JP2535347B2 - Cationic polymer flocculant - Google Patents
Cationic polymer flocculantInfo
- Publication number
- JP2535347B2 JP2535347B2 JP62103869A JP10386987A JP2535347B2 JP 2535347 B2 JP2535347 B2 JP 2535347B2 JP 62103869 A JP62103869 A JP 62103869A JP 10386987 A JP10386987 A JP 10386987A JP 2535347 B2 JP2535347 B2 JP 2535347B2
- Authority
- JP
- Japan
- Prior art keywords
- meth
- general formula
- salt
- monomer
- group
- 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.)
- Expired - Lifetime
Links
- 229920006317 cationic polymer Polymers 0.000 title claims description 9
- 239000000178 monomer Substances 0.000 claims description 42
- -1 halogen anion Chemical group 0.000 claims description 20
- 125000004432 carbon atom Chemical group C* 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 9
- 229920000642 polymer Polymers 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 7
- 150000001450 anions Chemical class 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 150000003863 ammonium salts Chemical class 0.000 claims description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 4
- 239000011707 mineral Substances 0.000 claims description 4
- 229920006395 saturated elastomer Polymers 0.000 claims description 4
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 3
- 230000004931 aggregating effect Effects 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 3
- 239000008394 flocculating agent Substances 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 claims description 3
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 2
- 125000005907 alkyl ester group Chemical group 0.000 claims description 2
- 125000004964 sulfoalkyl group Chemical group 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 claims 1
- 239000002184 metal Substances 0.000 claims 1
- 239000010802 sludge Substances 0.000 description 20
- 208000005156 Dehydration Diseases 0.000 description 13
- 230000018044 dehydration Effects 0.000 description 13
- 238000006297 dehydration reaction Methods 0.000 description 13
- 230000015271 coagulation Effects 0.000 description 12
- 238000005345 coagulation Methods 0.000 description 12
- 230000000694 effects Effects 0.000 description 9
- 239000004744 fabric Substances 0.000 description 8
- 239000010865 sewage Substances 0.000 description 8
- 235000014113 dietary fatty acids Nutrition 0.000 description 7
- 229930195729 fatty acid Natural products 0.000 description 7
- 239000000194 fatty acid Substances 0.000 description 7
- 239000000706 filtrate Substances 0.000 description 7
- 229920001577 copolymer Polymers 0.000 description 6
- 239000010800 human waste Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000000701 coagulant Substances 0.000 description 5
- 150000004665 fatty acids Chemical class 0.000 description 4
- 239000010801 sewage sludge Substances 0.000 description 4
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 description 3
- 239000004677 Nylon Substances 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 3
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 229920001778 nylon Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- 125000001302 tertiary amino group Chemical group 0.000 description 2
- 229920003169 water-soluble polymer Polymers 0.000 description 2
- SJIXRGNQPBQWMK-UHFFFAOYSA-N 2-(diethylamino)ethyl 2-methylprop-2-enoate Chemical compound CCN(CC)CCOC(=O)C(C)=C SJIXRGNQPBQWMK-UHFFFAOYSA-N 0.000 description 1
- QHVBLSNVXDSMEB-UHFFFAOYSA-N 2-(diethylamino)ethyl prop-2-enoate Chemical class CCN(CC)CCOC(=O)C=C QHVBLSNVXDSMEB-UHFFFAOYSA-N 0.000 description 1
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 1
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 150000003926 acrylamides Chemical class 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 229940073608 benzyl chloride Drugs 0.000 description 1
- ZGCZDEVLEULNLJ-UHFFFAOYSA-M benzyl-dimethyl-(2-prop-2-enoyloxyethyl)azanium;chloride Chemical compound [Cl-].C=CC(=O)OCC[N+](C)(C)CC1=CC=CC=C1 ZGCZDEVLEULNLJ-UHFFFAOYSA-M 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003623 enhancer Substances 0.000 description 1
- 230000003631 expected effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000003311 flocculating effect Effects 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229940050176 methyl chloride Drugs 0.000 description 1
- JZMJDSHXVKJFKW-UHFFFAOYSA-M methyl sulfate(1-) Chemical compound COS([O-])(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-M 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 229960002446 octanoic acid Drugs 0.000 description 1
- 238000004391 petroleum recovery Methods 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000001932 seasonal effect Effects 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- AIUAMYPYEUQVEM-UHFFFAOYSA-N trimethyl(2-prop-2-enoyloxyethyl)azanium Chemical class C[N+](C)(C)CCOC(=O)C=C AIUAMYPYEUQVEM-UHFFFAOYSA-N 0.000 description 1
- OEIXGLMQZVLOQX-UHFFFAOYSA-N trimethyl-[3-(prop-2-enoylamino)propyl]azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CCCNC(=O)C=C OEIXGLMQZVLOQX-UHFFFAOYSA-N 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は脱水性に優れたカチオン性高分子凝集剤に関
する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a cationic polymer flocculant having excellent dehydratability.
アクリル系高分子量水溶性重合体は、紙力増強剤、増
粘剤、凝集沈降剤、石油回収用薬剤などとして広く用い
られている。とくにカチオン性を有する重合体は、下水
処理や屎尿処理で発生する汚泥や各種産業廃水の凝集脱
水処理剤として使用されており、その使用量は近年増大
の一途をたどっている。Acrylic high molecular weight water-soluble polymers are widely used as paper strength enhancers, thickeners, flocculating and precipitating agents, petroleum recovery agents and the like. In particular, a polymer having a cationic property is used as a coagulation dehydration treatment agent for sludge generated in sewage treatment or human waste treatment and various industrial wastewaters, and the amount thereof is increasing in recent years.
種々のカチオン性重合体が凝集脱水処理剤として市場
に出回っているが、現在、ジメチルアミノエチルメタク
リレートをメチルクロライドで４級化した塩の（共）重
合性が最も多く使用されている。この適用範囲をさらに
拡げるため、メチルクロライドのかわりに鉱酸で塩にし
たジメチルアミノエチルメタクリレートを（共）重合さ
せたものや、ベンジルクロライドで４級塩にしたものを
（共）重合させたものなども使用されている。さらにそ
の効果の向上を狙って、ジメチルアミノエチルアクリレ
ート系重合体、ジメチルアミノアルキル（メタ）アクリ
ルアミド系重合体なども使用されてきている。Although various cationic polymers are on the market as coagulation dehydration treating agents, at present, the (co) polymerizability of a quaternized salt of dimethylaminoethyl methacrylate with methyl chloride is most often used. In order to further expand this application range, instead of methyl chloride, (co) polymerized dimethylaminoethyl methacrylate salted with mineral acid, or quaternary salt with benzyl chloride (co) polymerized Are also used. Further, dimethylaminoethyl acrylate-based polymers, dimethylaminoalkyl (meth) acrylamide-based polymers and the like have been used for the purpose of improving the effect.
下水処理や屎尿処理で生ずる汚泥の凝集脱水処理で
は、季節的要因、その他の外的条件などによって汚泥の
性質が大きく変動し、凝集剤の効果に影響を与えること
が多い。In the coagulation and dehydration treatment of sludge generated by sewage treatment or human waste treatment, the properties of the sludge greatly change due to seasonal factors and other external conditions, and the effect of the coagulant is often affected.
下水処理や屎尿処理で生ずる汚泥の凝集脱水処理で
は、いかに効果的に脱水し、スラッジの水分を少なくす
るかが重要なポイントであり、分離したスラッジの取扱
い易さや脱離液の透明度合なども重視される。In the coagulation and dewatering process of sludge generated by sewage treatment and human waste treatment, the important point is how to effectively dehydrate and reduce the water content of sludge, and the ease of handling the separated sludge and the transparency of the desorbed liquid are also important. Be valued.
下水処理、屎尿処理で生ずる汚泥の凝集脱水処理の効
果を高めるため、無機凝集剤の併用や木粉などを濾過脱
水助剤として使用することも試みられているが、処理コ
ストの増大、スラッジの増加などを伴ううえ、期待した
ほどの効果をうることができないばあいが多い。In order to enhance the effect of coagulation / dewatering of sludge produced by sewage treatment and human waste treatment, it has been attempted to use an inorganic coagulant in combination or to use wood powder as a filter / dehydration auxiliary agent. In addition to the increase, there are many cases where the expected effect cannot be obtained.
また、脱水効果向上のため、凝集剤として使用するカ
チオン性水溶性重合体に疎水性を付与させる方法も提案
され、ジメチルアミノエチル（メタ）アクリレート塩
（３級塩または４級塩）またはこれとアクリルアミドと
の混合物とアクリル酸メチル、アクリロニトリルなどの
疎水性セグメントとして作用する単量体との共重合体も
検討されている。これらの疎水性単量体を用いた共重合
体の脱水性能は一部の汚泥には改良された性能を示すこ
ともあるが、むしろ逆に脱水した汚泥・スラッジにべと
つきが生じたり、濾過脱水に使用する濾過機の濾布との
剥離性がわるくなり、目詰まりを起こすなどの問題の生
ずることが多い。In order to improve the dehydration effect, a method of imparting hydrophobicity to a cationic water-soluble polymer used as a coagulant is also proposed, and dimethylaminoethyl (meth) acrylate salt (tertiary salt or quaternary salt) or this Copolymers of a mixture with acrylamide and a monomer such as methyl acrylate or acrylonitrile that acts as a hydrophobic segment have also been investigated. The dehydration performance of copolymers using these hydrophobic monomers may show improved performance for some sludges, but on the contrary, the dehydrated sludge / sludge may become sticky, or may be filtered and dehydrated. In many cases, the peelability of the filter used for the above from the filter cloth becomes poor, and problems such as clogging occur.
また、このような疎水性単量体を共重合させることに
よってカチオン性重合体の水溶性が損われ、均一に溶解
しない部分が存在することによる有効成分量の実質的な
低下がおこり、充分な性能を発揮しなくなることも少な
くない。Further, by copolymerizing such a hydrophobic monomer, the water solubility of the cationic polymer is impaired, and the presence of a portion that does not dissolve uniformly causes a substantial decrease in the amount of the active ingredient, which is sufficient. It is not uncommon to lose performance.
本発明は、このような従来からあるカチオン性高分子
凝集剤の欠点を解消するためになされたものである。The present invention has been made to solve the above-mentioned drawbacks of conventional cationic polymer flocculants.
一般式（Ｉ）： （式中、R1は水素原子またはメチル基、R2およびR3はそ
れぞれ炭素数１〜３のアルキル基で、R2とR3とは同じで
ある必要はない、R4は水素原子、炭素数１〜３のアルキ
ル基またはベンジル基、Ｙは−Ｏ−または−NH−、ｍは
１〜３の整数、Ｘ はハロゲンアニオン、モノアルキル
硫酸アニオンまたは鉱酸に由来するアニオンを表わす）
で表わされる単量体および一般式（II）： （式中、R5は水素原子またはメチル基、R6およびR7はそ
れぞれ炭素数１〜３のアルキル基で、R6とR7とは同じで
ある必要はない、Ａは−Ｏ−または−NH−、ｎは１〜３
の整数、Ｚは炭素数８〜18の直鎖または分岐鎖を有す
る飽和モノカルボン酸に由来するアニオンを表わす）で
表わされる単量体の混合物または該混合物とその他の水
溶性（メタ）アクリル系単量体との混合物を共重合させ
てえられた重合体からなるカチオン性高分子凝集剤に関
する。 General formula (I):(Where R1Is a hydrogen atom or a methyl group, R2And R3Haso
Each is an alkyl group having 1 to 3 carbon atoms, R2And R3Is the same as
Need not be, RFourIs a hydrogen atom, an alkyl group having 1 to 3 carbon atoms
Group or benzyl group, Y is -O- or -NH-, and m is
An integer from 1 to 3, X Is a halogen anion, monoalkyl
(Represents a sulfate anion or an anion derived from mineral acid)
And a monomer represented by the general formula (II):(Where RFiveIs a hydrogen atom or a methyl group, R6And R7Haso
Each is an alkyl group having 1 to 3 carbon atoms, R6And R7Is the same as
Need not be, A is -O- or -NH-, n is 1-3
Z is a straight or branched chain having 8 to 18 carbon atoms
Represents an anion derived from a saturated monocarboxylic acid)
Mixtures of the represented monomers or said mixture and other water
Copolymerize a mixture with soluble (meth) acrylic monomers
Related to the cationic polymer flocculant consisting of the obtained polymer
I do.
本発明のカチオン性高分子凝集剤は、一般式（Ｉ）： （式中、R1は水素原子またはメチル基、R2およびR3はそ
れぞれ炭素数１〜３のアルキル基で、R2とR3とは同じで
ある必要はない、R4は水素原子、炭素数１〜３のアルキ
ル基またはベンジル基、Ｙは−Ｏ−または−NH−、ｍは
１〜３の整数、Ｘ はハロゲンアニオン、好ましくはCl
またはBr、モノアルキル硫酸アニオンまたは鉱酸に
由来するアニオンを表わす）で表わされる単量体および
一般式（II）： （式中、R5は水素原子またはメチル基、R6およびR7はそ
れぞれ炭素数１〜３のアルキル基で、R6とR7とは同じで
ある必要はない、Ａは−Ｏ−または−NH−、ｎは１〜３
の整数、Ｚ は炭素数８〜18の直鎖または分岐鎖を有す
る飽和モノカルボン酸に由来するアニオンを表わす）で
表わされる単量体からなる混合物が共重合せしめられた
ものである。 The cationic polymer flocculant of the present invention has the general formula (I):(Where R1Is a hydrogen atom or a methyl group, R2And R3Haso
Each is an alkyl group having 1 to 3 carbon atoms, R2And R3Is the same as
Need not be, RFourIs a hydrogen atom, an alkyl group having 1 to 3 carbon atoms
Group or benzyl group, Y is -O- or -NH-, and m is
An integer from 1 to 3, X Is a halogen anion, preferably Cl
Or to Br, monoalkyl sulfate anion or mineral acid
(Representing an anion derived from) and
General formula (II):(Where RFiveIs a hydrogen atom or a methyl group, R6And R7Haso
Each is an alkyl group having 1 to 3 carbon atoms, R6And R7Is the same as
Need not be, A is -O- or -NH-, n is 1-3
The integer of Z Has a straight or branched chain having 8 to 18 carbon atoms
Represents an anion derived from a saturated monocarboxylic acid)
A mixture of the indicated monomers was copolymerized.
Things.
前記一般式（Ｉ）で表わされる単量体の具体例として
は、たとえばＮ−（メタ）アクリロイルオキシエチル−
N,N,N−トリメチルアンモニウム塩（クロライド、メチ
ルサルフェート）、Ｎ−（メタ）アクリロイルオキシエ
チル−N,N−ジメチル−Ｎ−ベンジルアンモニウムクロ
ライド、Ｎ−（メタ）アクリロイルオキシエチル−N,N
−ジメチルアミン塩（塩酸塩、硫酸塩）、Ｎ−（メタ）
アクリロイルオキシエチル−N,N−ジエチルアミン塩、
Ｎ−（メタ）アクリルアミドプロピル−N,N,N−トリメ
チルアンモニウムクロライド、N,N−ジメチルアミノプ
ロピル（メタ）アクリルアミド塩（塩酸塩、硫酸塩）な
どがあげられ、これらは単独で用いてもよく、２種以上
併用してもよい。Specific examples of the monomer represented by the general formula (I) include N- (meth) acryloyloxyethyl-
N, N, N-trimethylammonium salt (chloride, methylsulfate), N- (meth) acryloyloxyethyl-N, N-dimethyl-N-benzylammonium chloride, N- (meth) acryloyloxyethyl-N, N
-Dimethylamine salt (hydrochloride, sulfate), N- (meth)
Acryloyloxyethyl-N, N-diethylamine salt,
Examples thereof include N- (meth) acrylamidopropyl-N, N, N-trimethylammonium chloride and N, N-dimethylaminopropyl (meth) acrylamide salts (hydrochloride, sulfate), which may be used alone. You may use 2 or more types together.
また、前記一般式（II）で表わされる単量体の具体例
としては、たとえばＮ−（メタ）アクリロイルオキシエ
チル−N,N−ジメチルアミン、Ｎ−メタクリロイルオキ
シエチル−N,N−ジエチルアミン、N,N−ジメチルアミノ
プロピル（メタ）アクリルアミドなどの第３級アミノ基
を有する化合物の少なくとも１種とカプリル酸、カプリ
ン酸、ラウリン酸、ミリスチン酸、パルミチン酸、ステ
アリン酸などの飽和高級脂肪酸の少なくとも１種とから
なる高級脂肪酸塩があげられ、これらは単独で用いても
よく、２種以上併用してもよい。Specific examples of the monomer represented by the general formula (II) include, for example, N- (meth) acryloyloxyethyl-N, N-dimethylamine, N-methacryloyloxyethyl-N, N-diethylamine, N. At least one compound having a tertiary amino group such as N, N-dimethylaminopropyl (meth) acrylamide and at least one saturated higher fatty acid such as caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid and stearic acid Examples of the higher fatty acid salt include a seed and a higher fatty acid salt. These may be used alone or in combination of two or more kinds.
前記一般式（Ｉ）で表わされるれ単量体および一般式
（II）で表わされる単量体の混合割合としては、モル比
で（Ｉ）／（II）＝85/15〜99.5/0.5であるのが好まし
く、また一般式（II）で表わされる単量体が全単量体中
に少なくとも0.2モル％存在するのが好ましく、１〜10
モル％であるのがさらに好ましい。The mixing ratio of the monomer represented by the general formula (I) and the monomer represented by the general formula (II) is (I) / (II) = 85/15 to 99.5 / 0.5 in molar ratio. It is preferable that the monomer represented by the general formula (II) is present in at least 0.2 mol% in all the monomers, and
More preferably, it is mol%.
本発明において、前記一般式（II）で表わされる単量
体の少なくとも１種を共重合の必須構成成分にすること
により、従来見られなかった特筆すべき効果、すなわ
ち、下水汚泥、屎尿汚泥などの凝集脱水処理に対して注
目に対する改良された性能をうることが可能になったも
のである。In the present invention, by using at least one of the monomers represented by the general formula (II) as an essential constituent component of the copolymerization, a remarkable effect which has not been heretofore seen, that is, sewage sludge, human waste sludge, etc. It is now possible to obtain improved performance for attention to the coagulation dehydration treatment of.
一般式（II）で表わされる単量体は本発明に不可欠の
成分であるが、無制限に多く使用できるものではなく、
該単量体を多量に含有する共重合体は水溶性において難
点が生じ、水に対する溶解が不充分となり、他方、該単
量体含有量が過少であるときは、本発明の効果が充分え
られない。したがって、本発明における一般式（II）で
表わされる単量体の使用量にはおのずと適正な範囲があ
るが、上記単量体の種類により該単量体を含有する共重
合体の水溶性に及ぼす影響度合が異なり、凝集脱水性能
にも違いが生じるので、それぞれの特徴を活かした適正
使用量を選ばなければならない。The monomer represented by the general formula (II) is an essential component of the present invention, but it is not limited to a large number and can be used.
A copolymer containing a large amount of the above-mentioned monomer has problems in water solubility, resulting in insufficient solubility in water. On the other hand, when the content of the monomer is too small, the effect of the present invention may be insufficient. I can't. Therefore, although the amount of the monomer represented by the general formula (II) used in the present invention has a proper range as a matter of course, the water solubility of the copolymer containing the monomer depends on the kind of the monomer. Since the degree of influence exerted differs and the coagulation / dewatering performance also differs, it is necessary to select an appropriate amount of use that takes advantage of each characteristic.
上記単量体は、第３級アミノ基を有するカチオン性ア
クリル系単量体の高級脂肪酸塩であるが、使用される高
級脂肪酸は炭素数８〜18のものである。高級脂肪酸の炭
素数が８未満のばあいには、えられる共重合体の凝集脱
水効果が改良されず、反対に炭素数が18をこえるばあい
には、該単量体と他の単量体との相溶性がわるく、重合
に適した均一な単量体水溶液をうるためにはごくわずか
の量しか使用できず、しかも水溶性のよくない共重合体
となり、所望する凝集脱水効果が期待しがたい。The above-mentioned monomer is a higher fatty acid salt of a cationic acrylic monomer having a tertiary amino group, and the higher fatty acid used has 8 to 18 carbon atoms. When the higher fatty acid has less than 8 carbon atoms, the coagulation / dehydration effect of the obtained copolymer is not improved. On the contrary, when the higher fatty acid has more than 18, the monomer and other monomer It has poor compatibility with the polymer and can be used only in a very small amount in order to obtain a uniform monomer aqueous solution suitable for polymerization, and it is a copolymer with poor water solubility, and the desired aggregation and dehydration effect is expected. It's hard to do.
本発明においては、前記一般式（Ｉ）および（II）で
表わされる単量体の混合物のみを重合させてもよいが、
この混合物をその他の水溶性（メタ）アクリル系単量体
と混合して重合させてもよい。In the present invention, only a mixture of the monomers represented by the general formulas (I) and (II) may be polymerized,
This mixture may be mixed with another water-soluble (meth) acrylic monomer and polymerized.
前記その他のアクリル系単量体としては、たとえば
（メタ）アクリルアミド、モノまたはジアルキル（メ
タ）アクリルアミド、（メタ）アクリロイルモルホリ
ン、スルホアルキル（メタ）アクリルアミド、その塩
（アルカリ金属塩、アルカリ土類金属塩、アンモニウム
塩、アミン塩）（メタ）アクリル酸、その塩（アルカリ
金属塩、アンモニウム塩、アミン塩）、（メタ）アクリ
ル酸アルキルエステル、（メタ）アクリル酸ヒドロキシ
アルキルエステル、（メタ）アクリル酸アルコキシアル
キルエステルおよび（メタ）アクリロニトリルなどがあ
げられ、これらは単独で併用してもよく、２種以上で併
用してもよいが、前記一般式（Ｉ）で表わされる単量体
および一般式（II）で表わされる単量体の混合物と混合
して均一な混合水溶液を形成するものが好ましい。Examples of the other acrylic monomer include (meth) acrylamide, mono- or dialkyl (meth) acrylamide, (meth) acryloylmorpholine, sulfoalkyl (meth) acrylamide, and salts thereof (alkali metal salts, alkaline earth metal salts). , Ammonium salt, amine salt) (meth) acrylic acid, its salt (alkali metal salt, ammonium salt, amine salt), (meth) acrylic acid alkyl ester, (meth) acrylic acid hydroxyalkyl ester, (meth) acrylic acid alkoxy Examples thereof include alkyl esters and (meth) acrylonitrile. These may be used alone or in combination of two or more, and the monomer represented by the general formula (I) and the general formula (II ) To form a homogeneous mixed aqueous solution. Shall is preferable.
その他のアクリル系単量体の全単量体中における割合
としては、通常90モル％以下が採用される。The proportion of other acrylic monomers in the total monomers is usually 90 mol% or less.
下水・屎尿汚泥の凝集脱水処理などに卓越した性能を
発揮する本発明のカチオン性（メタ）アクリル系高分子
凝集剤は、通常の公知の方法で製造することが可能であ
り、水溶液重合による方法が最も一般的である。The cationic (meth) acrylic polymer flocculant of the present invention, which exhibits excellent performance in coagulation and dehydration treatment of sewage / sewage sludge, can be produced by a commonly known method, and a method by aqueous solution polymerization. Is the most common.
製法のちがいが本発明の凝集剤の優れた性能に影響を
及ぼすことは少ないが、一般にいわれている凝集性能と
重合体分子量とが概ね比例的関係を有するということか
らして、高分子量重合体がえられ易く、かつ効率的な製
造が容易である光照射による水溶液重合方法が適してい
る。Although the difference in the production method does not affect the excellent performance of the aggregating agent of the present invention, it is generally said that the aggregating performance and the polymer molecular weight have a substantially proportional relationship. The aqueous solution polymerization method by light irradiation is suitable because it is easy to obtain and easy to produce efficiently.
このようにしてえられる本発明の凝集剤は下水・屎尿
汚泥に対する凝集脱水処理、とくに濾過脱水において明
らかに改良された性能を示すとともに、濾過機の濾布と
スラッジとの剥離性がきわめて良好である。The coagulant of the present invention thus obtained shows clearly improved performance in the coagulation / dewatering treatment of sewage / sewage sludge, especially in the filtration / dehydration, and the releasability between the filter cloth and the sludge is extremely good. is there.
以下に実施例に基づき本発明の凝集剤を具体的に説明
する。The flocculant of the present invention will be specifically described below based on Examples.
実施例１〜６および比較例１〜８ 第１表に記載のカチオン性高分子凝集剤を用いて、関
東地区某下水処理場の廃水を活性汚泥処理してえられた
固形分濃度21000ppmの余剰汚泥について、以下の凝集試
験を行なった。Examples 1 to 6 and Comparative Examples 1 to 8 Using the cationic polymer flocculants described in Table 1, the wastewater of a certain sewage treatment plant in the Kanto area was treated with activated sludge to obtain a surplus with a solid content of 21000 ppm. The following coagulation test was performed on the sludge.
汚泥200mlを300mlビーカーに採り、0.2％水溶液に調
整した凝集剤を汚泥に対して140ppmになるように添加
し、ジャーテスターで500rpm、30秒間攪拌したのちフロ
ックの形状を観察した。そののち96メッシュのナイロン
濾布をしいた内径70mmのヌッチェに汚泥を一気に注ぎ込
み、15秒、30秒、45秒、60秒後の濾液量を測定するとと
もに、濾液の濁りについても観察した。また、ナイロン
濾布上のケーキをスパーテルでヌッチェ内壁に押付けて
スラッジの脱水性を定性的に判定した。結果を第２表に
示す。200 ml of sludge was placed in a 300 ml beaker, a flocculant adjusted to a 0.2% aqueous solution was added so as to be 140 ppm with respect to the sludge, stirred with a jar tester at 500 rpm for 30 seconds, and then the shape of flocs was observed. After that, the sludge was poured all at once into a nutche having an inner diameter of 70 mm, which was covered with a 96-mesh nylon filter cloth, and the amount of the filtrate was measured after 15 seconds, 30 seconds, 45 seconds, and 60 seconds, and the turbidity of the filtrate was also observed. Further, the cake on the nylon filter cloth was pressed against the inner wall of the Nutsche with a spatula to qualitatively judge the dehydration property of the sludge. The results are shown in Table 2.
なお第１表における水溶性の◎は重合体粉末の0.5％
水溶液を肉眼にて評価し、不溶解物がなく透明なこと、
○は不溶解物がごくわずかで、ほとんど透明なこと、△
は不溶解物があり、濁りのあることを示す。The water-soluble ⊚ in Table 1 is 0.5% of the polymer powder.
The aqueous solution was evaluated with the naked eye, and it was transparent with no insoluble matter,
○ means that the insoluble matter is very small and almost transparent, △
Indicates that there is insoluble matter and there is turbidity.
また水溶液粘度は重合体粉末の0.5％水溶液をブルッ
クフィールド粘度計、ローターNo.3、12rpm、25℃にて
測定した値である。The aqueous solution viscosity is a value obtained by measuring a 0.5% aqueous solution of polymer powder with a Brookfield viscometer, rotor No. 3, 12 rpm, and 25 ° C.
さらに第２表のフロック径の◎は径４〜5mmの良好な
フロック、○は２〜3mmの良好なフロック、△は1mm程度
の弱いフロックを表わし、濾液の清澄性の○は濁りな
し、△は少し濁るを表わし、スラッジの脱水性の○はよ
くしぼれる、△はしぼれるが若干含水率が高い、×はベ
タベタでしぼれないを表わす。Further, in Table 2, the floc diameter ◎ indicates a good floc with a diameter of 4 to 5 mm, ○ indicates a good floc of 2 to 3 mm, △ indicates a weak floc of about 1 mm, and ○ in the clarity of the filtrate indicates no turbidity, △ Indicates that the sludge is slightly turbid, ○ of the dehydration property of sludge is well squeezed, Δ is squeezed but has a slightly high water content, and x is sticky and not squeezed.
実施例２ 第１表に記載の凝集剤を用いて、関西地区某屎尿処理
場の固形分濃度18500ppmの消化混合汚泥について、実施
例１と同様に凝集試験を行なった。ただし凝集剤添加量
は250ppmであった。このばあいにも実施例１のばあいと
同様に、ヌッチェによる濾液量を測定するとともに濾液
の濁りを観察した。そののち、ヌッチェに残留したフロ
ック約30mlを採り、60メッシュナイロン濾布２枚の間に
はさみ、油圧プレス機にかけて1kg/cm2×１分、4kg/cm2
×１分の順に加圧したのち、脱水ケーキの濾布からの剥
離性を観察した。またケーキ含水率を乾燥法により測定
した。結果を第３表に示す。Example 2 Using the coagulant shown in Table 1, a coagulation test was conducted in the same manner as in Example 1 on digested mixed sludge having a solid content concentration of 18500 ppm at a certain human waste treatment plant in the Kansai region. However, the amount of the flocculant added was 250 ppm. In this case, as in the case of Example 1, the amount of filtrate by Nutsche was measured and the turbidity of the filtrate was observed. After that, collect about 30 ml of floc remaining on the nutche, sandwich it between two 60 mesh nylon filter cloths, and apply it to a hydraulic press machine at 1 kg / cm 2 × 1 minute, 4 kg / cm 2
After pressing in the order of × 1 minute, the peelability of the dehydrated cake from the filter cloth was observed. The water content of the cake was measured by the dry method. The results are shown in Table 3.
なお第３表におけるフロック径、濾液の清澄性の評価
は実施例１と同様にして行なった。また脱水ケーキの剥
離性の◎は濾液にケーキが全く残らない、○は濾布にケ
ーキが少々付着する、×は濾布からケーキが剥れないこ
とを表わす。The floc diameter and the clarity of the filtrate in Table 3 were evaluated in the same manner as in Example 1. Further, ⊚ of the peelability of the dehydrated cake means that no cake remains in the filtrate, ◯ means that a small amount of cake adheres to the filter cloth, and × means that the cake does not separate from the filter cloth.
［発明の効果］ 本発明の凝集剤を用いると、下水・屎尿汚泥中の固形
分の凝集性および過性が良好であり、かつケーキの
布からの剥離性も良好となる。 [Effects of the Invention] When the flocculant of the present invention is used, the solid content in sewage / sewage sludge is excellent in cohesiveness and transitivity, and the releasability of the cake from the cloth is also good.
Claims (3)
れぞれ炭素数１〜３のアルキル基で、R2とR3とは同じで
ある必要はない、R4は水素原子、炭素数１〜３のアルキ
ル基またはベンジル基、Ｙは−Ｏ−または−NH−、ｍは
１〜３の整数、Ｘ はハロゲンアニオン、モノアルキル
硫酸アニオンまたは鉱酸に由来するアニオンを表わす）
で表わされる単量体および一般式（II）： （式中、R5は水素原子またはメチル基、R6およびR7はそ
れぞれ炭素数１〜３のアルキル基で、R6とR7とは同じで
ある必要はない、Ａは−Ｏ−または−NH−、ｎは１〜３
の整数、Ｚ は炭素数８〜18の直鎖または分岐鎖を有す
る飽和モノカルボン酸に由来するアニオンを表わす）で
表わされる単量体の混合物または該混合物とその他の水
溶性（メタ）アクリル系単量体との混合物を共重合させ
てえられた重合体からなるカチオン性高分子凝集剤。1. General formula (I):(Where R1Is a hydrogen atom or a methyl group, R2And R3Haso
Each is an alkyl group having 1 to 3 carbon atoms, R2And R3Is the same as
Need not be, RFourIs a hydrogen atom, an alkyl group having 1 to 3 carbon atoms
Group or benzyl group, Y is -O- or -NH-, and m is
An integer from 1 to 3, X Is a halogen anion, monoalkyl
(Represents a sulfate anion or an anion derived from mineral acid)
And a monomer represented by the general formula (II):(Where RFiveIs a hydrogen atom or a methyl group, R6And R7Haso
Each is an alkyl group having 1 to 3 carbon atoms, R6And R7Is the same as
Need not be, A is -O- or -NH-, n is 1-3
The integer of Z Has a straight or branched chain having 8 to 18 carbon atoms
Represents an anion derived from a saturated monocarboxylic acid)
Mixtures of the represented monomers or said mixture and other water
Copolymerize a mixture with soluble (meth) acrylic monomers
Cationic polymer flocculant consisting of the obtained polymer.
般式（II）で表わされる単量体との割合がモル比で
（Ｉ）／（II）＝85/15〜99.5/0.5であり、かつ、一般
式（II）で表わされる単量体が全単量体中に少なくとも
0.2モル％含有されている特許請求の範囲第１項記載の
凝集剤。2. The molar ratio of the monomer represented by the general formula (I) to the monomer represented by the general formula (II) is (I) / (II) = 85/15 to 99.5 / 0.5, and the monomer represented by the general formula (II) is at least in all the monomers.
The aggregating agent according to claim 1, which contains 0.2 mol%.
量体が、（メタ）アクリルアミド、モノまたはジアルキ
ル（メタ）アクリルアミド、（メタ）アクリロイルモル
ホリン、スルホアルキル（メタ）アクリルアミド、その
塩（アルカリ金属塩、アルカリ土類金属塩、アンモニウ
ム塩、アミン塩）、（メタ）アクリル酸、その塩（アル
カリ金属塩、アンモニウム塩、アミン塩）、（メタ）ア
クリル酸アルキルエステル、（メタ）アクリル酸ヒドロ
キシアルキルエステル、（メタ）アクリル酸アルコキシ
アルキルエステルおよび（メタ）アクリロニトリルより
なる群から選ばれた少なくとも１種であり、前記一般式
（Ｉ）で表わされる単量体および一般式（II）で表わさ
れる単量体の混合物と混合して均一な水溶液を形成する
単量体である特許請求の範囲第１項記載の凝集剤。3. The other water-soluble (meth) acrylic monomer is (meth) acrylamide, mono- or dialkyl (meth) acrylamide, (meth) acryloylmorpholine, sulfoalkyl (meth) acrylamide, or a salt thereof (alkali). Metal salt, alkaline earth metal salt, ammonium salt, amine salt), (meth) acrylic acid, its salt (alkali metal salt, ammonium salt, amine salt), (meth) acrylic acid alkyl ester, (meth) acrylic acid hydroxy It is at least one selected from the group consisting of alkyl ester, (meth) acrylic acid alkoxyalkyl ester and (meth) acrylonitrile, and is represented by the monomer represented by the general formula (I) and the general formula (II). Patent that is a monomer that forms a uniform aqueous solution when mixed with a mixture of monomers Flocculants range first claim of seeking.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62103869A JP2535347B2 (en) | 1987-04-27 | 1987-04-27 | Cationic polymer flocculant |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62103869A JP2535347B2 (en) | 1987-04-27 | 1987-04-27 | Cationic polymer flocculant |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63267408A JPS63267408A (en) | 1988-11-04 |
| JP2535347B2 true JP2535347B2 (en) | 1996-09-18 |
Family
ID=14365444
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62103869A Expired - Lifetime JP2535347B2 (en) | 1987-04-27 | 1987-04-27 | Cationic polymer flocculant |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2535347B2 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5120449A (en) * | 1987-03-27 | 1992-06-09 | Societe Nationale Elf Aquitaine (Production) | Treatment of aqueous drilling mud effluents containing lignosulfonates |
| JPH02269715A (en) * | 1989-04-11 | 1990-11-05 | Sumitomo Chem Co Ltd | Cationic emulsion |
| JPH0630800B2 (en) * | 1989-11-27 | 1994-04-27 | 栗田工業株式会社 | Sludge dehydrator |
| US5437792A (en) * | 1994-07-27 | 1995-08-01 | Eastman Kodak Company | Process of recovering silver from photographic solutions |
| DE102005009809B4 (en) * | 2005-03-03 | 2007-02-22 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Process for separating suspended solids |
-
1987
- 1987-04-27 JP JP62103869A patent/JP2535347B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63267408A (en) | 1988-11-04 |
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