JPH1053617A - Polymer coagulant - Google Patents
Polymer coagulantInfo
- Publication number
- JPH1053617A JPH1053617A JP9118794A JP11879497A JPH1053617A JP H1053617 A JPH1053617 A JP H1053617A JP 9118794 A JP9118794 A JP 9118794A JP 11879497 A JP11879497 A JP 11879497A JP H1053617 A JPH1053617 A JP H1053617A
- Authority
- JP
- Japan
- Prior art keywords
- monomer
- polymer
- polymer flocculant
- water
- vinyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/52—Amides or imides
- C08F20/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F20/60—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing nitrogen in addition to the carbonamido nitrogen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D21/00—Separation of suspended solid particles from liquids by sedimentation
- B01D21/01—Separation of suspended solid particles from liquids by sedimentation using flocculating agents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D21/00—Separation of suspended solid particles from liquids by sedimentation
- B01D21/26—Separation of sediment aided by centrifugal force or centripetal force
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5272—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using specific organic precipitants
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/12—Treatment of sludge; Devices therefor by de-watering, drying or thickening
- C02F11/14—Treatment of sludge; Devices therefor by de-watering, drying or thickening with addition of chemical agents
- C02F11/147—Treatment of sludge; Devices therefor by de-watering, drying or thickening with addition of chemical agents using organic substances
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C249/02—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of compounds containing imino groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C251/02—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups
- C07C251/04—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C251/06—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of a saturated carbon skeleton
- C07C251/08—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of a saturated carbon skeleton being acyclic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/10—Esters
- C08F20/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は下水、し尿などの微
生物処理で生じる有機性汚泥の脱水に用いる新規な高分
子凝集剤に関する。さらに詳しくは、遠心脱水、ベルト
プレス脱水において優れた脱水率を発揮する高分子凝集
剤に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel polymer flocculant used for dehydrating organic sludge generated by treating microorganisms such as sewage and night soil. More specifically, the present invention relates to a polymer flocculant exhibiting an excellent dewatering rate in centrifugal dewatering and belt press dewatering.
【０００２】[0002]
【従来の技術】従来、下水、し尿などの微生物処理で生
じる有機性汚泥の脱水に対しては、ポリメタアクリロイ
ルオキシエチルトリメチルアンモニウムクロライド、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
ンモニウムクロライドコポリマー、ポリビニルアミジン
等のカチオン性高分子凝集剤が広く使用されてきた。ま
た、最近ではアクリルアミド−アクリル酸−アクリロイ
ルオキシエチルトリメチルアンモニウムクロライドコポ
リマー等の両性高分子凝集剤が提案されている（特開昭
６３−２６０９２８号公報など）。2. Description of the Related Art Conventionally, for the dehydration of organic sludge generated by the treatment of microorganisms such as sewage and night soil, cations such as polymethacryloyloxyethyltrimethylammonium chloride, acrylamide-acryloyloxyethyltrimethylammonium chloride copolymer, and polyvinylamidine are used. Polymeric flocculants have been widely used. Recently, an amphoteric polymer flocculant such as acrylamide-acrylic acid-acryloyloxyethyltrimethylammonium chloride copolymer has been proposed (JP-A-63-260928).
【０００３】[0003]
【発明が解決しようとする課題】しかし、従来の技術で
は遠心脱水、ベルトプレス脱水等において充分な脱水率
が得られなかった。とくに最近は、汚泥中の有機物含量
の増加、腐敗の進行が顕著に見られ、これとともに脱水
率は悪化傾向にある。脱水率の低下は得られるケーキの
含水率を上げ、したがってケーキ焼却時の燃料費を増加
させる問題があった。However, in the prior art, a sufficient dehydration rate could not be obtained in centrifugal dehydration, belt press dehydration and the like. In recent years, in particular, an increase in organic matter content in sludge and progress of decay have been remarkably observed, and at the same time, a dehydration rate has been deteriorating. A decrease in the dehydration rate raises the water content of the obtained cake, and thus has a problem of increasing the fuel cost when the cake is incinerated.
【０００４】[0004]
【課題を解決するための手段】本発明者等はこうした下
水、し尿などの微生物処理で生じる有機性汚泥の遠心脱
水、ベルトプレス脱水において優れた脱水率を発揮する
高分子凝集剤を見い出すべく鋭意検討した結果、本発明
に到った。すなわち本発明は、１級アミン塩基を有する
ラジカル重合性（メタ）アクリル系モノマー（ｍ）を必
須単位とするビニル系水溶性重合体（Ａ）からなり、重
合体（Ａ）のｐＨ４、７、１０におけるコロイド当量値
をそれぞれａ、ｂ、ｃとしたとき、ｂ／ａ＝０．１〜
０．５およびｃ／ａ＝０〜０．１であることを特徴とす
る高分子凝集剤、並びに、該高分子凝集剤を汚泥に添加
してフロックを形成して固液分離を行うことを特徴とす
る汚泥の脱水方法である。Means for Solving the Problems The present inventors diligently seek to find a polymer flocculant exhibiting an excellent dewatering rate in centrifugal dewatering and belt press dewatering of organic sludge generated by the treatment of microorganisms such as sewage and night soil. As a result of the study, the present invention has been reached. That is, the present invention comprises a vinyl-based water-soluble polymer (A) having a radically polymerizable (meth) acrylic monomer (m) having a primary amine base as an essential unit, and the polymer (A) has a pH of 4, 7, When the colloid equivalent values at 10 are a, b, and c, respectively, b / a = 0.1 to
0.5 and c / a = 0 to 0.1; and a method of adding the polymer flocculant to sludge to form a floc to perform solid-liquid separation. This is a characteristic sludge dewatering method.
【０００５】[0005]
【発明の実施の形態】本発明における１級アミン塩基を
有するラジカル重合性（メタ）アクリル系モノマー
（ｍ）としては、たとえば下記一般式（１）で示される
モノマーがあげられる。 ［式中、ＲはＨまたはＣＨ3 ；ＸはＯまたはＮＨ；Ｑは
ＣＨ2ＣＨ2、ＣＨ2ＣＨ2ＣＨ2またはＣＨ2ＣＨ（ＯＨ）
ＣＨ2 ；ＺはＣｌ、Ｂｒ、Ｉ、ＮＯ3、1/2ＳＯ4 、ＣＨ
3ＳＯ3、Ｈ2ＰＯ4またはＣＨ3ＣＯＯである］ 具体例としては、アミノエチル（メタ）アクリレート塩
酸塩、アミノエチル（メタ）アクリレート硫酸塩、アミ
ノプロピル（メタ）アクリルアミド塩酸塩等があげら
れ、これらの１種以上が使用できる。BEST MODE FOR CARRYING OUT THE INVENTION The radically polymerizable (meth) acrylic monomer (m) having a primary amine base in the present invention includes, for example, a monomer represented by the following general formula (1). Wherein R is H or CH 3 ; X is O or NH; Q is CH 2 CH 2 , CH 2 CH 2 CH 2 or CH 2 CH (OH)
CH 2 ; Z is Cl, Br, I, NO 3 , 1 / 2SO 4 , CH
3 SO 3 , H 2 PO 4 or CH 3 COO] Specific examples include aminoethyl (meth) acrylate hydrochloride, aminoethyl (meth) acrylate sulfate, aminopropyl (meth) acrylamide hydrochloride and the like. And one or more of these can be used.
【０００６】これらの中で工業的製造の容易さから、式
（１）でＸがＯ、ＱがＣＨ2ＣＨ2である化合物、すなわ
ち、アミノエチル（メタ）アクリレート塩酸塩、アミノ
エチル（メタ）アクリレート硫酸塩等が好ましく、アミ
ノエチル（メタ）アクリレート塩酸塩が更に好ましく、
アミノエチルメタアクリレート塩酸塩が最も好ましい。Among them, compounds having the formula (1) wherein X is O and Q is CH 2 CH 2 , ie, aminoethyl (meth) acrylate hydrochloride, aminoethyl (meth) Acrylate sulfate and the like are preferred, and aminoethyl (meth) acrylate hydrochloride is more preferred,
Aminoethyl methacrylate hydrochloride is most preferred.
【０００７】本発明において、ビニル系水溶性重合体
（Ａ）は、モノマー（ｍ）の単独重合体であっても、他
の公知のビニルモノマーとの共重合体であってもよい。
その場合に使用される他のビニルモノマーの例としては
アクリルアミド、アクリロニトリル、ビニルピロリドン
などの非イオン性ビニルモノマー、アクリル酸（塩）、
アクリルアミドメチルプロパンスルホン酸（塩）、イタ
コン酸（塩）などのアニオン性ビニルモノマー、（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
クロライド、（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クロライド、（メタ）アクリロ
イルアミノエチルトリメチルアンモニウムクロライド、
ジメチルジアリルアンモニウムメチルサルフェート、ビ
ニルピリジンなどのカチオン性ビニルモノマーなどがあ
げられ、これらの１種以上が使用できる。In the present invention, the vinyl-based water-soluble polymer (A) may be a homopolymer of the monomer (m) or a copolymer with another known vinyl monomer.
Examples of other vinyl monomers used in such a case include acrylamide, acrylonitrile, nonionic vinyl monomers such as vinylpyrrolidone, acrylic acid (salt),
Anionic vinyl monomers such as acrylamidomethylpropanesulfonic acid (salt) and itaconic acid (salt), (meth) acryloyloxyethyltrimethylammonium chloride, (meth) acryloyloxyethyldimethylbenzylammonium chloride, (meth) acryloylaminoethyltrimethylammonium Chloride,
Examples include cationic vinyl monomers such as dimethyldiallylammonium methyl sulfate and vinylpyridine, and one or more of these can be used.
【０００８】これらの中で工業的観点から、アクリルア
ミドと（メタ）アクリロイルオキシエチルトリメチルア
ンモニウムクロライドなどのカチオン性ビニルモノマー
が好ましく、より好ましくは、アクリルアミドおよび
（メタ）アクリロイルオキシエチルトリメチルアンモニ
ウムクロライドである。Among them, from the industrial viewpoint, acrylamide and cationic vinyl monomers such as (meth) acryloyloxyethyltrimethylammonium chloride are preferable, and acrylamide and (meth) acryloyloxyethyltrimethylammonium chloride are more preferable.
【０００９】モノマー（ｍ）と他のビニルモノマーを共
重合する場合、モノマー（ｍ）の共重合割合は目的に応
じて自由に選びうるが、ポリマーの性能、特に高分子凝
集剤として用いた時の脱水率の観点から、カチオン性ビ
ニルモノマーの合計量に対するモノマー（ｍ）の含量
は、好ましくは５０モル％以上、より好ましくは７０モ
ル％以上、さらに好ましくは８０モル％以上である。ま
た、非イオン性、アニオン性も含めた全ビニルモノマー
の合計量に対するモノマー（ｍ）の含量も、同じ理由
で、好ましくは５０モル％以上、より好ましくは７０モ
ル％以上、さらに好ましくは８０モル％以上である。When the monomer (m) is copolymerized with another vinyl monomer, the copolymerization ratio of the monomer (m) can be freely selected according to the purpose. From the viewpoint of the dehydration rate, the content of the monomer (m) with respect to the total amount of the cationic vinyl monomers is preferably 50 mol% or more, more preferably 70 mol% or more, and further preferably 80 mol% or more. For the same reason, the content of the monomer (m) with respect to the total amount of all vinyl monomers including nonionic and anionic is preferably 50 mol% or more, more preferably 70 mol% or more, and further preferably 80 mol% or more. % Or more.
【００１０】本発明において、ビニル系水溶性重合体
（Ａ）がモノマー（ｍ）を必須単位とすることから、
（Ａ）のｐＨ４、７、１０におけるコロイド当量値をそ
れぞれａ、ｂ、ｃとしたとき、ｂとａ、ｃとａの比は、
通常ｂ／ａ＝０．１〜０．５およびｃ／ａ＝０〜０．１
である。In the present invention, since the vinyl water-soluble polymer (A) contains the monomer (m) as an essential unit,
When the colloid equivalent values at pH 4, 7, and 10 in (A) are a, b, and c, respectively, the ratio of b to a and c to a is:
Usually b / a = 0.1-0.5 and c / a = 0-0.1
It is.
【００１１】また、重合体（Ａ）のｐＨ４におけるコロ
イド等量値は、高分子凝集剤として用いた時の脱水性能
から、５．０以上が好ましく、より好ましくは５．５〜
１３．０、さらに好ましくは６．０〜１２．０である。
モノマー（ｍ）を必須単位とすることにより、ｐＨ４に
おけるコロイド等量値が５．０以上の重合体も容易に得
ることができる。The colloid equivalent value of the polymer (A) at pH 4 is preferably 5.0 or more, more preferably 5.5 to 5, from the viewpoint of dehydration performance when used as a polymer flocculant.
13.0, more preferably 6.0 to 12.0.
By using the monomer (m) as an essential unit, a polymer having a colloid equivalent value at pH 4 of 5.0 or more can be easily obtained.
【００１２】本発明において、コロイド当量値は以下に
示すコロイド滴定法により求めることができる。 （１）試料５０ｐｐｍ水溶液の調整 試料０．２ｇ（乾品換算したもの）を精秤し、三角フラ
スコにとり、イオン交換水１００ｍｌで溶解する。さら
にこの溶液を１０ｍｌとりイオン交換水３９０ｍｌを加
え均一溶液として測定試料とする。 （２）コロイド当量値の測定 測定試料１００ｍｌをコニカルビーカーにとり撹拌しな
がら０．５％水酸化ナトリウム水溶液を徐々に加え測定
ｐＨに調整する。つぎにトルイジンブルー指示薬を２〜
３滴加え、Ｎ／４００ポリビニル硫酸カリウム（Ｎ／４
００ＰＶＳＫ）試薬で滴定する。滴定速度は２ｍｌ／分
とし、測定試料が青から赤紫色に変色し、３０秒以上保
持する時点を終点とする。 （３）空試験 イオン交換水１００ｍｌで（２）と同様の操作をおこな
う。 （４）計算法 コロイド当量値（ｍｅｑ／ｇ）＝１／２×（試料の滴定
量−空試験の滴定量）×（Ｎ／４００ＰＶＳＫの力価）In the present invention, the colloid equivalent value can be determined by the following colloid titration method. (1) Preparation of 50 ppm aqueous solution of sample 0.2 g of sample (converted to dry product) is precisely weighed, placed in an Erlenmeyer flask, and dissolved with 100 ml of ion-exchanged water. Further, 10 ml of this solution is taken, and 390 ml of ion-exchanged water is added to obtain a uniform sample as a measurement sample. (2) Measurement of Colloid Equivalent Value A measurement sample (100 ml) is placed in a conical beaker, and a 0.5% aqueous sodium hydroxide solution is gradually added thereto with stirring to adjust the measurement pH. Then add toluidine blue indicator
Add 3 drops and add N / 400 polyvinyl potassium sulfate (N / 4
00PVSK) Titrate with reagent. The titration speed is 2 ml / min, and the time when the measurement sample changes color from blue to magenta and is held for 30 seconds or more is the end point. (3) Blank test The same operation as (2) is performed with 100 ml of ion-exchanged water. (4) Calculation method Colloid equivalent value (meq / g) = 1/2 × (titer of sample−titer of blank test) × (titer of N / 400 PVSK)
【００１３】本発明の高分子凝集剤の分子量は、固有粘
度（１ＮーＮａＮＯ3 中、３０℃で測定、単位：ｄｌ／
ｇ、以下同様）で通常２以上のものである。２未満では
分子量が小さすぎて一般にはポリマーとして特性が出に
くい。一般に凝集性能は分子量が高いものほど良好であ
るので、固有粘度は４以上が好ましく、より好ましくは
５以上、特に好ましくは８以上である。The molecular weight of the polymer flocculant of the present invention is determined by the intrinsic viscosity (measured in 1N NaNO 3 at 30 ° C., unit: dl /
g, the same applies hereinafter) and usually 2 or more. If it is less than 2, the molecular weight is too small, and it is generally difficult to obtain characteristics as a polymer. In general, the higher the molecular weight, the better the cohesion performance. Therefore, the intrinsic viscosity is preferably 4 or more, more preferably 5 or more, and particularly preferably 8 or more.
【００１４】本発明の高分子凝集剤製品形状は、粉末
状、フィルム状、水溶液状、ｗ／ｏエマルション状、懸
濁液状等公知の任意形状でよい。The polymer coagulant product of the present invention may be in any known form such as powder, film, aqueous solution, w / o emulsion, suspension and the like.
【００１５】本発明の高分子凝集剤は、公知の方法、た
とえば水溶液重合、水と有機溶剤を用いた乳化重合、懸
濁重合などにより製造できる。水溶液重合の場合、モノ
マー濃度が通常１０〜８０質量％となるようにモノマー
水溶液として系内を不活性ガスで置換した後、公知の重
合触媒（過硫酸塩たとえば過硫酸アンモニウムおよび過
硫酸カリウム；有機過酸化物たとえばベンゾイルパーオ
キシド；アゾ系化合物たとえば２，２′−アゾビス−
（アミジノプロパン）ハイドロクロライドおよびアゾビ
スシアノバレリン酸；およびレドックス触媒（過酸化物
（Ｈ2Ｏ2、過硫酸カリウムなど）と還元剤（重亜硫酸ソ
ーダ、硫酸第一鉄など）との組合せ）を加えて２０〜１
００℃程度で数時間重合を行う。また、光増感剤を加え
た後、紫外線等を照射してもよい。粉末化を行うには、
このようにして得られた重合物を適宜細断して熱風乾
燥、溶剤沈澱・乾燥し、粉砕すればよい。The polymer flocculant of the present invention can be produced by a known method, for example, aqueous polymerization, emulsion polymerization using water and an organic solvent, suspension polymerization and the like. In the case of aqueous solution polymerization, after the inside of the system is replaced with an inert gas so as to have a monomer concentration of usually 10 to 80% by mass, a known polymerization catalyst (for example, a persulfate such as ammonium persulfate and potassium persulfate; Oxides such as benzoyl peroxide; azo compounds such as 2,2'-azobis-
(Amidinopropane) hydrochloride and azobiscyanovaleric acid; and a redox catalyst (a combination of a peroxide (H 2 O 2 , potassium persulfate, etc.) and a reducing agent (sodium bisulfite, ferrous sulfate, etc.)) In addition, 20-1
Polymerization is performed at about 00 ° C. for several hours. After the addition of the photosensitizer, irradiation with ultraviolet light or the like may be performed. To perform powdering,
The polymer thus obtained may be appropriately chopped, dried with hot air, precipitated and dried with a solvent, and pulverized.
【００１６】本発明の高分子凝集剤は、水中の懸濁粒子
に高い吸着性を示して効果的な凝集性（フロック形成
性）を示すので、公知の水系懸濁液の固液分離促進にと
くに限定なく使用できるが、実用的価値の面から、下
水、し尿などの微生物処理で生じる有機性汚泥（いわゆ
る生汚泥、余剰汚泥、混合生汚泥、消化汚泥、凝沈・浮
上汚泥およびこれらの混合物）の脱水により有用であ
る。これらのなかでも、同じ理由で、有機分含有量（Ｖ
ＳＳ／ＳＳ）が７０％以上の汚泥により有用である。The polymer flocculant of the present invention exhibits high adsorptivity to suspended particles in water and exhibits effective flocculation (floc-forming properties). Although it can be used without particular limitation, organic sludge (so-called raw sludge, surplus sludge, mixed raw sludge, digested sludge, coagulated / floated sludge, and mixtures thereof) generated from the treatment of microorganisms such as sewage and human waste are practically useful. ) Is more useful. Among these, for the same reason, the organic content (V
(SS / SS) is more useful with sludge of 70% or more.
【００１７】本発明の高分子凝集剤は、単独でも使用で
きるが、目的に応じて、たとえば他のカチオン性ラジカ
ル重合性ビニルモノマー（ｎ）を必須単位とする、カチ
オン性または両性のビニル系水溶性重合体（Ｂ）からな
る高分子凝集剤と併用してもよい。モノマー（ｎ）とし
ては、（メタ）アクリロイルオキシエチルトリメチルア
ンモニウムクロライド、（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クロライド、（メ
タ）アクリロイルアミノエチルトリメチルアンモニウム
クロライド、ジメチルジアリルアンモニウムメチルサル
フェート、ビニルピリジンなどが挙げられる。（Ｂ）の
具体例としては、ポリ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クロライド、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クロラ
イドコポリマー、ポリビニルアミジン等のカチオン性ビ
ニル系水溶性重合体、アクリルアミド−アクリル酸−ア
クリロイルオキシエチルトリメチルアンモニウムクロラ
イドコポリマー等の両性ビニル系水溶性重合体があげら
れるが、中でも、両性ビニル系水溶性重合体および、ｐ
Ｈ４におけるコロイド等量値が４．０以上であるカチオ
ン性ビニル系水溶性重合体が好ましく、ポリメタアクリ
ロイルオキシエチルトリメチルアンモニウムクロライド
が特に好ましい。The polymer flocculant of the present invention can be used alone, but depending on the purpose, for example, a cationic or amphoteric vinyl-based aqueous solution containing another cationic radically polymerizable vinyl monomer (n) as an essential unit. You may use together with the polymer flocculant which consists of an ionic polymer (B). Examples of the monomer (n) include (meth) acryloyloxyethyltrimethylammonium chloride, (meth) acryloyloxyethyldimethylbenzylammonium chloride, (meth) acryloylaminoethyltrimethylammonium chloride, dimethyldiallylammonium methyl sulfate, and vinylpyridine. . Specific examples of (B) include cationic vinyl water-soluble polymers such as polymethacryloyloxyethyltrimethylammonium chloride, acrylamide-acryloyloxyethyltrimethylammonium chloride copolymer, polyvinylamidine, and acrylamide-acrylic acid-acryloyloxyethyltrimethyl. Examples include amphoteric vinyl-based water-soluble polymers such as ammonium chloride copolymers.
A cationic vinyl water-soluble polymer having a colloid equivalent value of 4.0 or more in H4 is preferable, and polymethacryloyloxyethyltrimethylammonium chloride is particularly preferable.
【００１８】また、本発明の高分子凝集剤を添加され形
成されたフロック状の汚泥の脱水方法としては、公知の
遠心脱水、ベルトプレス脱水、フィルタープレス脱水、
キャピラリー脱水等がとれるが、効果の点から遠心脱
水、ベルトプレス脱水がより好ましい。The method for dewatering the floc-like sludge formed by adding the polymer flocculant of the present invention includes known centrifugal dewatering, belt press dewatering, filter press dewatering, and the like.
Capillary dehydration and the like can be obtained, but centrifugal dehydration and belt press dehydration are more preferable from the viewpoint of effects.
【００１９】本発明の高分子凝集剤は、０．１質量％濃
度の水溶液とした時の水溶液ｐＨが、好ましくは４．０
以下、特に好ましくは３．０以下である。水溶液ｐＨが
４．０を上回ると十分な脱水性能が得られないことがあ
る。The polymer flocculant of the present invention preferably has an aqueous solution pH of 0.1% by mass when the aqueous solution has a pH of 4.0.
The value is particularly preferably 3.0 or less. If the pH of the aqueous solution exceeds 4.0, sufficient dehydration performance may not be obtained.
【００２０】０．１質量％水溶液とした時の水溶液ｐＨ
を４．０以下とするために、本発明の高分子凝集剤は酸
性物質を併用してもよい。酸性物質としては公知の無機
もしくは有機の酸性物質酸が使用でき、具体例としては
硫酸、塩酸、リン酸などの鉱酸；酸性リン酸ソーダ、酸
性ぼう硝、塩化アンモニウム、硫酸アンモニウム、重硫
酸アンモニウム、スルファミン酸などの無機固体酸性物
質；シュウ酸などの有機酸があげられるが、効果および
経済性から無機固体酸性物質が好ましく、中でもスルフ
ァミン酸、酸性ぼう硝が特に好ましい。Aqueous solution pH as 0.1 mass% aqueous solution
To 4.0 or less, the polymer flocculant of the present invention may use an acidic substance in combination. As the acidic substance, known inorganic or organic acidic substances can be used, and specific examples thereof include mineral acids such as sulfuric acid, hydrochloric acid, and phosphoric acid; acidic sodium phosphate, acidic sodium nitrate, ammonium chloride, ammonium sulfate, ammonium bisulfate, and sulfamine. An inorganic solid acidic substance such as an acid; an organic acid such as oxalic acid can be mentioned, but an inorganic solid acidic substance is preferred from the viewpoint of effect and economy, and sulfamic acid and acidic oxalate are particularly preferred.
【００２１】本発明の高分子凝集剤は、通常０．１質量
％程度の濃度の水溶液にして使用されるが、その際、使
用目的に応じて、前記の酸性物質のほか、増粘剤、加重
剤、分散剤、防腐剤および無機塩などを併用することが
できる。The polymer flocculant of the present invention is usually used in the form of an aqueous solution having a concentration of about 0.1% by mass. At this time, in addition to the above-mentioned acidic substance, a thickener, Weighting agents, dispersants, preservatives, inorganic salts and the like can be used in combination.
【００２２】[0022]
【実施例】以下、実施例および比較例により本発明をさ
らに説明するが、本発明はこれに限定されるものではな
い。 実施例１〜４、比較例１〜３ 表１に示す組成のモノマーを重合させて得た高分子凝集
剤をそれぞれイオン交換水に溶解してｐＨ４、７、１０
におけるコロイド当量値を測定した。The present invention will be further described below with reference to examples and comparative examples, but the present invention is not limited to these examples. Examples 1 to 4, Comparative Examples 1 to 3 Polymer flocculants obtained by polymerizing monomers having the compositions shown in Table 1 were respectively dissolved in ion-exchanged water to obtain pH 4, 7, 10
Was measured.
【００２３】[0023]
【表１】 AEMC ： アミノエチルメタアクリレート塩酸塩 AEAS ： アミノエチルアクリレート硫酸塩 METAC： 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クロライド METAS： 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メチルサルフェ ート AAm ： アクリルアミド[Table 1] AEMC: Aminoethyl methacrylate hydrochloride AEAS: Aminoethyl acrylate sulfate METAC: Methacryloyloxyethyltrimethylammonium chloride METAS: Methacryloyloxyethyltrimethylammonium methyl sulfate AAm: Acrylamide
【００２４】実施例５〜８、比較例４〜６ 表２に示す組成のモノマーを重合させて得た高分子凝集
剤をそれぞれイオン交換水にとかして０．１％水溶液と
し、Ｋ市下水処理場余剰汚泥（ｐＨ６．９、ＴＳ（総固
形分）２．３％、有機分８１％）にポリマーとして０．
８５％／ＴＳずつ添加して小型ベルトプレス脱水機を用
いて脱水試験を行い、得られた脱水ケーキの含水率を測
定した。試験結果を表２に示すが、本発明の高分子凝集
剤（実施例５〜８）は、比較例４〜６に比べて、高い脱
水性（低いケーキ含水率）を示した。Examples 5 to 8 and Comparative Examples 4 and 6 Polymer flocculants obtained by polymerizing monomers having the compositions shown in Table 2 were each dissolved in ion-exchanged water to form a 0.1% aqueous solution. In the excess sludge (pH 6.9, TS (total solid content) 2.3%, organic content 81%) as polymer, 0.1
A dehydration test was performed using a small-size belt press dehydrator by adding 85% / TS each, and the water content of the obtained dehydrated cake was measured. The test results are shown in Table 2, and the polymer flocculants of the present invention (Examples 5 to 8) showed higher dehydration properties (lower cake moisture content) than Comparative Examples 4 and 6.
【００２５】[0025]
【表２】 （注） 記号は表１と同じ。[Table 2] (Note) Symbols are the same as Table 1.
【００２６】[0026]
【発明の効果】本発明の高分子凝集剤は下水、し尿など
の微生物処理で生じる有機性汚泥に対し優れた脱水効果
を有する。とくに従来脱水が困難であった有機分含有量
（ＶＳＳ／ＳＳ）の高い汚泥に対し際だった効果を発揮
することから、高分子凝集剤として極めて有用である。The polymer flocculant of the present invention has an excellent dewatering effect on organic sludge generated by treating microorganisms such as sewage and human waste. In particular, it has a remarkable effect on sludge having a high organic content (VSS / SS), which has conventionally been difficult to dehydrate, and is therefore extremely useful as a polymer flocculant.
Claims (8)
（メタ）アクリル系モノマー（ｍ）を必須単位とするビ
ニル系水溶性重合体（Ａ）からなり、重合体（Ａ）のｐ
Ｈ４、７、１０におけるコロイド当量値をそれぞれａ、
ｂ、ｃとしたとき、ｂ／ａ＝０．１〜０．５およびｃ／
ａ＝０〜０．１であることを特徴とする高分子凝集剤。1. A vinyl-based water-soluble polymer (A) having a radically polymerizable (meth) acrylic monomer (m) having a primary amine base as an essential unit, wherein p of the polymer (A) is
The colloid equivalent values at H4, 7, 10 are a,
When b and c are set, b / a = 0.1 to 0.5 and c /
A polymer flocculant, wherein a = 0 to 0.1.
で示されるモノマーである請求項１記載の高分子凝集
剤。 ［式中、ＲはＨまたはＣＨ3 ；ＸはＯまたはＮＨ；Ｑは
ＣＨ2ＣＨ2、ＣＨ2ＣＨ2ＣＨ2またはＣＨ2ＣＨ（ＯＨ）
ＣＨ2 ；ＺはＣｌ、Ｂｒ、Ｉ、ＮＯ3、1/2ＳＯ4 、ＣＨ
3ＳＯ3、Ｈ2ＰＯ4またはＣＨ3ＣＯＯである］2. The monomer (m) is represented by the following general formula (1)
The polymer flocculant according to claim 1, which is a monomer represented by the formula: Wherein R is H or CH 3 ; X is O or NH; Q is CH 2 CH 2 , CH 2 CH 2 CH 2 or CH 2 CH (OH)
CH 2 ; Z is Cl, Br, I, NO 3 , 1 / 2SO 4 , CH
3 SO 3 , H 2 PO 4 or CH 3 COO]
2ＣＨ2である請求項２記載の高分子凝集剤。3. X is O and Q is CH in the general formula (1).
3. The polymer flocculant according to claim 2, which is 2 CH2.
のカチオン性ビニルモノマーを構成単位とする共重合体
であって（Ａ）中のカチオン性ビニルモノマーの合計量
に対する（ｍ）の含量が５０モル％以上である請求項１
〜３のいずれか記載の高分子凝集剤。4. A copolymer comprising acrylamide and / or another cationic vinyl monomer as a constitutional unit, wherein the content of (m) is at least 50 mol% based on the total amount of the cationic vinyl monomer in (A). Claim 1
4. The polymer flocculant according to any one of items 1 to 3.
におけるコロイド等量値が５．０以上である請求項１〜
４のいずれか記載の高分子凝集剤。5. The water-soluble vinyl polymer (A) having a pH of 4
The colloid equivalent value in the above is 5.0 or more.
5. The polymer flocculant according to any one of 4.
固有粘度（ｄｌ／ｇ）が４以上である請求項１〜５のい
ずれか記載の高分子凝集剤。6. The polymer flocculant according to claim 1, which has an intrinsic viscosity (dl / g) of 4 or more measured at 30 ° C. in 1N NaNO 3 .
集剤を汚泥に添加してフロックを形成して固液分離を行
うことを特徴とする汚泥の脱水方法。7. A method for dewatering sludge, comprising adding the polymer flocculant according to any one of claims 1 to 6 to sludge to form flocs and performing solid-liquid separation.
ニルモノマー（ｎ）を必須単位とするビニル系水溶性重
合体（Ｂ）からなる高分子凝集剤を併用する請求項７記
載の汚泥の脱水方法。8. The method for dewatering sludge according to claim 7, further comprising a polymer coagulant comprising a vinyl-based water-soluble polymer (B) containing another cationic radically polymerizable vinyl monomer (n) as an essential unit. .
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9118794A JP2976283B2 (en) | 1996-04-22 | 1997-04-21 | Polymer flocculant |
| AU47225/97A AU4722597A (en) | 1996-04-22 | 1997-10-22 | Water-soluble polymer, process for the production of the same, and use thereof as polymeric coagulant |
| PCT/JP1997/003824 WO1999020667A1 (en) | 1996-04-22 | 1997-10-22 | Water-soluble polymer, process for the production of the same, and use thereof as polymeric coagulant |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8-126443 | 1996-04-22 | ||
| JP12644396 | 1996-04-22 | ||
| JP9118794A JP2976283B2 (en) | 1996-04-22 | 1997-04-21 | Polymer flocculant |
| PCT/JP1997/003824 WO1999020667A1 (en) | 1996-04-22 | 1997-10-22 | Water-soluble polymer, process for the production of the same, and use thereof as polymeric coagulant |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14163999A Division JP3766564B2 (en) | 1999-05-21 | 1999-05-21 | Sludge dewatering method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH1053617A true JPH1053617A (en) | 1998-02-24 |
| JP2976283B2 JP2976283B2 (en) | 1999-11-10 |
Family
ID=27308296
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9118794A Expired - Fee Related JP2976283B2 (en) | 1996-04-22 | 1997-04-21 | Polymer flocculant |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP2976283B2 (en) |
| AU (1) | AU4722597A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014069140A (en) * | 2012-09-28 | 2014-04-21 | Sanyo Chem Ind Ltd | Polymer flocculant for sludge concentrating process |
| JP2015051428A (en) * | 2013-08-06 | 2015-03-19 | 三洋化成工業株式会社 | Polymer flocculant |
| JP2015057274A (en) * | 2013-08-09 | 2015-03-26 | 三洋化成工業株式会社 | Polymer flocculant |
| JP2015057276A (en) * | 2013-08-09 | 2015-03-26 | 三洋化成工業株式会社 | Polymer flocculant |
| JP2015150534A (en) * | 2014-02-18 | 2015-08-24 | ハイモ株式会社 | Flocculation treatment agent, and dewatering method of sludge using the same |
| JP2016129884A (en) * | 2015-01-09 | 2016-07-21 | 三洋化成工業株式会社 | Polymer flocculant |
| KR20210018191A (en) * | 2018-06-06 | 2021-02-17 | 쿠리타 고교 가부시키가이샤 | Sludge dehydration agent and sludge dehydration method |
-
1997
- 1997-04-21 JP JP9118794A patent/JP2976283B2/en not_active Expired - Fee Related
- 1997-10-22 AU AU47225/97A patent/AU4722597A/en not_active Abandoned
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014069140A (en) * | 2012-09-28 | 2014-04-21 | Sanyo Chem Ind Ltd | Polymer flocculant for sludge concentrating process |
| JP2015051428A (en) * | 2013-08-06 | 2015-03-19 | 三洋化成工業株式会社 | Polymer flocculant |
| JP2015057274A (en) * | 2013-08-09 | 2015-03-26 | 三洋化成工業株式会社 | Polymer flocculant |
| JP2015057276A (en) * | 2013-08-09 | 2015-03-26 | 三洋化成工業株式会社 | Polymer flocculant |
| JP2015150534A (en) * | 2014-02-18 | 2015-08-24 | ハイモ株式会社 | Flocculation treatment agent, and dewatering method of sludge using the same |
| JP2016129884A (en) * | 2015-01-09 | 2016-07-21 | 三洋化成工業株式会社 | Polymer flocculant |
| KR20210018191A (en) * | 2018-06-06 | 2021-02-17 | 쿠리타 고교 가부시키가이샤 | Sludge dehydration agent and sludge dehydration method |
Also Published As
| Publication number | Publication date |
|---|---|
| AU4722597A (en) | 1999-05-10 |
| JP2976283B2 (en) | 1999-11-10 |
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