JPH07256300A - Dehydration of sludge using both inorganic flocculant and amphoteric polymeric flocculant - Google Patents

Dehydration of sludge using both inorganic flocculant and amphoteric polymeric flocculant

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Publication number
JPH07256300A
JPH07256300A JP6078203A JP7820394A JPH07256300A JP H07256300 A JPH07256300 A JP H07256300A JP 6078203 A JP6078203 A JP 6078203A JP 7820394 A JP7820394 A JP 7820394A JP H07256300 A JPH07256300 A JP H07256300A
Authority
JP
Japan
Prior art keywords
sludge
unit
flocculant
formula
added
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
Application number
JP6078203A
Other languages
Japanese (ja)
Other versions
JP2991611B2 (en
Inventor
Hiromasa Fukuda
寛允 福田
Toshihiro Arai
俊博 荒井
Shinobu Kawaguchi
忍 川口
Yasuhiro Oi
康裕 大井
Shigeru Sato
茂 佐藤
Hisao Ooshimizu
久夫 大清水
Shoji Matsushima
尚司 松島
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
NIPPON GESUIDO JIGYODAN
Kurita Water Industries Ltd
Sanyo Chemical Industries Ltd
Original Assignee
NIPPON GESUIDO JIGYODAN
Kurita Water Industries Ltd
Sanyo Chemical Industries Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by NIPPON GESUIDO JIGYODAN, Kurita Water Industries Ltd, Sanyo Chemical Industries Ltd filed Critical NIPPON GESUIDO JIGYODAN
Priority to JP6078203A priority Critical patent/JP2991611B2/en
Publication of JPH07256300A publication Critical patent/JPH07256300A/en
Application granted granted Critical
Publication of JP2991611B2 publication Critical patent/JP2991611B2/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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  • Treatment Of Sludge (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

PURPOSE:To increase the treatment amt. of sludge and to obtain a cake with low water content by a method wherein an inorg. flocculant is added to sludge and the pH of the sludge after addition is adjusted to a specific value and an amphoteric polymeric flocculant is added to the sludge to flocculate the same and the sludge is mechanically dehydrated. CONSTITUTION:An inorg. flocculant is added to sludge and the pH of the sludge after addition is adjusted to below 5 and a specific amphoteric polymeric flocculant is added to the sludge to flocculate the same and this sludge is subjected to dehydration treatment. The effective component of this amphoteric polymeric flocculant is composed of an amphoteric copolymer containing a cationic constitutional unit A represented by formula I, a cationic constitutional unit B represented by formula II, an anionic constitutional unit C represented by a specific formula and a nonionic constitutional unit D represented by a specific formula as essential constitutional units and having a compositional mol ratio satisfying the relation of 0.5<A-unit/[A-unit + B-unit]<1.0 and C-unit/[A-unit + B-unit]<0.8 and having intrinsic viscosity of 2.0dl/g (30 deg.C, 1N- NaNO3) or more.

Description

【発明の詳細な説明】Detailed Description of the Invention

【0001】[0001]

【産業上の利用分野】本発明は汚泥の脱水方法の改良に
関するものである。さらに詳しくいえば、本発明は、従
来法に比べて大幅に処理量を増やすことができるととも
に、低含水率のケーキを得ることのできる無機凝集剤と
両性高分子凝集剤を併用する汚泥の脱水方法に関するも
のである。
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an improved sludge dewatering method. More specifically, the present invention is capable of significantly increasing the treatment amount as compared with the conventional method, and dehydrating sludge using an inorganic flocculant and an amphoteric polymer flocculant capable of obtaining a cake having a low water content. It is about the method.

【0002】[0002]

【従来の技術】これまで、汚泥の脱水方法には、カチオ
ン性高分子凝集剤が単独で使用されているが、近年、汚
泥発生量の増加及び汚泥性状の悪化により、従来のカチ
オン性高分子凝集剤では、汚泥の処理量に限界があるこ
とや、脱水ケーキ含水率、SS回収率、ケーキのろ布か
らの剥離性などの点で処理状態は必ずしも満足できるも
のではなく、改善が求められている。これら従来のカチ
オン性高分子凝集剤の欠点を改善する方法として、無機
凝集剤とポリマーとを併用する方法が種々提案されてい
るが、必ずしも十分に満足しうるものではない。例え
ば、(1)ポリ硫酸鉄を汚泥と反応させ、pH調整剤でpH
を4.5〜6にしたのち、高分子凝集剤(カチオン性ポ
リマー又はアニオン性ポリマー)で脱水する方法(特開
昭64−3160号公報)や、(2)無機凝集剤添加後
のpHが5〜8の汚泥に対し、両性ポリマーを使用して凝
集脱水する方法(特開昭63−158200号公報)な
どが開示されている。しかしながら、前記(1)の方法
においては、カチオン性ポリマーを使用する場合には、
ポリ硫酸鉄がカチオン性を有するため、ケーキ含水率は
低下しても凝集性が大幅に劣り、フロックが弱く、処理
量が上がらないし、また、アニオン性ポリマーを使用す
る場合には、ポリ硫酸鉄とポリマーとが反応し、大きな
フロックは得られるものの、フロックが弱く、処理量の
改善にはほとんど寄与しないなどの問題がある。一方、
前記(2)の方法においては、無機凝集剤添加後pHが5
〜8では、汚泥の荷電の中和が不十分であるため、ケー
キの含水率は従来のカチオン性高分子凝集剤による単独
の処理と大差がなく、効果の向上は僅かである。このよ
うに、無機凝集剤を汚泥に添加して高分子凝集剤で処理
を行う提案はされているものの、まだ十分に満足しうる
技術には至っていないのが実状である。
2. Description of the Related Art Up to now, a cationic polymer flocculant has been used alone in a sludge dewatering method, but in recent years, due to an increase in sludge generation and deterioration of sludge properties, conventional cationic polymer flocculants have been used. With the coagulant, the treatment state is not always satisfactory in terms of the sludge treatment amount, the dehydrated cake water content, the SS recovery rate, and the removability of the cake from the filter cloth. ing. Various methods of using an inorganic flocculant and a polymer in combination have been proposed as methods for improving the drawbacks of these conventional cationic polymer flocculants, but they are not always sufficiently satisfactory. For example, (1) reacting polyiron sulfate with sludge and adjusting the pH with a pH adjuster.
After adjusting to 4.5 to 6 and dehydrating with a polymer flocculant (cationic polymer or anionic polymer) (JP-A-64-3160), or (2) pH after addition of inorganic flocculant A method of coagulating and dehydrating sludges of 5 to 8 using an amphoteric polymer (JP-A-63-158200) is disclosed. However, in the above method (1), when a cationic polymer is used,
Since poly iron sulfate has a cationic property, even if the water content of the cake is lowered, the cohesiveness is significantly inferior, the floc is weak, the treatment amount does not increase, and when an anionic polymer is used, poly iron sulfate is used. Although a large amount of flocs can be obtained by reacting with the polymer, there is a problem that the flocs are weak and hardly contribute to the improvement of the throughput. on the other hand,
In the method (2), the pH is 5 after the addition of the inorganic coagulant.
In Nos. 8 to 8, the neutralization of the electric charge of the sludge was insufficient, so that the water content of the cake was not so different from the conventional treatment with the cationic polymer flocculant, and the effect was slightly improved. As described above, although it has been proposed to add an inorganic coagulant to sludge and to treat with a polymer coagulant, the fact is that the technology is not yet sufficiently satisfactory.

【0003】[0003]

【発明が解決しようとする課題】本発明は、このような
従来技術が有する欠点を克服し、従来法に比べて大幅に
処理量を増やすことができるとともに、低含水率のケー
キを得ることのできる無機凝集剤と両性高分子凝集剤を
併用する汚泥の脱水方法を提供することを目的としてな
されたものである。
DISCLOSURE OF THE INVENTION The present invention overcomes the drawbacks of the prior art as described above, can significantly increase the throughput as compared with the conventional method, and can obtain a cake having a low water content. The purpose of the present invention is to provide a sludge dewatering method using a combination of an inorganic flocculant and an amphoteric polymer flocculant.

【0004】[0004]

【課題を解決するための手段】本発明者らは、前記目的
を達成するために鋭意研究を重ねた結果、まず、汚泥に
無機凝集剤を添加し、該添加後のpHを5未満にしたの
ち、特定の両性高分子凝集剤を添加して凝集させ、機械
的に汚泥を脱水することにより、その目的を達成しうる
ことを見い出した。本発明は、かかる知見に基づいて完
成したものである。
Means for Solving the Problems As a result of intensive studies to achieve the above-mentioned object, the present inventors firstly added an inorganic coagulant to sludge and adjusted the pH after the addition to less than 5. After that, it was found that the purpose can be achieved by adding a specific amphoteric polymer coagulant to coagulate and mechanically dehydrate the sludge. The present invention has been completed based on such findings.

【0005】すなわち、本発明は、汚泥に無機凝集剤を
添加し、次いで両性高分子凝集剤を添加して凝集させ、
機械的に汚泥を脱水させるに当たり、無機凝集剤添加後
の汚泥のpHを5未満にしたのち、該両性高分子凝集剤と
して、(A)一般式
That is, according to the present invention, an inorganic coagulant is added to sludge, and then an amphoteric polymer coagulant is added to cause coagulation.
In mechanically dehydrating sludge, the pH of the sludge after addition of the inorganic coagulant is adjusted to less than 5, and then the amphoteric polymer coagulant (A) having the general formula

【化5】 [式中のR1は炭化水素基またはヒドロキシアルキル
基、R2及びR3はそれぞれ炭素数1〜4のアルキル基で
あり、それらはたがいに同一でも異なっていてもよく、
(X1)-は陰イオンである]で表されるカチオン性構成単
位と、(B)一般式
[Chemical 5] [Wherein R 1 is a hydrocarbon group or a hydroxyalkyl group, R 2 and R 3 are each an alkyl group having 1 to 4 carbon atoms, and they may be the same or different from each other,
(X 1) - is a cationic structural unit represented by an anion], (B) the general formula

【化6】 [式中のR4は炭化水素基またはヒドロキシアルキル
基、R5及びR6はそれぞれ炭素数1〜4のアルキル基で
あり、それらはたがいに同一でも異なっていてもよく、
(X2)-は陰イオンである]で表されるカチオン性構成単
位と、(C)一般式
[Chemical 6] [In the formula, R 4 is a hydrocarbon group or a hydroxyalkyl group, and R 5 and R 6 are each an alkyl group having 1 to 4 carbon atoms, and they may be the same or different,
(X 2) - is a cationic structural unit represented by an anion], (C) the general formula

【化7】 [式中のR7は水素原子又はメチル基、Mは水素原子、
アンモニウムイオン又はアルカリ金属イオンである]で
表されるアニオン性構成単位と、(D)一般式
[Chemical 7] [Wherein R 7 is a hydrogen atom or a methyl group, M is a hydrogen atom,
Is an ammonium ion or an alkali metal ion], and (D) a general formula

【化8】 [式中のR8及びR9はそれぞれ水素原子又はメチル基で
あり、それらはたがいに同一でも異なっていてもよく、
10は水素原子又は炭素数1〜3のアルキル基である]
で表されるノニオン性構成単位とを必須構成単位とする
共重合体であって、組成モル比が 0.5≦(B)単位/[(A)単位+(B)単位]<1.
0 及び (C)単位/[(A)単位+(B)単位]>0.8 の関係を満たし、かつ1N−硝酸ナトリウム又は1N−
塩化ナトリウム水溶液中、温度30℃での固有粘度が
2.0デシリットル/g以上である両性高分子共重合体
を有効成分とするものを添加することを特徴とする無機
凝集剤と両性高分子凝集剤を併用する汚泥の脱水方法を
提供するものである。
[Chemical 8] [In the formula, R 8 and R 9 are each a hydrogen atom or a methyl group, and they may be the same or different,
R 10 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms]
A copolymer having a nonionic constitutional unit represented by the following as an essential constitutional unit and having a composition molar ratio of 0.5 ≦ (B) units / [(A) units + (B) units] <1.
0 and (C) unit / [(A) unit + (B) unit]> 0.8, and 1N-sodium nitrate or 1N-
Inorganic coagulant and amphoteric polymer coagulation characterized by adding an amphoteric polymer copolymer having an intrinsic viscosity of 2.0 deciliter / g or more at a temperature of 30 ° C. in an aqueous sodium chloride solution as an active ingredient It is intended to provide a method for dehydrating sludge, which uses an agent together.

【0006】以下、本発明を詳細に説明する。本発明方
法において用いられる無機凝集剤の種類については特に
制限はなく、従来汚泥の脱水方法に慣用されているもの
の中から任意のものを選択して用いることができる。こ
の無機凝集剤の具体例としては、ポリ塩化アルミニウ
ム、硫酸アルミニウム、塩化第二鉄、硫酸第一鉄、ポリ
硫酸鉄、その他一般の水処理で用いられている多価金属
塩などが挙げられる。これらの無機凝集剤は1種用いて
もよいし、2種以上を組み合わせて用いてもよい。必要
とする前記無機凝集剤の量は、汚泥の種類や汚泥性状に
よって異なるが、本発明においては、該無機凝集剤を添
加した後の汚泥のpHが5未満になるまで添加することが
必要である。このpHが5以上では無機凝集剤により汚泥
の中和が不充分で、脱水ケーキの含水率が高く、本発明
の意図する効果は得られない。該無機凝集剤のみでpH5
未満にしてもよいが、最初に多めの無機凝集剤を加え、
その後アルカリ剤でpH5未満になるようにpHを調整して
もよい。また、無機凝集剤と有機酸や鉱酸を併用してpH
を5未満にしてもよい。
The present invention will be described in detail below. The type of the inorganic flocculant used in the method of the present invention is not particularly limited, and any one can be selected and used from those conventionally used in the sludge dewatering method. Specific examples of the inorganic coagulant include polyaluminum chloride, aluminum sulfate, ferric chloride, ferrous sulfate, polyiron sulfate, and other polyvalent metal salts used in general water treatment. These inorganic coagulants may be used alone or in combination of two or more. The required amount of the inorganic coagulant varies depending on the type of sludge and sludge properties, but in the present invention, it is necessary to add the inorganic coagulant until the pH of the sludge after adding the inorganic coagulant becomes less than 5. is there. When the pH is 5 or more, the sludge is not sufficiently neutralized by the inorganic coagulant, and the dehydrated cake has a high water content, so that the effect intended by the present invention cannot be obtained. PH of only 5 with the inorganic coagulant
May be less than, but first add a large amount of inorganic coagulant,
Thereafter, the pH may be adjusted with an alkaline agent so that the pH becomes less than 5. It is also possible to use an inorganic flocculant in combination with an organic acid or mineral acid to adjust the pH.
May be less than 5.

【0007】本発明方法においては、このように無機凝
集剤を添加し、かつ添加後のpHを5未満にしたのち、両
性高分子凝集剤が添加される。この両性高分子凝集剤
は、(A)一般式
In the method of the present invention, the amphoteric polymer flocculant is added after the inorganic flocculant has been added and the pH after the addition is adjusted to less than 5. This amphoteric polymer flocculant has the general formula (A)

【化9】 [式中のR1、R2、R3及び(X1)-は前記と同じ意味を
もつ]で表されるカチオン性構成単位と、(B)一般式
[Chemical 9] [And R 1, R 2, R 3 in the formula (X 1) - have the same meanings as defined above] and the cationic structural unit represented by, (B) the general formula

【化10】 [式中のR4、R5、R6及び(X2)-は前記と同じ意味を
もつ]で表されるカチオン性構成単位と、(C)一般式
[Chemical 10] [R 4, R 5 in the formula, R 6 and (X 2) - have the same meanings as defined above] and the cationic structural unit represented by, (C) the general formula

【化11】 [式中のR7及びMは前記と同じ意味をもつ]で表され
るアニオン性構成単位と、(D)一般式
[Chemical 11] An anionic constitutional unit represented by [R 7 and M in the formula have the same meanings as described above], and (D) a general formula

【化12】 [式中のR8、R9及びR10は前記と同じ意味をもつ]で
表されるノニオン性構成単位とを必須構成単位とする両
性高分子共重合体を有効成分とするものである。
[Chemical 12] An amphoteric polymer copolymer having a nonionic constitutional unit represented by the formula [R 8 , R 9 and R 10 in the formula have the same meaning as described above] as an essential constitutional unit is used as an active ingredient.

【0008】前記一般式[1]及び[2]において、R
1及びR4は、例えばメチル基、エチル基、ベンジル基な
どの炭化水素基又はヒドロキシメチル基などのヒドロキ
シアルキル基である。また、R2、R3、R5及びR6はメ
チル基やエチル基などの炭素数1〜4のアルキル基であ
り、該R2とR3、R5とR6は、それぞれにおいてたがい
に同一であってもよいし、異なっていてもよい。さら
に、(X1)-及び(X2)-はCl-、Br-、I-、HS
4 -、1/2SO4 2-、NO3 -、CH3COO-、HCO
-、CH3SO4 -、C25SO4 -などの陰イオンであ
る。一方、一般式[3]において、R7は水素原子又は
メチル基、Mは水素原子又はナトリウムやカリウムなど
のアルカリ金属イオンである。また、一般式[4]にお
いて、R8及びR9は、それぞれ水素原子又はメチル基で
あり、それらはたがいに同一であってもよいし、異なっ
ていてもよく、R10は水素原子又はメチル基、エチル
基、プロピル基などの炭素数1〜3のアルキル基であ
る。前記(A)単位である一般式[1]で表されるカチ
オン性構成単位を形成するカチオン性モノマーはジアル
キルアミノエチルメタクリレートの四級アンモニウム塩
であり、このようなものの具体例としては、ジメチルア
ミノエチルメタクリレートの塩化メチル四級化物やジメ
チルアミノエチルメタクリレートの塩化ベンジル四級化
物などを挙げることができ、これらは1種用いてもよい
し、2種以上を組み合わせて用いてもよい。
In the above general formulas [1] and [2], R
1 and R 4 are, for example, a hydrocarbon group such as a methyl group, an ethyl group, a benzyl group or a hydroxyalkyl group such as a hydroxymethyl group. R 2 , R 3 , R 5 and R 6 are alkyl groups having 1 to 4 carbon atoms such as methyl group and ethyl group, and R 2 and R 3 , R 5 and R 6 are, respectively, It may be the same or different. Further, (X 1) - and (X 2) - is Cl -, Br -, I - , HS
O 4 -, 1 / 2SO 4 2-, NO 3 -, CH 3 COO -, HCO
Anions such as O , CH 3 SO 4 and C 2 H 5 SO 4 . On the other hand, in the general formula [3], R 7 is a hydrogen atom or a methyl group, and M is a hydrogen atom or an alkali metal ion such as sodium or potassium. In the general formula [4], R 8 and R 9 are each a hydrogen atom or a methyl group, and they may be the same or different, and R 10 is a hydrogen atom or a methyl group. And an alkyl group having 1 to 3 carbon atoms such as a group, an ethyl group and a propyl group. The cationic monomer forming the cationic constitutional unit represented by the general formula [1], which is the unit (A), is a quaternary ammonium salt of dialkylaminoethyl methacrylate, and specific examples of such a compound include dimethylamino. Examples thereof include a methyl chloride quaternary product of ethyl methacrylate and a benzyl chloride quaternary product of dimethylaminoethyl methacrylate. These may be used alone or in combination of two or more.

【0009】前記(B)単位である一般式[2]で表さ
れるカチオン性構成単位を形成するカチオン性モノマー
はジアルキルアミノエチルアクリレートの四級アンモニ
ウム塩であり、このようなものの具体例としては、ジメ
チルアミノエチルアクリレートの塩化メチル四級化物や
ジメチルアミノエチルアクリレートの塩化ベンジル四級
化物などを挙げることができ、これらは1種用いてもよ
いし、2種以上を組み合わせて用いてもよい。また、前
記(C)単位である一般式[3]で表されるアニオン性
構成単位を形成するアニオン性モノマーとしては、例え
ばアクリル酸、メタクリル酸及びそれらのアンモニウム
塩、アルカリ金属塩を挙げることができ、それらは1種
用いてもよいし、2種以上を組み合わせて用いてもよ
い。一方、前記(D)単位である一般式[4]で表され
るノニオン性構成単位を形成するノニオン性モノマーと
しては、例えばアクリルアミド、メタクリルアミド、ジ
メチルアクリルアミド、イソプロピルアクリルアミドな
どを挙げることができ、これらは1種用いてもよいし、
2種以上を組み合わせて用いてもよい。
The cationic monomer forming the cationic constitutional unit represented by the general formula [2] which is the unit (B) is a quaternary ammonium salt of dialkylaminoethyl acrylate, and specific examples of such a compound include Examples thereof include methyl chloride quaternary product of dimethylaminoethyl acrylate and benzyl chloride quaternary product of dimethylaminoethyl acrylate. These may be used alone or in combination of two or more. Examples of the anionic monomer forming the anionic constitutional unit represented by the general formula [3], which is the unit (C), include acrylic acid, methacrylic acid, their ammonium salts, and alkali metal salts. They may be used alone or in combination of two or more. On the other hand, examples of the nonionic monomer forming the nonionic structural unit represented by the general formula [4], which is the unit (D), include acrylamide, methacrylamide, dimethylacrylamide, and isopropylacrylamide. May be used alone,
You may use it in combination of 2 or more type.

【0010】該両性高分子共重合体は、前記(A)、
(B)、(C)、及び(D)構成単位を必須単位として
含有するものであるが、これらの単位を形成するモノマ
ーと共重合可能な他のモノマーとを所望に応じ共重合さ
せたものであってもよい。この共重合可能な他のモノマ
ーの中で、カチオン性モノマーとしては、例えばジアル
キルアミノエチル(メタ)アクリレート若しくはこれら
の塩酸塩、硫酸塩、硝酸塩、酢酸塩などの三級モノマ
ー、ジアルキルアミノエチル(メタ)アクリルアミド若
しくはこれらの塩酸塩、硫酸塩、硝酸塩、酢酸塩などの
三級モノマー、ジアルキルアミノプロピル(メタ)アク
リルアミド若しくはこれらの塩酸塩、硫酸塩、硝酸塩、
酢酸塩などの三級モノマー及び塩化メチル、臭化メチ
ル、ヨウ化メチル、ジメチル硫酸、塩化ベンジル、臭化
ベンジルなどの四級化剤を反応させた四級アンモニウム
塩モノマー、ビニルピリジン、ビニルピリジンの四級化
誘導体、ビニルイミタゾール、アリルアミンなどを挙げ
ることができる。また、アニオン性モノマーとしては、
例えばビニルスルホン酸、2−アクリルアミド−2−メ
チルプロパンスルホン酸、マレイン酸など、及びそれら
のアルカリ金属塩を挙げることができ、一方、ノニオン
性モノマーとしては、例えばスチレン、アクリロニトリ
ル、酢酸ビニル、アクリル酸アルキル、メタクリル酸ア
ルキルなどを挙げることができる。これらの共重合可能
な他のモノマーは1種用いてもよいし、2種以上を組み
合わせて用いてもよい。
The amphoteric polymer copolymer is the above-mentioned (A),
(B), (C), and (D) contain the constitutional unit as an essential unit, but the monomer forming these units and other copolymerizable monomers are copolymerized as desired. May be Among the other copolymerizable monomers, examples of the cationic monomer include dialkylaminoethyl (meth) acrylate or tertiary salts thereof such as hydrochloride, sulfate, nitrate and acetate, and dialkylaminoethyl (meth) acrylate. ) Acrylamide or a tertiary salt of these hydrochlorides, sulfates, nitrates, acetates, etc., dialkylaminopropyl (meth) acrylamide or a hydrochloride thereof, sulfates, nitrates,
Of quaternary ammonium salt monomers, vinyl pyridine and vinyl pyridine, which have been reacted with tertiary monomers such as acetate and quaternizing agents such as methyl chloride, methyl bromide, methyl iodide, dimethylsulfate, benzyl chloride and benzyl bromide. Examples thereof include quaternized derivatives, vinylimidazole, allylamine and the like. Further, as the anionic monomer,
Examples thereof include vinyl sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, maleic acid and the like, and alkali metal salts thereof, while examples of the nonionic monomer include styrene, acrylonitrile, vinyl acetate and acrylic acid. Examples thereof include alkyl and alkyl methacrylate. These other copolymerizable monomers may be used alone or in combination of two or more.

【0011】該両性高分子共重合体における各構成単位
の含有量は(A)単位が5〜20モル%、(B)単位が
10〜40モル%、(C)単位が15〜40モル%及び
(D)単位が10〜70モル%の範囲にあるのが望まし
い。さらに、本発明においては、該構成単位の含有割合
は、モル比で 0.5≦(B)単位/[(A)単位+(B)単位]<1.
0 及び (C)単位/[(A)単位+(B)単位]>0.8 の関係を満たすことが必要である。各構成単位の含有割
合が前記関係式を満たさない場合は、本発明の目的が達
せられない。また、該(D)単位も重要な成分で、前記
範囲内にあることが重要で、この範囲を逸脱すると、
(A)及び(B)のカチオン性構成単位と(C)のアニ
オン性構成単位とが有効に作用しにくく、好ましくな
い。該両性高分子共重合体の分子量については、分子量
の指標である固有粘度で示すと、1N−硝酸ナトリウム
又は1N−塩化ナトリウム水溶液中、温度30℃での測
定値が2デシリットル/g以上であることが必要である
が、安定した脱水処理を達成するには5デシリットル/
g以上が好ましい。この両性高分子共重合体の重合方法
については特に制限はなく、一般的な重合方法を採用す
ることができる。例えば、水溶液重合であれば、重合開
始剤として過硫酸カリウム、過硫酸アンモニウム、2,
2'−アゾビス(2−アミジノプロパン)二塩酸塩や、
レドックス系の開始剤などを用いることができる。ま
た、逆相の懸濁重合であれば、重合開始剤として前記と
同様なものを用いることができるし、一方逆相エマルシ
ョン重合であれば、前記重合開始剤以外に、アゾビスイ
ソブチロニトリルや過酸化ベンゾイルなどの水不溶性開
始剤を用いて重合を行ってもよい。
The content of each structural unit in the amphoteric polymer is 5 to 20 mol% for the (A) unit, 10 to 40 mol% for the (B) unit, and 15 to 40 mol% for the (C) unit. And (D) units are preferably in the range of 10 to 70 mol%. Furthermore, in the present invention, the content ratio of the structural unit is 0.5 ≦ (B) unit / [(A) unit + (B) unit] <1.
It is necessary to satisfy the relationship of 0 and (C) unit / [(A) unit + (B) unit]> 0.8. If the content ratio of each structural unit does not satisfy the above relational expression, the object of the present invention cannot be achieved. The unit (D) is also an important component, and it is important that it is within the above range.
The cationic constitutional units of (A) and (B) and the anionic constitutional unit of (C) hardly act effectively, which is not preferable. Regarding the molecular weight of the amphoteric polymer, the measured value at a temperature of 30 ° C. in a 1N-sodium nitrate or 1N-sodium chloride aqueous solution is 2 deciliter / g or more, as indicated by the intrinsic viscosity which is an index of the molecular weight. Is necessary, but 5 deciliter /
It is preferably g or more. The method for polymerizing the amphoteric polymer is not particularly limited, and a general polymerization method can be adopted. For example, in the case of aqueous solution polymerization, potassium persulfate, ammonium persulfate as a polymerization initiator, 2,
2'-azobis (2-amidinopropane) dihydrochloride,
A redox type initiator or the like can be used. Further, in the case of reverse phase suspension polymerization, the same one as described above can be used as a polymerization initiator, while in the case of reverse phase emulsion polymerization, in addition to the polymerization initiator, azobisisobutyronitrile Polymerization may be carried out using a water-insoluble initiator such as or benzoyl peroxide.

【0012】本発明方法において用いられる両性高分子
凝集剤は、前記のようにして得られた両性高分子共重合
体を有効成分とするものであって、その製品形態につい
ては特に制限はなく、粉末、溶液、エマルションなど、
目的に応じて任意に選ぶことができる。この両性高分子
凝集剤が有効に作用する汚泥としては、例えば下水、し
尿、一般産業排水処理で生じる有機性汚泥及び凝集沈殿
汚泥を含む混合汚泥などを挙げることができるが、特に
対象は限定されるものではない。また、該両性高分子凝
集剤の使用に際しては、他のカチオン性ポリマーやアニ
オン性ポリマーと併用したり、混合一液としたり、硫酸
水素ナトリウム、硫酸ナトリウム、スルファミン酸な
ど、脱水処理に悪影響がでないかぎり、公知の添加剤と
混合して使用してもよい。本発明方法においては、この
ようにして凝集された汚泥を機械的に脱水するが、この
際使用する脱水機については特に制限はなく、例えばベ
ルトプレス脱水機、遠心脱水機、スクリュープレス脱水
機、フィルタープレス脱水機などを用いることができ
る。
The amphoteric polymer flocculant used in the method of the present invention comprises the amphoteric polymer copolymer obtained as described above as an active ingredient, and its product form is not particularly limited. Powders, solutions, emulsions, etc.
It can be arbitrarily selected according to the purpose. Examples of the sludge in which the amphoteric polymer flocculant effectively acts include sewage, night soil, mixed sludge including organic sludge generated in general industrial wastewater treatment and coagulation sedimentation sludge, but the target is not particularly limited. Not something. Further, when the amphoteric polymer flocculant is used, it does not adversely affect the dehydration treatment such as sodium bisulfate, sodium sulfate, sulfamic acid, etc. in combination with other cationic polymers or anionic polymers, or as a mixed single liquid. As long as it is mixed with a known additive, it may be used. In the method of the present invention, the sludge thus aggregated is mechanically dehydrated, but the dehydrator used at this time is not particularly limited, and for example, a belt press dehydrator, a centrifugal dehydrator, a screw press dehydrator, A filter press dehydrator or the like can be used.

【0013】[0013]

【作用】特公昭58−15491号公報に記載されてい
るように、カチオン性モノマー単位として、(B)単位
を含むポリマーは、カチオン性モノマー単位として
(A)単位を含むポリマーより凝集性が良く、必要添加
量が下がることが知られている。この理由は、前記公報
に記載されているとおり、モノマーの共重合反応性比よ
り、(B)単位を形成するモノマーは比較的均一ないし
ランダムに重合体に取り込まれやすいのに対し、(A)
単位を形成するモノマーはブロック的に重合体に取り込
まれやすい。したがって、本発明の(A)、(B)、
(C)及び(D)単位を必須構成単位として含有するポ
リマーにすることにより、優れた性能が出る理由は、
(1)凝集性の良い(B)単位を含んでいるため、凝集
性が高く、添加量の低減が図られていること、(2)反
応性の異なる(A)単位と(B)単位とが、今回見い出
した一定の範囲の比において、(C)単位のアニオン性
基が効果的に働くようなポリマーの組成分布になってい
ることが考えられるが、詳細は必ずしも明らかではな
い。
As described in JP-B-58-15491, a polymer containing (B) units as cationic monomer units has better cohesiveness than a polymer containing (A) units as cationic monomer units. It is known that the required addition amount decreases. The reason for this is that, as described in the above-mentioned publication, due to the copolymerization reactivity ratio of the monomers, the monomer forming the (B) unit is relatively uniformly or randomly incorporated into the polymer, whereas
The monomer forming the unit is easily incorporated into the polymer in a block manner. Therefore, (A), (B), and
The reason why excellent performance is obtained by using a polymer containing the units (C) and (D) as essential constituent units is as follows.
(1) Since it contains the (B) unit having good cohesiveness, the cohesiveness is high and the addition amount is reduced, and (2) the (A) unit and the (B) unit having different reactivities. However, it is considered that the composition distribution of the polymer is such that the anionic group of the unit (C) works effectively in the ratio within a certain range found this time, but the details are not always clear.

【0014】[0014]

【実施例】次に、実施例により本発明をさらに詳細に説
明するが、本発明はこれらの例によってなんら限定され
るものではない。 製造例1 第1表及び第2表に、それぞれ本発明に係わるポリマー
及び比較ポリマーを示す。以下に、これらのポリマーの
代表的な製造例を示す。第1表及び第2表に示す組成
で、2.0モル/リットルに調整したモノマー水溶液を
室温にて20分間窒素ガスバブリングを行い、全モノマ
ーに対して0.01〜0.20モル%の過硫酸カリウムを
加え、40〜50℃で6〜10時間重合させた。次い
で、得られたポリマー水溶液ゲルを細断して、多量のア
セトンに投入したのち、ろ過して粉末化した。最後に真
空乾燥を行い、白色の粉末ポリマーを得た。なお、固有
粘度[η]は常法に従い、1N−NaNO3水溶液中、
30℃の条件にて測定した。結果を第1表及び第2表に
示す。第1表及び第2表に示す記号は次を意味する。 DAM(CH3Cl):ジメチルアミノエチルメタクリレ
ートのメチルクロリド四級化物 DAA(CH3Cl):ジメチルアミノエチルアクリレー
トのメチルクロリド四級化物 AA:アクリル酸 AAm:アクリルアミド DAM(Me2SO4):ジメチルアミノエチルメタクリレ
ートのジメチル硫酸四級化物 DAA(BzCl):ジメチルアミノエチルアクリレート
のベンジルクロリド四級化物 DAM(1/2H2SO4):ジメチルアミノエチルメタク
リレートの硫酸塩
The present invention will be described in more detail by way of examples, which should not be construed as limiting the invention thereto. Production Example 1 Tables 1 and 2 show the polymers according to the present invention and comparative polymers, respectively. Below, typical production examples of these polymers are shown. Nitrogen gas bubbling was performed for 20 minutes at room temperature with an aqueous monomer solution adjusted to 2.0 mol / liter in the composition shown in Table 1 and Table 2 to obtain 0.01 to 0.20 mol% of all monomers. Potassium persulfate was added and polymerized at 40-50 ° C for 6-10 hours. Next, the obtained polymer aqueous solution gel was shredded, poured into a large amount of acetone, and then filtered to be powdered. Finally, vacuum drying was performed to obtain a white powder polymer. In addition, the intrinsic viscosity [η] is determined by a conventional method in a 1N-NaNO 3 aqueous solution,
It was measured under the condition of 30 ° C. The results are shown in Tables 1 and 2. The symbols shown in Tables 1 and 2 mean the following. DAM (CH 3 Cl): dimethylaminoethylmethacrylate quaternary methyl chloride DAA (CH 3 Cl): dimethylaminoethyl acrylate quaternary methyl chloride AA: acrylic acid AAm: acrylamide DAM (Me 2 SO 4 ): dimethyl Dimethylsulfate quaternary product of aminoethyl methacrylate DAA (BzCl): Benzyl chloride quaternary product of dimethylaminoethyl acrylate DAM (1 / 2H 2 SO 4 ): Sulfate salt of dimethylaminoethyl methacrylate

【0015】[0015]

【表1】 [Table 1]

【0016】[0016]

【表2】 [Table 2]

【0017】実施例1 下水処理場混合生汚泥(pH6.4、SS1.92%)を用
い、ヌッチェテスト及び圧搾テストを行った。操作は次
のとおりである。300ミリリットルビーカーに汚泥2
00ミリリットルをとり、これに10wt%ポリ塩化アル
ミニウム3500ppmを加え、750rpmで15秒間撹拌
した。その際のpHは4.4であった。次いで0.2wt%に
調整したポリマー水溶液を所定量加え、タービン羽根を
備えた撹拌機で200rpm、30秒間撹拌した。その際の
フロック径を測定したのち、ナイロンろ布を敷いたブフ
ナーロートに、内径5cmのポリ塩化ビニルパイプを置
き、その中へ凝集させた汚泥を注ぎ込み、10秒後のろ
液量を測定するとともに、その際のろ液の清浄性を目視
で評価した。ろ過後の汚泥については、その一定量をベ
ルトプレス用ろ布にはさみ、面圧0.5kg/cm2、1.0k
g/cm2で1分間圧搾を行い、脱水ケーキのろ布からの剥
離性及びケーキ含水率を測定した。剥離性については、
ろ布からケーキをヘラでかき取ったのち、高圧水でろ布
に付着している固形物を洗い出して、その洗浄液をろ過
し、回収した固形物を乾燥して重量を測定することによ
り、次の式で表した。 剥離性(%)=W2/(W1+W2)×100 ただし、W1はろ布に付着していた固形物の乾燥重量
(g)、W2はヘラでかき取ったケーキの乾燥重量
(g)である。結果を第3表に示す。 比較例1 実施例1と同じ汚泥を用い、10wt%ポリ塩化アルミニ
ウムの添加量を1500ppmとし、かつpH5.6にて、実
施例1と同様な方法で操作を行った。結果を第3表に示
す。 比較例2 実施例1と同じ汚泥及び比較ポリマーを用い、実施例1
と同様な方法で操作を行った結果を第3表に示す。
Example 1 A Nutsche test and a squeezing test were conducted using mixed raw sludge (pH 6.4, SS 1.92%) of a sewage treatment plant. The operation is as follows. Sludge 2 in a 300 ml beaker
00 ml was taken, 3500 ppm of 10 wt% polyaluminum chloride was added thereto, and the mixture was stirred at 750 rpm for 15 seconds. The pH at that time was 4.4. Then, a predetermined amount of an aqueous polymer solution adjusted to 0.2 wt% was added, and the mixture was stirred with a stirrer equipped with a turbine blade at 200 rpm for 30 seconds. After measuring the floc diameter at that time, place a polyvinyl chloride pipe with an inner diameter of 5 cm on a Buchner funnel lined with nylon filter cloth, pour the agglomerated sludge into it, and measure the amount of filtrate after 10 seconds. At the same time, the cleanliness of the filtrate at that time was visually evaluated. After filtering, a certain amount of sludge is sandwiched between filter cloths for belt press and the surface pressure is 0.5kg / cm 2 , 1.0k.
Pressing was performed at g / cm 2 for 1 minute, and the peelability of the dehydrated cake from the filter cloth and the water content of the cake were measured. For releasability,
After scraping off the cake from the filter cloth with a spatula, the solid matter adhering to the filter cloth is washed out with high pressure water, the washing liquid is filtered, and the recovered solid matter is dried and weighed. Expressed as a formula. Peelability (%) = W 2 / (W 1 + W 2 ) × 100 where W 1 is the dry weight (g) of the solids attached to the filter cloth, and W 2 is the dry weight of the cake scraped with a spatula ( g). The results are shown in Table 3. Comparative Example 1 The same sludge as in Example 1 was used, and the operation was performed in the same manner as in Example 1 except that the addition amount of 10 wt% polyaluminum chloride was 1500 ppm and the pH was 5.6. The results are shown in Table 3. Comparative Example 2 Using the same sludge and comparative polymer as in Example 1, Example 1
Table 3 shows the results of the operation performed in the same manner as.

【0018】[0018]

【表3】 [Table 3]

【0019】実施例2 下水処理場余剰汚泥(pH6.2、SS0.96%)を用
い、38wt%塩化第二鉄を2000ppm加え、汚泥pHを
4.6としたこと以外は、実施例1と同様な方法で操作
を行った。結果を第4表に示す。 比較例3 実施例2と同じ汚泥を用い、38wt%塩化第二鉄の添加
量を1000ppmとし、かつpH5.3にて、実施例2と同
様な方法で操作を行った。結果を第4表に示す。 比較例4 実施例2と同じ汚泥及び比較ポリマーを用い、実施例2
と同様な方法で操作を行った。結果を第4表に示す。
Example 2 Except that the sludge pH was 4.6 using sewage treatment plant excess sludge (pH 6.2, SS 0.96%) and adding 38 wt% ferric chloride at 2000 ppm. The operation was performed in a similar manner. The results are shown in Table 4. Comparative Example 3 Using the same sludge as in Example 2, the addition amount of 38 wt% ferric chloride was 1000 ppm, and the pH was 5.3, and the same operation as in Example 2 was carried out. The results are shown in Table 4. Comparative Example 4 Using the same sludge and comparative polymer as in Example 2, Example 2
The operation was performed in the same manner as. The results are shown in Table 4.

【0020】[0020]

【表4】 [Table 4]

【0021】[0021]

【発明の効果】本発明の汚泥の脱水方法は、(1)フロ
ック強度が強く、ろ布からの剥離が良い、(2)ケーキ
含水率が低い、(3)汚泥の処理量が多い、(4)汚泥
種や汚泥性状の変化に対して、安定した処理効果が得ら
れる、などの特徴を有している。
The sludge dewatering method of the present invention comprises (1) a high floc strength and good peeling from the filter cloth, (2) a low cake water content, and (3) a large amount of sludge to be treated. 4) It has a feature that a stable treatment effect can be obtained against changes in sludge type and sludge properties.

───────────────────────────────────────────────────── フロントページの続き (72)発明者 荒井 俊博 東京都足立区谷中1−10−4 (72)発明者 川口 忍 京都府京都市東山区一橋野本町11番地の1 三洋化成工業株式会社内 (72)発明者 大井 康裕 東京都新宿区西新宿3丁目4番7号 栗田 工業株式会社内 (72)発明者 佐藤 茂 東京都新宿区西新宿3丁目4番7号 栗田 工業株式会社内 (72)発明者 大清水 久夫 東京都新宿区西新宿3丁目4番7号 栗田 工業株式会社内 (72)発明者 松島 尚司 東京都新宿区西新宿3丁目4番7号 栗田 工業株式会社内 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Toshihiro Arai 1-10-4 Yanaka, Adachi-ku, Tokyo (72) Inventor Shinobu Kawaguchi 11-1 Hitotino-honmachi, Higashiyama-ku, Kyoto, Kyoto Prefecture Sanyo Chemical Industry Co., Ltd. ( 72) Inventor Yasuhiro Oi 3-4-7 Nishishinjuku, Shinjuku-ku, Tokyo Kurita Industry Co., Ltd. (72) Inventor Shigeru Sato 3-4-7 Nishishinjuku, Shinjuku-ku, Tokyo Kurita Industry Co., Ltd. (72) Inventor Hisao Oshimizu 3-4-7 Nishi-Shinjuku, Shinjuku-ku, Tokyo Kurita Industry Co., Ltd. (72) Inventor Shoji Matsushima 3-4-7 Nishi-Shinjuku, Shinjuku-ku, Tokyo Kurita Industry Co., Ltd.

Claims (1)

【特許請求の範囲】[Claims] 【請求項1】汚泥に無機凝集剤を添加し、次いで両性高
分子凝集剤を添加して凝集させ、機械的に汚泥を脱水さ
せるに当たり、無機凝集剤添加後の汚泥のpHを5未満に
したのち、該両性高分子凝集剤として、(A)一般式 【化1】 [式中のR1は炭化水素基またはヒドロキシアルキル
基、R2及びR3はそれぞれ炭素数1〜4のアルキル基で
あり、それらはたがいに同一でも異なっていてもよく、
(X1)-は陰イオンである]で表されるカチオン性構成単
位と、(B)一般式 【化2】 [式中のR4は炭化水素基またはヒドロキシアルキル
基、R5及びR6はそれぞれ炭素数1〜4のアルキル基で
あり、それらはたがいに同一でも異なっていてもよく、
(X2)-は陰イオンである]で表されるカチオン性構成単
位と、(C)一般式 【化3】 [式中のR7は水素原子又はメチル基、Mは水素原子、
アンモニウムイオン又はアルカリ金属イオンである]で
表されるアニオン性構成単位と、(D)一般式 【化4】 [式中のR8及びR9はそれぞれ水素原子又はメチル基で
あり、それらはたがいに同一でも異なっていてもよく、
10は水素原子又は炭素数1〜3のアルキル基である]
で表されるノニオン性構成単位とを必須構成単位とする
共重合体であって、組成モル比が 0.5≦(B)単位/[(A)単位+(B)単位]<1.
0 及び (C)単位/[(A)単位+(B)単位]>0.8 の関係を満たし、かつ1N−硝酸ナトリウム又は1N−
塩化ナトリウム水溶液中、温度30℃での固有粘度が
2.0デシリットル/g以上である両性高分子共重合体
を有効成分とするものを添加することを特徴とする無機
凝集剤と両性高分子凝集剤を併用する汚泥の脱水方法。
1. A sludge having an inorganic flocculant is added to the sludge, and then an amphoteric polymer flocculant is added to the sludge so that the sludge is mechanically dehydrated. Then, as the amphoteric polymer flocculant, (A) the general formula: [Wherein R 1 is a hydrocarbon group or a hydroxyalkyl group, R 2 and R 3 are each an alkyl group having 1 to 4 carbon atoms, and they may be the same or different from each other,
(X 1) - a cationic structural unit represented by an anion] is, (B) the general formula ## STR2 ## [In the formula, R 4 is a hydrocarbon group or a hydroxyalkyl group, and R 5 and R 6 are each an alkyl group having 1 to 4 carbon atoms, and they may be the same or different,
(X 2) - a cationic structural unit represented by an anion] is, (C) the general formula ## STR3 ## [Wherein R 7 is a hydrogen atom or a methyl group, M is a hydrogen atom,
An anionic structural unit represented by ammonium ion or alkali metal ion], and (D) the general formula: [In the formula, R 8 and R 9 are each a hydrogen atom or a methyl group, and they may be the same or different,
R 10 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms]
A copolymer having a nonionic constitutional unit represented by the following as an essential constitutional unit and having a composition molar ratio of 0.5 ≦ (B) units / [(A) units + (B) units] <1.
0 and (C) unit / [(A) unit + (B) unit]> 0.8, and 1N-sodium nitrate or 1N-
Inorganic coagulant and amphoteric polymer coagulation characterized by adding an amphoteric polymer copolymer having an intrinsic viscosity of 2.0 deciliter / g or more at a temperature of 30 ° C. in an aqueous sodium chloride solution as an active ingredient A method for dehydrating sludge that also uses agents.
JP6078203A 1994-03-24 1994-03-24 Sludge dewatering method using inorganic coagulant and amphoteric polymer coagulant together Expired - Lifetime JP2991611B2 (en)

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Cited By (12)

* Cited by examiner, † Cited by third party
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JPH07328644A (en) * 1994-06-01 1995-12-19 Kurita Water Ind Ltd Flocculating method of sewage
WO2000011052A1 (en) * 1998-08-24 2000-03-02 Green Technology Inc. Method and composition of a hydrophilic polymer dispersion containing an inorganic flocculant to be used for the treatment of waste water
JP2001030000A (en) * 1999-07-19 2001-02-06 Kurita Water Ind Ltd Sludge dehydrating method
JP2001286900A (en) * 2000-04-07 2001-10-16 Konan Kagaku Kogyo Kk Method for flocculating organic sludge and polymer flocculating agent
JP2001300599A (en) * 2000-04-24 2001-10-30 Kurita Water Ind Ltd Sludge dehydrating method
JP2002045900A (en) * 2000-08-08 2002-02-12 Toagosei Co Ltd Method for dewatering sludge
WO2002100944A1 (en) 2001-06-11 2002-12-19 Hymo Corporation Amphoteric water-soluble polymer dispersion and use thereof
JP2005131572A (en) * 2003-10-31 2005-05-26 Daiyanitorikkusu Kk Method for dehydrating sludge
US7745529B2 (en) 2006-08-03 2010-06-29 Hymo Corporation Flocculant composition and method for manufacturing the same
JP2012012540A (en) * 2010-07-02 2012-01-19 Daiyanitorikkusu Kk Method for producing powdery cationic water-soluble polymer compound, sludge dehydrating agent, and method for dehydrating sludge
CN102701381A (en) * 2012-06-14 2012-10-03 四川师范大学 Water-soluble organic amphoteric polymeric flocculant and preparation method thereof
CN102701367A (en) * 2012-06-12 2012-10-03 四川师范大学 Water-soluble organic copolymerized amphiprotic polymer flocculating agent and preparation method

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CN102718305A (en) * 2012-06-13 2012-10-10 四川师范大学 Water-soluble organic amphoteric polymeric flocculant and preparation method thereof
CN102774945A (en) * 2012-06-14 2012-11-14 四川师范大学 Organic amphoteric polymeric flocculant and preparation method thereof
US20230020603A1 (en) * 2019-12-06 2023-01-19 Kurita Water Industries Ltd. Sludge dehydrating agent and sludge dehydrating method

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JPH02180700A (en) * 1988-12-29 1990-07-13 Kurita Water Ind Ltd Dehydration of organic sludge
JPH03293100A (en) * 1990-04-11 1991-12-24 Kurita Water Ind Ltd Sludge dehydrating agent
JPH0459100A (en) * 1990-06-20 1992-02-25 Nippon Gesuidou Jigyodan Method for dehydrating organic sludge
JPH04298300A (en) * 1991-03-27 1992-10-22 Kurita Water Ind Ltd Sludge dehydrating agent and method for dehydrating sludge by using this agent
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JPH02180700A (en) * 1988-12-29 1990-07-13 Kurita Water Ind Ltd Dehydration of organic sludge
JPH03293100A (en) * 1990-04-11 1991-12-24 Kurita Water Ind Ltd Sludge dehydrating agent
JPH0459100A (en) * 1990-06-20 1992-02-25 Nippon Gesuidou Jigyodan Method for dehydrating organic sludge
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JPH04322800A (en) * 1991-04-19 1992-11-12 Kurita Water Ind Ltd Method for dehydrating sludge

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07328644A (en) * 1994-06-01 1995-12-19 Kurita Water Ind Ltd Flocculating method of sewage
WO2000011052A1 (en) * 1998-08-24 2000-03-02 Green Technology Inc. Method and composition of a hydrophilic polymer dispersion containing an inorganic flocculant to be used for the treatment of waste water
US6531531B1 (en) 1998-08-24 2003-03-11 Green Technology Inc. Method and composition of a hydrophilic polymer dispersion containing an inorganic flocculant to be used for the treatment of waste water
JP2001030000A (en) * 1999-07-19 2001-02-06 Kurita Water Ind Ltd Sludge dehydrating method
JP2001286900A (en) * 2000-04-07 2001-10-16 Konan Kagaku Kogyo Kk Method for flocculating organic sludge and polymer flocculating agent
JP2001300599A (en) * 2000-04-24 2001-10-30 Kurita Water Ind Ltd Sludge dehydrating method
JP4660896B2 (en) * 2000-08-08 2011-03-30 東亞合成株式会社 Sludge dewatering method
JP2002045900A (en) * 2000-08-08 2002-02-12 Toagosei Co Ltd Method for dewatering sludge
WO2002100944A1 (en) 2001-06-11 2002-12-19 Hymo Corporation Amphoteric water-soluble polymer dispersion and use thereof
US7250462B2 (en) 2001-06-11 2007-07-31 Hymo Corporation Amphoteric water-soluble polymer dispersion and use thereof
JP2005131572A (en) * 2003-10-31 2005-05-26 Daiyanitorikkusu Kk Method for dehydrating sludge
JP4689156B2 (en) * 2003-10-31 2011-05-25 ダイヤニトリックス株式会社 Sludge dewatering method
US7745529B2 (en) 2006-08-03 2010-06-29 Hymo Corporation Flocculant composition and method for manufacturing the same
JP2012012540A (en) * 2010-07-02 2012-01-19 Daiyanitorikkusu Kk Method for producing powdery cationic water-soluble polymer compound, sludge dehydrating agent, and method for dehydrating sludge
CN102701367A (en) * 2012-06-12 2012-10-03 四川师范大学 Water-soluble organic copolymerized amphiprotic polymer flocculating agent and preparation method
CN102701381A (en) * 2012-06-14 2012-10-03 四川师范大学 Water-soluble organic amphoteric polymeric flocculant and preparation method thereof

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