐＨ６．９、ＳＳ分５２００ｐｐｍ、ＴＳ１２９６０ｐｐｍ、濁度＞１０００ＮＴＵ）を対象に凝集性能を評価した。排水を水道水にて二倍に希釈したものを２００ｍＬ採取し、メスシリンダーにセット、表１の本発明における水溶性重合体分散液試料１の０．２質量％溶解液を対排水５ｐｐｍあるいは１０ｐｐｍ添加、上下転倒強攪拌５回、弱撹拌５回行い静置し、対排水の沈降性を比較するため３０分後の沈降界面容積、フロック径、沈降速度を測定した。その結果を表４に示す。
(Example 2)
Aggregation performance was evaluated for livestock wastewater (pH 6.9, SS content 5200 ppm, TS12960 ppm, turbidity> 1000 NTU). 200 mL of waste water diluted twice with tap water is collected, set in a graduated cylinder, and 0.2% by mass solution of the water-soluble polymer dispersion sample 1 of the present invention in Table 1 is 5 ppm or 10 ppm against waste water. The mixture was allowed to stand by addition, upside down strong stirring 5 times, and weak stirring 5 times, and the sedimentation interface volume, floc diameter, and sedimentation speed after 30 minutes were measured in order to compare the sedimentation property of the drainage. The results are shown in Table 4.
（比較例２）
比較試験として実施例２と同様な試験を比較試料１、２あるいは表２の市販品水溶性高分子試料０．２質量％溶解液を対排水１０ｐｐｍ添加後、上下転倒強攪拌５回、弱撹拌５回行い静置し、対排水の沈降性を比較するため３０分後の沈降界面容積、フロック径、沈降速度を測定した。その結果を表４に示す。
(Comparative Example 2)
As a comparative test, the same test as in Example 2 was performed. After adding 10 ppm of a 0.2% by mass solution of a commercially available water-soluble polymer sample in Comparative Samples 1 and 2 or Table 2, up and down strong stirring 5 times, weak stirring The sample was allowed to stand for 5 times, and the sedimentation interface volume, the floc diameter, and the sedimentation rate after 30 minutes were measured in order to compare the sedimentation properties of the wastewater. The results are shown in Table 4.
（表４）
(Table 4)
本発明における水溶性重合体分散液試料１を１０ｐｐｍ添加時、比較例よりも大きいフロックを形成し、沈降速度が速く凝集性能が高いことが確認できた。
５ｐｐｍの低添加時でも比較例と同等以上の凝集効果が得られた。
When 10 ppm of the water-soluble polymer dispersion sample 1 in the present invention was added, a floc larger than the comparative example was formed, and it was confirmed that the sedimentation rate was high and the aggregation performance was high.
Even at a low addition of 5 ppm, the same or better agglomeration effect as that of the comparative example was obtained.
（実施例３）
食品加工排水（ｐＨ８．４、ＳＳ分２５５０ｐｐｍ、ＣＯＤ３３８０ｐｐｍ、濁度＞１０００ＮＴＵ、アンモニア態窒素０．２６ｐｐｍ、ノルマルヘキサン抽出物質６５６０ｐｐｍ、色相 黄色）を対象に加圧浮上試験を実施した。排水１Ｌをビーカーに採取しジャーテスターにセット、硫酸２３００ｐｐｍ（対排水）を添加、１５０ｒｐｍ６０秒撹拌、ｐＨを調整した後、表１の本発明における水溶性重合体分散液試料１の０．２質量％溶解液を対排水１０ｐｐｍ添加、１５０ｒｐｍ３０秒、８０ｒｐｍ３０秒、４０ｒｐｍ３０秒攪拌して凝集させ、加圧浮上処理試験に供した。加圧水には水道水を用い、空気溶解圧力４ｋｇ／ｃｍ２、水量比２５％の加圧水を加え、５分間静置浮上分離後の処理水をＪＩＳＫ０１０２法に則り分析した。結果を表５に示す。
(Example 3)
A pressure levitation test was carried out on food processing wastewater (pH 8.4, SS content 2550 ppm, COD 3380 ppm, turbidity> 1000 NTU, ammonia nitrogen 0.26 ppm, normal hexane extract 6560 ppm, hue yellow). Collect 1 L of waste water in a beaker, set it in a jar tester, add 2300 ppm sulfuric acid (to waste water), stir at 150 rpm for 60 seconds, adjust pH, then 0.2 mass of water-soluble polymer dispersion sample 1 in Table 1 of the present invention. % Solution was added to 10 ppm of wastewater, stirred at 150 rpm for 30 seconds, 80 rpm for 30 seconds, and 40 rpm for 30 seconds to be agglomerated and subjected to a pressure levitation treatment test. Tap water was used as the pressurized water, pressurized water having an air dissolution pressure of 4 kg / cm 2 and a water volume ratio of 25% was added, and the treated water after standing and separation by standing for 5 minutes was analyzed according to JISK0102. The results are shown in Table 5.
（比較例３）
実施例３と同じ排水を対象に同様な試験を表１の比較試料１、２あるいは表２の市販品水溶性高分子試料を用いて行なった。これらの結果を表５に示す。
(Comparative Example 3)
A similar test was conducted using the same waste water as in Example 3 using Comparative Samples 1 and 2 in Table 1 or commercially available water-soluble polymer samples in Table 2. These results are shown in Table 5.
（表５）
(Table 5)
本発明における水溶性重合体分散液試料１を添加した実施例３では比較例よりも、濁度、ＣＯＤ、アンモニア態窒素も低減し水質が改善することが確認できた。ノルマルヘキサン抽出物量も排水処理用の高分子凝集剤として汎用されている試料Ａよりも低下を示した。同様に試料２、３についても実施例３と同様な試験を実施した結果、同様な効果が得られた。 In Example 3 to which the water-soluble polymer dispersion sample 1 in the present invention was added, it was confirmed that the water quality was improved by reducing turbidity, COD and ammonia nitrogen as compared with the comparative example. The amount of normal hexane extract was also lower than that of Sample A, which is widely used as a polymer flocculant for wastewater treatment. Similarly, as for the samples 2 and 3, the same test as in Example 3 was performed. As a result, the same effect was obtained.
（実施例４）
下水沈降余剰汚泥（ｐＨ６．７、ＳＳ分６８２０ｐｐｍ、濁度＞１０００ＮＴＵ、アンモニア態窒素２３．１ｐｐｍ、ノルマルヘキサン抽出物質１５４ｐｐｍ、色相 茶色）を対象にジャーテスターを用いて沈澱処理試験を実施した。排水２００ｍＬをビーカーに採取し、表１の試料１の０．２質量％溶解液を対排水２０ｐｐｍ添加、１５０ｒｐｍ３０秒、８０ｒｐｍ３０秒、４０ｒｐｍ３０秒攪拌、フロック径を測定、５分間静置後のＳＶ（汚泥沈澱率）、上澄み液の濁度、アンモニア態窒素、ノルマルヘキサン抽出物量をＪＩＳＫ０１０２法に則り測定した。その結果を表６に示す。
Example 4
A sedimentation test was conducted using a jar tester on sewage sedimentation excess sludge (pH 6.7, SS content 6820 ppm, turbidity> 1000 NTU, ammonia nitrogen 23.1 ppm, normal hexane extract 154 ppm, hue brown). 200 mL of waste water was collected in a beaker, 0.2 ppm by mass of Sample 1 in Table 1 was added to 20 ppm of waste water, stirred at 150 rpm for 30 seconds, 80 rpm for 30 seconds, 40 rpm for 30 seconds, the floc diameter was measured, and the SV after standing for 5 minutes ( (Sludge precipitation rate), turbidity of supernatant, ammonia nitrogen, and normal hexane extract amount were measured according to JISK0102. The results are shown in Table 6.
（比較例４）
実施例４と同様な試験を比較試料１、２あるいは表２の市販品水溶性高分子試料を用いて実施した。結果を表６に示す。
(Comparative Example 4)
A test similar to Example 4 was carried out using Comparative Samples 1 and 2 or commercially available water-soluble polymer samples shown in Table 2. The results are shown in Table 6.
（表６）
(Table 6)
本発明における水溶性重合体分散液を添加した実施例４では比較例よりも、フロック径が大きく、ＳＶが低い値を示し凝集処理効果が優れている。又、濁度、アンモニア態窒素、ノルマルヘキサン抽出物量も比較例と同等以上の低減効果が確認できた。同様に試料２、３についても実施例４と同様な試験を実施した結果、同様な効果が得られた。
In Example 4 to which the water-soluble polymer dispersion in the present invention was added, the floc diameter was larger and the SV was lower than in the comparative example, and the aggregating effect was excellent. Moreover, the turbidity, ammonia nitrogen, and the amount of normal hexane extract were confirmed to have the same or better reduction effect than the comparative example. Similarly, as for the samples 2 and 3, the same test as in Example 4 was performed. As a result, the same effect was obtained.
Claims (3)
一般式（１）
Ｒ１は水素又はメチル基、Ｒ２、Ｒ３は炭素数１〜３のアルキル基、アルコキシ基、Ｒ４は炭素数７〜２０のアルキル基あるいはアリール基である。Ａは酸素またはＮＨ、Ｂは炭素数２〜４のアルキレン基またはアルコキシレン基、Ｘ１は陰イオンをそれぞれ表わす。 In a salt aqueous solution containing a chloride ion and a polyvalent anion, a monomer or monomer mixture aqueous solution containing the monomer represented by the following general formula (1) as an essential component is constituted in the salt aqueous solution. It is a water-soluble polymer dispersion obtained by co-existing a polymer dispersant containing diallyldimethylammonium chloride as a unit and stirring and dispersing, and an inorganic salt relative to the total amount of the water-soluble polymer dispersion A wastewater treatment method comprising: adding a water-soluble polymer dispersion having a total amount of less than 15% by mass to a wastewater, mixing and aggregating the mixture, followed by solid-liquid separation.
General formula (1)
R 1 is hydrogen or a methyl group, R 2 and R 3 are alkyl groups having 1 to 3 carbon atoms, alkoxy groups, and R 4 is an alkyl group or aryl group having 7 to 20 carbon atoms. A represents oxygen or NH, B represents an alkylene group or alkoxylene group having 2 to 4 carbon atoms, and X 1 represents an anion.
The wastewater treatment method according to claim 1 or 2, wherein the solid-liquid separation is a coagulation sedimentation treatment or a coagulation flotation treatment.
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