JP5601704B2 - Sludge dewatering agent and sludge dewatering method - Google Patents
Sludge dewatering agent and sludge dewatering method Download PDFInfo
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- JP5601704B2 JP5601704B2 JP2010155430A JP2010155430A JP5601704B2 JP 5601704 B2 JP5601704 B2 JP 5601704B2 JP 2010155430 A JP2010155430 A JP 2010155430A JP 2010155430 A JP2010155430 A JP 2010155430A JP 5601704 B2 JP5601704 B2 JP 5601704B2
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- Prior art keywords
- water
- group
- soluble polymer
- general formula
- hydrogen
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- 239000010802 sludge Substances 0.000 title claims description 70
- 239000003795 chemical substances by application Substances 0.000 title claims description 19
- 238000000034 method Methods 0.000 title claims description 12
- 229920003169 water-soluble polymer Polymers 0.000 claims description 89
- 239000000178 monomer Substances 0.000 claims description 87
- 239000007864 aqueous solution Substances 0.000 claims description 46
- 125000000129 anionic group Chemical group 0.000 claims description 36
- 125000002091 cationic group Chemical group 0.000 claims description 34
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 33
- 239000001257 hydrogen Substances 0.000 claims description 30
- 229910052739 hydrogen Inorganic materials 0.000 claims description 30
- 239000000203 mixture Substances 0.000 claims description 24
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 20
- 125000004432 carbon atom Chemical group C* 0.000 claims description 20
- 239000004094 surface-active agent Substances 0.000 claims description 16
- 239000007762 w/o emulsion Substances 0.000 claims description 16
- 125000000217 alkyl group Chemical group 0.000 claims description 15
- 150000001450 anions Chemical class 0.000 claims description 15
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 15
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 15
- 239000003431 cross linking reagent Substances 0.000 claims description 12
- 125000003545 alkoxy group Chemical group 0.000 claims description 10
- 150000002431 hydrogen Chemical class 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 8
- 238000006116 polymerization reaction Methods 0.000 claims description 8
- 230000000379 polymerizing effect Effects 0.000 claims description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 7
- 239000012986 chain transfer agent Substances 0.000 claims description 6
- 125000002947 alkylene group Chemical group 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 150000001768 cations Chemical class 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 230000002209 hydrophobic effect Effects 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 description 31
- 238000004132 cross linking Methods 0.000 description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 239000002245 particle Substances 0.000 description 16
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- 238000006243 chemical reaction Methods 0.000 description 12
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- 150000002500 ions Chemical class 0.000 description 11
- -1 tertiary amine salt Chemical class 0.000 description 10
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- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 8
- 239000011591 potassium Substances 0.000 description 8
- 229910052700 potassium Inorganic materials 0.000 description 8
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 8
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- NJSSICCENMLTKO-HRCBOCMUSA-N [(1r,2s,4r,5r)-3-hydroxy-4-(4-methylphenyl)sulfonyloxy-6,8-dioxabicyclo[3.2.1]octan-2-yl] 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)O[C@H]1C(O)[C@@H](OS(=O)(=O)C=2C=CC(C)=CC=2)[C@@H]2OC[C@H]1O2 NJSSICCENMLTKO-HRCBOCMUSA-N 0.000 description 3
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- RRHXZLALVWBDKH-UHFFFAOYSA-M trimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)OCC[N+](C)(C)C RRHXZLALVWBDKH-UHFFFAOYSA-M 0.000 description 3
- XFCMNSHQOZQILR-UHFFFAOYSA-N 2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOC(=O)C(C)=C XFCMNSHQOZQILR-UHFFFAOYSA-N 0.000 description 2
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- 238000000149 argon plasma sintering Methods 0.000 description 2
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- ZORQXIQZAOLNGE-UHFFFAOYSA-N 1,1-difluorocyclohexane Chemical compound FC1(F)CCCCC1 ZORQXIQZAOLNGE-UHFFFAOYSA-N 0.000 description 1
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- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 1
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 1
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 description 1
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 description 1
- OMNKZBIFPJNNIO-UHFFFAOYSA-N n-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical compound CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 0.000 description 1
- WSSBCLYTBCEJFV-UHFFFAOYSA-N n-[2-(dimethylamino)ethyl]prop-2-enamide;hydrochloride Chemical compound Cl.CN(C)CCNC(=O)C=C WSSBCLYTBCEJFV-UHFFFAOYSA-N 0.000 description 1
- RQAKESSLMFZVMC-UHFFFAOYSA-N n-ethenylacetamide Chemical compound CC(=O)NC=C RQAKESSLMFZVMC-UHFFFAOYSA-N 0.000 description 1
- ZQXSMRAEXCEDJD-UHFFFAOYSA-N n-ethenylformamide Chemical compound C=CNC=O ZQXSMRAEXCEDJD-UHFFFAOYSA-N 0.000 description 1
- DYUWTXWIYMHBQS-UHFFFAOYSA-N n-prop-2-enylprop-2-en-1-amine Chemical compound C=CCNCC=C DYUWTXWIYMHBQS-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007717 redox polymerization reaction Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000010801 sewage sludge Substances 0.000 description 1
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 1
- 235000019254 sodium formate Nutrition 0.000 description 1
- 229940079827 sodium hydrogen sulfite Drugs 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- SZHIIIPPJJXYRY-UHFFFAOYSA-M sodium;2-methylprop-2-ene-1-sulfonate Chemical compound [Na+].CC(=C)CS([O-])(=O)=O SZHIIIPPJJXYRY-UHFFFAOYSA-M 0.000 description 1
- 239000001593 sorbitan monooleate Substances 0.000 description 1
- 235000011069 sorbitan monooleate Nutrition 0.000 description 1
- 229940035049 sorbitan monooleate Drugs 0.000 description 1
- 235000011071 sorbitan monopalmitate Nutrition 0.000 description 1
- 239000001570 sorbitan monopalmitate Substances 0.000 description 1
- 229940031953 sorbitan monopalmitate Drugs 0.000 description 1
- 239000001587 sorbitan monostearate Substances 0.000 description 1
- 235000011076 sorbitan monostearate Nutrition 0.000 description 1
- 229940035048 sorbitan monostearate Drugs 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- VPYJNCGUESNPMV-UHFFFAOYSA-N triallylamine Chemical compound C=CCN(CC=C)CC=C VPYJNCGUESNPMV-UHFFFAOYSA-N 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Separation Of Suspended Particles By Flocculating Agents (AREA)
- Treatment Of Sludge (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
本発明は、汚泥脱水剤および汚泥脱水方法に関するものであり、詳しくは特定のカチオン性単量体、（メタ）アクリルアミド、およびアニオン性単量体１〜５モル％からなる単量体混合物を重合した両性水溶性高分子を含有する汚泥脱水剤に関する。また前記単量体混合物に対し、いずれも質量換算で連鎖移動剤を１００〜１，０００ｐｐｍ、架橋剤を５〜１００ｐｐｍ共存させ重合した架橋性両性水溶性高分子を含有する汚泥脱水剤に関する。 The present invention relates to a sludge dewatering agent and a sludge dewatering method, and more specifically, a monomer mixture composed of a specific cationic monomer, (meth) acrylamide, and 1 to 5 mol% of an anionic monomer is polymerized. The present invention relates to a sludge dewatering agent containing an amphoteric water-soluble polymer. The present invention also relates to a sludge dewatering agent containing a crosslinkable amphoteric water-soluble polymer which is polymerized by coexisting 100 to 1,000 ppm of a chain transfer agent and 5 to 100 ppm of a crosslinking agent in terms of mass with respect to the monomer mixture.
従来、下水、し尿等で生じる有機性汚泥の脱水に対しては、カチオン性高分子凝集剤が広く使用され、その後両性高分子凝集剤が提案されている（特許文献１）。近年では下水処理場が脱水ケーキの含水率低下を要求する傾向が強く、上記の単なるカチオン性あるいは両性高分子では対応ができない状況である。また下水余剰汚泥や下水消化汚泥のように繊維分の少ないいわゆる難脱水汚泥では、特別の性能を要する凝集剤が必要になり、二種以上配合する凝集剤が提案される所以である。例えば特許文献２は、メタアクリル系カチオンポリマー（Ａ）と（メタ）アクリル系両性ポリマーが、特許文献３ではカチオン性高分子（Ａ）と、酸基の３〜３０モル％がアルカリにより中和されてなるアニオン性単量体単位を含む両性高分子（Ｂ）の配合が、さらに特許文献４では、カチオン化度を規定し、カチオン性基とアニオン性基の比率を規定した両性高分子との配合をそれぞれ提案している。これらは上記いわゆる難脱水汚泥の処理を意図したものであるが、下水処理場の脱水ケーキ含水率低下の要求には到底満足されるものではない。また上記いわゆる難脱水汚泥には、架橋あるいは分岐した水溶性高分子が有効とされているが（特許文献５など）、薬剤添加量が増加し処理コストを押し上げるのが問題となっている。配合する場合は、工場における生産性が悪く、また架橋あるいは分岐した水溶性高分子は、優れた汚泥脱水剤であるが、薬剤添加量が増加し処理コストを押し上げる。この問題をなんとか解決できないかが課題として存在するのが現状である。
本発明の課題は、下水処理場における下水余剰汚泥や下水消化汚泥のように繊維分の少ない所謂難脱水汚泥に対し、脱水ケーキ含水率低下の要求を満足し、
架橋あるいは分岐した水溶性高分子においても添加量増加を極力抑えた汚泥脱水剤を開発することである。
The problem of the present invention is to satisfy the requirement of dewatering cake moisture content reduction for so-called hardly dewatered sludge with low fiber content such as sewage surplus sludge and sewage digested sludge in a sewage treatment plant,
The aim is to develop a sludge dewatering agent that minimizes the increase in the amount of water-soluble polymer that has been crosslinked or branched.
上記課題を解決するため鋭意検討をした結果、以下に述べる発明に到達した。すなわち請求項１の発明は、下記一般式（１）および／または下記一般式（２）で表されるカチオン性単量体、（メタ）アクリルアミド、および下記一般式（３）で表されるアニオン性単量体１〜５モル％の単量体混合物を重合した両性水溶性高分子であり、当該両性水溶性高分子の０．２質量％水溶液をＡＱＶ、０．５質量％１Ｎ食塩水溶液中粘度をＳＬＶとすると、両方の比が３０≦ＡＱＶ／ＳＬＶ≦１００（２５℃において）であり、重量平均分子量が３００万〜１０００万である両性水溶性高分子を含有する汚泥脱水剤である。
Ｒ１は水素又はメチル基、Ｒ２およびＲ３は炭素数１〜３のアルキル基、アルコキシ基あるいはベンジル基、Ｒ４は水素、炭素数１〜３のアルキル基、アルコキシル基あるいはベンジル基であり、同種でも異種でも良い。Ａは酸素またはＮＨ、Ｂは炭素数２〜４のアルキレン基またはアルコキシレン基、Ｘ１は陰イオンをそれぞれ表わす。
Ｒ４は水素又はメチル基、Ｒ５、Ｒ６は炭素数１〜３のアルキル基、あるいはベンジル基、Ｘ２ −は陰イオンをそれぞれ表す。
Ｒ８は水素またはＣＨ２ＣＯＯ−Ｙ２、ＱはＳＯ３ −、Ｃ６Ｈ５ＳＯ３ −、
ＣＯＮＨＣ（ＣＨ２）２ＣＨ２ＳＯ３ −、Ｃ６Ｈ５ＣＯＯ−あるいはＣＯＯ−、Ｒ９は水素、メチル基またはＣＯＯＹ２であり、Ｙ１、Ｙ２は水素または陽イオンをそれぞれ表わす。
As a result of intensive studies to solve the above problems, the inventors have reached the invention described below. That is, the invention of claim 1 is a cationic monomer represented by the following general formula (1) and / or the following general formula (2), (meth) acrylamide, and an anion represented by the following general formula (3). An amphoteric water-soluble polymer obtained by polymerizing a monomer mixture of 1 to 5 mol% of an ionic monomer, and a 0.2 wt% aqueous solution of the amphoteric water soluble polymer in AQV and 0.5 wt% 1N saline solution. When the viscosity is SLV, the ratio is 30 ≦ AQV / SLV ≦ 100 (at 25 ° C.), and the sludge dewatering agent contains an amphoteric water-soluble polymer having a weight average molecular weight of 3 million to 10 million .
R 1 is hydrogen or a methyl group, R 2 and R 3 are an alkyl group having 1 to 3 carbon atoms, an alkoxy group or a benzyl group, and R 4 is hydrogen, an alkyl group having 1 to 3 carbon atoms, an alkoxyl group or a benzyl group. , Same or different. A represents oxygen or NH, B represents an alkylene group or alkoxylene group having 2 to 4 carbon atoms, and X 1 represents an anion.
R 4 represents hydrogen or a methyl group, R 5 and R 6 each represent an alkyl group having 1 to 3 carbon atoms, or a benzyl group, and X 2 − represents an anion.
R 8 is hydrogen or CH 2 COO — Y 2 , Q is SO 3 − , C 6 H 5 SO 3 − ,
CONHC (CH 2 ) 2 CH 2 SO 3 − , C 6 H 5 COO − or COO − , R 9 is hydrogen, a methyl group or COOY 2 , and Y 1 and Y 2 each represent hydrogen or a cation.
請求項２の発明は、前記両性水溶性高分子が、前記単量体混合物の水溶液を調製した後、界面活性剤により水に非混和性有機液体を連続相、該単量体混合物水溶液を分散相となるよう乳化し、重合して製造された油中水型エマルジョンであることを特徴とする請求項１に記載の汚泥脱水剤である。 In the invention of claim 2, the amphoteric water-soluble polymer is prepared by preparing an aqueous solution of the monomer mixture, then dispersing a water-immiscible organic liquid in a continuous phase with a surfactant and dispersing the aqueous monomer mixture solution. The sludge dewatering agent according to claim 1 , wherein the sludge dewatering agent is a water-in-oil emulsion produced by emulsifying and polymerizing into a phase.
請求項３の発明は、前記界面活性剤が、ＨＬＢ（親水性疎水性バランス）１０〜１５の親水性界面活性剤であることを特徴とする請求項２に記載の汚泥脱水剤である。 A third aspect of the present invention, prior Symbol surfactant is a sludge dehydrating agent of claim 2, characterized in that the hydrophilic surfactant HLB (hydrophilic hydrophobic balance) 10-15.
請求項４の発明は、下記一般式（１）および／または下記一般式（２）で表されるカチオン性単量体、（メタ）アクリルアミド、および下記一般式（３）で表されるアニオン性単量体１〜５モル％の単量体混合物を重合した両性水溶性高分子であり、当該両性水溶性高分子の０．２質量％水溶液をＡＱＶ、０．５質量％１Ｎ食塩水溶液中粘度をＳＬＶとすると、両方の比が３０≦ＡＱＶ／ＳＬＶ≦１００（２５℃において）であり、重量平均分子量が３００万〜１０００万である両性水溶性高分子を含有する汚泥脱水剤を、汚泥に添加し脱水処理することを特徴とする汚泥脱水方法である。
Ｒ１は水素又はメチル基、Ｒ２およびＲ３は炭素数１〜３のアルキル基、アルコキシ基あるいはベンジル基、Ｒ４は水素、炭素数１〜３のアルキル基、アルコキシル基あるいはベンジル基であり、同種でも異種でも良い。Ａは酸素またはＮＨ、Ｂは炭素数２〜４のアルキレン基またはアルコキシレン基、Ｘ１は陰イオンをそれぞれ表わす。
Ｒ４は水素又はメチル基、Ｒ５、Ｒ６は炭素数１〜３のアルキル基、あるいはベンジル基、Ｘ２ −は陰イオンをそれぞれ表す。
Ｒ８は水素またはＣＨ２ＣＯＯ−Ｙ２、ＱはＳＯ３ −、Ｃ６Ｈ５ＳＯ３ −、
ＣＯＮＨＣ（ＣＨ２）２ＣＨ２ＳＯ３ −、Ｃ６Ｈ５ＣＯＯ−あるいはＣＯＯ−、Ｒ９は水素、メチル基またはＣＯＯＹ２であり、Ｙ１、Ｙ２は水素または陽イオンをそれぞれ表わす。
The invention of claim 4 is a cationic monomer represented by the following general formula (1) and / or the following general formula (2), (meth) acrylamide, and an anionic property represented by the following general formula (3). It is an amphoteric water-soluble polymer obtained by polymerizing a monomer mixture of 1 to 5 mol% of a monomer. A 0.2% by mass aqueous solution of the amphoteric water-soluble polymer is AQV and a viscosity in a 0.5% by mass 1N saline solution. SLV is 30 ≦ AQV / SLV ≦ 100 (at 25 ° C.), and a sludge dewatering agent containing an amphoteric water-soluble polymer having a weight average molecular weight of 3 million to 10 million is added to sludge. It is a sludge dewatering method characterized by adding and dewatering.
R 1 is hydrogen or a methyl group, R 2 and R 3 are an alkyl group having 1 to 3 carbon atoms, an alkoxy group or a benzyl group, and R 4 is hydrogen, an alkyl group having 1 to 3 carbon atoms, an alkoxyl group or a benzyl group. , Same or different. A represents oxygen or NH, B represents an alkylene group or alkoxylene group having 2 to 4 carbon atoms, and X 1 represents an anion.
R 4 represents hydrogen or a methyl group, R 5 and R 6 each represent an alkyl group having 1 to 3 carbon atoms, or a benzyl group, and X 2 − represents an anion.
R 8 is hydrogen or CH 2 COO — Y 2 , Q is SO 3 − , C 6 H 5 SO 3 − ,
CONHC (CH 2 ) 2 CH 2 SO 3 − , C 6 H 5 COO − or COO − , R 9 is hydrogen, a methyl group or COOY 2 , and Y 1 and Y 2 each represent hydrogen or a cation.
請求項５の発明は、無機凝集剤を併用することを特徴とする請求項４に記載の汚泥脱水方法である。 The invention of claim 5 is the sludge dewatering method according to claim 4 , wherein an inorganic flocculant is used in combination.
本発明の汚泥脱水剤は、下記一般式（１）および／または下記一般式（２）で表されるカチオン性単量体、（メタ）アクリルアミド、および下記一般式（３）で表されるアニオン性単量体１〜５モル％の単量体混合物を重合した両性水溶性高分子を含有することを特徴とする。また前記単量体混合物に対しいずれも質量換算で連鎖移動剤を１００〜１，０００ｐｐｍ、架橋剤を５〜１００ｐｐｍ共存させ架橋性の両性水溶性高分子を重合することもできる。従来、両性高分子凝集剤というとアニオン性単量体を５〜２０モル％の範囲で共重合させる重合物であった。しかし両性高分子凝集剤の機能は、分子内あるいは分子間イオンコンプレックスを形成させ、見掛けの分子量を増加させ凝集力を高める、あるいは生成したイオンコンプレックスの疎水的な性質（イオン結合により高分子のイオン性が減少するため）を利用してフロック径やフロック強度の調節を行うものである。 The sludge dehydrating agent of the present invention includes a cationic monomer represented by the following general formula (1) and / or the following general formula (2), (meth) acrylamide, and an anion represented by the following general formula (3) It is characterized by containing an amphoteric water-soluble polymer obtained by polymerizing a monomer mixture of 1 to 5 mol% of a polymerizable monomer. Moreover, 100 to 1,000 ppm of chain transfer agent and 5 to 100 ppm of a crosslinking agent can coexist in terms of mass with respect to the monomer mixture to polymerize a crosslinkable amphoteric water-soluble polymer. Conventionally, an amphoteric polymer flocculant was a polymer obtained by copolymerizing an anionic monomer in the range of 5 to 20 mol%. However, the function of the amphoteric polymer flocculant is to form an intramolecular or intermolecular ion complex, increase the apparent molecular weight and increase the cohesive force, or the hydrophobic properties of the resulting ion complex (ionic ions of the polymer due to ionic bonds). The floc diameter and the floc strength are adjusted by using the method.
従ってアニオン性単量体は、上記範囲の共重合率は必ずしも必要ではなく、カチオン性基が無駄に使用されるだけでなく、返って凝集剤の性能を低下させる場合もある。汚泥はアニオン性の安定な親水性コロイドであり、凝集処理にはカチオン性基による表面電荷の中和が不可欠である。分子内のアニオン性基自体は、汚泥の表面電荷の中和作用には直接的な関係はない。本発明に掛かる両性水溶性高分子は、イオンコンプレックスの形成など効果の増強に作用するために必要なだけのアニオン性基を導入した。その結果余分なアニオン性基によってカチオン性基の消費の減少し、処理添加量も削減することができた。 Therefore, the anionic monomer does not necessarily require a copolymerization rate in the above range, and not only the cationic group is wasted but also the performance of the flocculant may be lowered. Sludge is an anionic and stable hydrophilic colloid, and neutralization of the surface charge by cationic groups is indispensable for the coagulation treatment. The anionic group in the molecule itself is not directly related to the neutralizing action of the sludge surface charge. The amphoteric water-soluble polymer according to the present invention introduced anionic groups as much as necessary to act to enhance effects such as the formation of ion complexes. As a result, the consumption of the cationic group was reduced by the excess anionic group, and the amount of treatment added could be reduced.
さらにアニオン性を減少させることによって、架橋剤の架橋反応も向上し架橋剤の添加量が同じなら架橋度が増加することが分かった。これは電荷内包率を測定することで確認することができた。以上の理由により本発明に掛かる両性水溶性高分子は、従来に較べ優れた凝集性能を発揮し、難脱水汚泥に対しても十分な凝集と脱水ケーキ含水率を達成できる。
Ｒ１は水素又はメチル基、Ｒ２およびＲ３は炭素数１〜３のアルキル基、アルコキシ基あるいはベンジル基、Ｒ４は水素、炭素数１〜３のアルキル基、アルコキシル基あるいはベンジル基であり、同種でも異種でも良い。Ａは酸素またはＮＨ、Ｂは炭素数２〜４のアルキレン基またはアルコキシレン基、Ｘ１は陰イオンをそれぞれ表わす。
Ｒ４は水素又はメチル基、Ｒ５、Ｒ６は炭素数１〜３のアルキル基、あるいはベンジル基、Ｘ２ −は陰イオンをそれぞれ表す。
Ｒ８は水素またはＣＨ２ＣＯＯ−Ｙ２、ＱはＳＯ３ −、Ｃ６Ｈ５ＳＯ３ −、
ＣＯＮＨＣ（ＣＨ２）２ＣＨ２ＳＯ３ −、Ｃ６Ｈ５ＣＯＯ−あるいはＣＯＯ−、Ｒ９は水素、メチル基またはＣＯＯＹ２であり、Ｙ１、Ｙ２は水素または陽イオンをそれぞれ表わす。
Furthermore, it was found that by reducing the anionic property, the crosslinking reaction of the crosslinking agent was also improved, and the degree of crosslinking increased if the amount of the crosslinking agent added was the same. This could be confirmed by measuring the charge inclusion rate. For the reasons described above, the amphoteric water-soluble polymer according to the present invention exhibits excellent flocculation performance as compared with the prior art, and can achieve sufficient flocculation and dehydrated cake moisture content even for hardly dewatered sludge.
R 1 is hydrogen or a methyl group, R 2 and R 3 are an alkyl group having 1 to 3 carbon atoms, an alkoxy group or a benzyl group, and R 4 is hydrogen, an alkyl group having 1 to 3 carbon atoms, an alkoxyl group or a benzyl group. , Same or different. A represents oxygen or NH, B represents an alkylene group or alkoxylene group having 2 to 4 carbon atoms, and X 1 represents an anion.
R 4 represents hydrogen or a methyl group, R 5 and R 6 each represent an alkyl group having 1 to 3 carbon atoms, or a benzyl group, and X 2 − represents an anion.
R 8 is hydrogen or CH 2 COO — Y 2 , Q is SO 3 − , C 6 H 5 SO 3 − ,
CONHC (CH 2 ) 2 CH 2 SO 3 − , C 6 H 5 COO − or COO − , R 9 is hydrogen, a methyl group or COOY 2 , and Y 1 and Y 2 each represent hydrogen or a cation.
本発明の両性水溶性高分子を製造するために、重合時あるいは重合後に構造改質剤、すなわち高分子を構造変性する架橋性単量体を使用する。この架橋性単量体は、単量体総量に対し質量換算で５〜１００ｐｐｍ、また好ましくは１０〜５０ｐｐｍ存在させる。架橋性単量体の例としては、Ｎ，Ｎ−メチレンビス（メタ）アクリルアミド、トリアリルアミン、ジメタクリル酸エチレングリコール、ジメタクリル酸ジエチレングリコール、ジメタクリル酸トリエチレングリコール、ジメタクリル酸テトラエチレングリコール、ジメタクリル酸―１，３−ブチレングリコール、ジ（メタ）アクリル酸ポリエチレングリコール、Ｎ−ビニル（メタ）アクリルアミド、Ｎ−メチルアリルアクリルアミド、アクリル酸グリシジル、ポリエチレングリコールジグリシジルエーテル、アクロレイン、グリオキザール、ビニルトリメトキシシランなどがあるが、この場合の架橋剤としては、水溶性ポリビニル化合物がより好ましく、最も好ましいのはＮ，Ｎ−メチレンビス（メタ）アクリルアミドである。またギ酸ナトリウム、イソプロピルアルコール、メタリルスルホン酸ナトリウム等の連鎖移動剤を併用することも架橋性を調節する手法として効果的である。添加量としては、単量体総量に対し質量換算で１００〜１，０００ｐｐｍ、また好ましくは２００〜７００ｐｐｍ存在させる。 In order to produce the amphoteric water-soluble polymer of the present invention, a structural modifier, that is, a crosslinkable monomer that structurally modifies the polymer is used during or after polymerization. This crosslinkable monomer is present in an amount of 5 to 100 ppm, preferably 10 to 50 ppm in terms of mass relative to the total amount of monomers. Examples of the crosslinkable monomer include N, N-methylenebis (meth) acrylamide, triallylamine, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, and dimethacrylic acid. Acid-1,3-butylene glycol, polyethylene glycol di (meth) acrylate, N-vinyl (meth) acrylamide, N-methylallylacrylamide, glycidyl acrylate, polyethylene glycol diglycidyl ether, acrolein, glyoxal, vinyltrimethoxysilane In this case, the crosslinking agent is more preferably a water-soluble polyvinyl compound, and most preferably N, N-methylenebis (meth) acrylamide. Also, using a chain transfer agent such as sodium formate, isopropyl alcohol, sodium methallyl sulfonate, etc. is also effective as a method for adjusting the cross-linking property. The amount added is 100 to 1,000 ppm, preferably 200 to 700 ppm in terms of mass relative to the total amount of monomers.
本発明の両性水溶性高分子は、アニオン性が低いことが特徴であるが、架橋性の両性水溶性高分子を合成し、それを汚泥脱水剤として使用することもできる。
架橋性水溶性高分子は、前に述べたように難脱水性汚泥に対し優れた凝集性能を有するが、脱水ケーキの含水率を低下させるには直鎖水溶性高分子に較べ添加量が増加する。低アニオン性の両性水溶性高分子にすることと、架橋性水溶性高分子にすることの関係について以下説明する。直鎖状水溶性高分子は伸びた状態にあり、そこに懸濁粒子を吸着させ生成した凝集フロックは、大きいがふわふわして強固になりにくい。強度を増すため添加量を増加していってもフロックの改善はない。その原因は、伸びた状態にあるため懸濁粒子との接触サイトが多く、その結果見かけ上の電荷的飽和になりやすい。攪拌強度を増加させ生成フロックを破壊し新しい吸着面を作ればよいが、上記のような現象がまた起こり、結局小さく強固なフロックは生成しない。
The amphoteric water-soluble polymer of the present invention is characterized by low anionicity, but a cross-linkable amphoteric water-soluble polymer can be synthesized and used as a sludge dehydrating agent.
As mentioned earlier, crosslinkable water-soluble polymers have excellent coagulation performance against difficult-to-dehydrate sludge, but the amount added is increased compared to linear water-soluble polymers to reduce the water content of dehydrated cake. To do. The relationship between making a low anionic amphoteric water-soluble polymer and making it a cross-linkable water-soluble polymer will be described below. The linear water-soluble polymer is in an extended state, and the aggregated floc produced by adsorbing the suspended particles therein is large but fluffy and difficult to become strong. Even if the amount added is increased to increase the strength, there is no improvement in floc. The cause of this is an extended state, so there are many contact sites with the suspended particles, and as a result, apparent charge saturation is likely to occur. It is only necessary to increase the agitation strength and destroy the generated floc to create a new adsorption surface. However, the above phenomenon occurs again, and eventually a small and strong floc is not generated.
これに対し架橋性水溶性高分子が汚泥中に添加されると懸濁粒子に吸着し、粒子同士の接着剤として作用し結果として粒子の凝集が起こる。この時「密度の詰まった」分子形態であるため粒子表面と多点で結合し、より締った強度の高いフロックを形成すると推定される。多点で結合することは、懸濁粒子への吸着性能が優れ、そのため未吸着の水溶性高分子が少なく、汚泥中に遊離せず汚泥粘性の増加が発生しない。またまるまった形態をした分子の内側に存在するカチオン性基は、懸濁粒子の電荷中和には寄与せず、見かけ上カチオン化度の低い分子として作用し、カチオン性飽和による再分散作用は少なくなる。結果として小さなサイズで絞まった強固なフロックが形成され機械脱水時、水切れが良くケーキ含水率が低下すると考えられる。 In contrast, when a crosslinkable water-soluble polymer is added to the sludge, it adsorbs to the suspended particles and acts as an adhesive between the particles, resulting in aggregation of the particles. At this time, it is presumed that since it is in a “dense packed” molecular form, it binds to the particle surface at multiple points to form a tighter and stronger floc. Bonding at multiple points is excellent in adsorption performance to suspended particles, so that there are few unadsorbed water-soluble polymers, they are not released into sludge, and sludge viscosity does not increase. In addition, the cationic group present inside the molecule in a round shape does not contribute to charge neutralization of the suspended particles, but acts as a molecule with an apparently low degree of cationization, and is redispersed by cationic saturation. Will be less. As a result, it is considered that a strong floc that has been squeezed with a small size is formed, and when the machine is dehydrated, the water drainage is good and the moisture content of the cake is reduced.
一方、本発明において両性水溶性高分子は、アニオン性単量体の共重合率を１〜５モル％と少量に限定している。この理由として以下のように論理付けられる。従来、両性高分子凝集剤というとアニオン性単量体を５〜２０モル％の範囲で共重合させる重合物が多かった。しかし両性高分子凝集剤の機能は、分子内あるいは分子間イオンコンプレックスを形成させ、見掛けの分子量を増加させ凝集力を高める、あるいは生成したイオンコンプレックスの疎水的な性質（イオン結合により高分子のイオン性が減少するため）を利用してフロック径やフロック強度の調節を行うものである。 On the other hand, in the present invention, the amphoteric water-soluble polymer limits the copolymerization rate of the anionic monomer to a small amount of 1 to 5 mol%. The reason is logical as follows. Conventionally, amphoteric polymer flocculants were often polymerized by copolymerizing anionic monomers in the range of 5 to 20 mol%. However, the function of the amphoteric polymer flocculant is to form an intramolecular or intermolecular ion complex, increase the apparent molecular weight and increase the cohesive force, or the hydrophobic properties of the resulting ion complex (ionic ions of the polymer due to ionic bonds). The floc diameter and the floc strength are adjusted by using the method.
従ってアニオン性単量体は、上記範囲の共重合率は必ずしも必要ではなく、カチオン性基が無駄に使用されるだけでなく、返って凝集剤の性能を低下させる場合もある。汚泥はアニオン性の安定な親水性コロイドであり、凝集処理にはカチオン性基による表面電荷の中和が不可欠である。分子内アニオン性基自体は、汚泥の表面電荷の中和作用には直接的な関係はない。本発明に掛かる両性水溶性高分子は、イオンコンプレックスの形成など効果の増強に作用するために必要なだけのアニオン性基を導入した。その結果余分なアニオン性基によってカチオン性基の消費が減少し、処理添加量も削減することができた。 Therefore, the anionic monomer does not necessarily require a copolymerization rate in the above range, and not only the cationic group is wasted but also the performance of the flocculant may be lowered. Sludge is an anionic and stable hydrophilic colloid, and neutralization of the surface charge by cationic groups is indispensable for the coagulation treatment. The intramolecular anionic group itself is not directly related to the neutralizing action of the sludge surface charge. The amphoteric water-soluble polymer according to the present invention introduced anionic groups as much as necessary to act to enhance effects such as the formation of ion complexes. As a result, the consumption of cationic groups was reduced by the excess anionic group, and the amount of treatment added could be reduced.
さらにアニオン性を減少させることによって、架橋性単量体の架橋反応も向上し架橋剤の添加量が同じなら架橋度が増加することが分かった。これは実施例でも示されるように電荷内包率を測定することで確認することができた。以上の理由により本発明に掛かる両性水溶性高分子は、従来に較べ優れた凝集性能を発揮し、難脱水汚泥に対しても十分な凝集と脱水ケーキ含水率を達成できる。 Further, it was found that by reducing the anionic property, the crosslinking reaction of the crosslinkable monomer was also improved, and the degree of crosslinking was increased if the addition amount of the crosslinking agent was the same. This could be confirmed by measuring the charge inclusion rate as shown in the examples. For the reasons described above, the amphoteric water-soluble polymer according to the present invention exhibits excellent flocculation performance as compared with the prior art, and can achieve sufficient flocculation and dehydrated cake moisture content even for hardly dewatered sludge.
両性水溶性高分子を製造するため使用するカチオン性単量体は、前記一般式（１）で表わされる単量体である。すなわちカチオン性単量体の例として（メタ）アクリロイルオキシアルキル４級アンモニウム塩である（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）アクリロイルオキシ−２−ヒドロキシプロピルトリメチルアンモニウムクロライドなどであり、また（メタ）アクリロイルオキシアルキル３級アミン塩としては、（メタ）アクリロイルオキシエチルジメチルアミン硫酸塩、（メタ）アクリロイルオキシプロピルジメチルアミン塩酸塩などである。また（メタ）アクリロイルアミノアルキル４級アンモニウム塩としては、（メタ）アクリロイルアミノプロピルトリメチルアンモニウムクロライド、（メタ）アクリロイルアミノプロピルトリメチルアンモニウムメチルサルフェートなどである。さらに（メタ）アクリロイルアミノ（ヒドロキシ）アルキル３級アミン塩の（メタ）アクリロイルアミノエチルジメチルアミン塩酸塩などである。また前記一般式（２）で表わされる単量体の例としてジアリルジメチルアンモニウム塩、ジアリルメチルベンジルアンモニウム塩、ジアリルジエチルアンモニウム塩などである。 The cationic monomer used for producing the amphoteric water-soluble polymer is a monomer represented by the general formula (1). That is, as examples of the cationic monomer, (meth) acryloyloxyethyltrimethylammonium chloride which is a (meth) acryloyloxyalkyl quaternary ammonium salt, (meth) acryloyloxyethyldimethylbenzylammonium chloride, (meth) acryloyloxy-2- Examples thereof include hydroxypropyltrimethylammonium chloride, and examples of the (meth) acryloyloxyalkyl tertiary amine salt include (meth) acryloyloxyethyldimethylamine sulfate and (meth) acryloyloxypropyldimethylamine hydrochloride. Examples of the (meth) acryloylaminoalkyl quaternary ammonium salt include (meth) acryloylaminopropyltrimethylammonium chloride and (meth) acryloylaminopropyltrimethylammonium methyl sulfate. Further, (meth) acryloylamino (hydroxy) alkyl tertiary amine salt (meth) acryloylaminoethyldimethylamine hydrochloride and the like. Examples of the monomer represented by the general formula (2) include diallyldimethylammonium salt, diallylmethylbenzylammonium salt and diallyldiethylammonium salt.
アニオン性単量体の例は、ビニルスルホン酸、ビニルベンゼンスルホン酸あるいは２−アクリルアミド２−メチルプロパンスルホン酸、メタクリル酸、アクリル酸、イタコン酸、マレイン酸あるいはｐ−カルボキシスチレンなどである。 Examples of the anionic monomer are vinyl sulfonic acid, vinyl benzene sulfonic acid or 2-acrylamido 2-methylpropane sulfonic acid, methacrylic acid, acrylic acid, itaconic acid, maleic acid or p-carboxystyrene.
両性水溶性高分子を製造する場合、非イオン性単量体を共重合してもよくその例としては以下のようなものがある。すなわちアクリルアミド、Ｎ，Ｎ−ジメチルアクリルアミド、酢酸ビニル、アクリロニトリル、アクリル酸メチル、（メタ）アクリル酸２−ヒドロキシエチル、ジアセトンアクリルアミド、Ｎ−ビニルピロリドン、Ｎ−ビニルホルムアミド、Ｎ−ビニルアセトアミド、アクリロイルモルホリンなどがあげられる。 In producing an amphoteric water-soluble polymer, a nonionic monomer may be copolymerized, and examples thereof include the following. That is, acrylamide, N, N-dimethylacrylamide, vinyl acetate, acrylonitrile, methyl acrylate, 2-hydroxyethyl (meth) acrylate, diacetone acrylamide, N-vinylpyrrolidone, N-vinylformamide, N-vinylacetamide, acryloylmorpholine Etc.
これら両性水溶性高分子におけるカチオン性単量体のモル％は、１０〜９５モル％であることが好ましく、更に好ましくは２０〜９５モル％である。またアニオン性単量体のモル％は、１〜５モル％であり、好ましくは２〜５モル％である。また分子量は重量平均分子量で３００万〜１５００万であり、好ましくは３００万〜１０００万である。 The mol% of the cationic monomer in these amphoteric water-soluble polymers is preferably 10 to 95 mol%, more preferably 20 to 95 mol%. Moreover, the mol% of an anionic monomer is 1-5 mol%, Preferably it is 2-5 mol%. The molecular weight is 3 million to 15 million in weight average molecular weight, preferably 3 million to 10 million.
本発明の両性水溶性高分子は、重合する前の単量体混合物に対し、いずれも質量換算で連鎖移動剤を１００〜１，０００ｐｐｍ、架橋剤を５〜１００ｐｐｍ共存させ架橋性の両性水溶性高分子を合成することもできる。その０．２質量％水溶液粘度をＡＱＶ、前記両性水溶性高分子の０．５質量％１Ｎ食塩水溶液中粘度をＳＬＶとすると、両方の比が
３０≦ＡＱＶ／ＳＬＶ≦１００（２５℃において）
であることが好ましい。この数値は架橋の度合いを表すのに使用することができる。架橋性のイオン性水溶性高分子は、分子内で架橋しているために、水中においても分子が広がりにくい性質を有し、直鎖状高分子に較べれば水中での広がりは小さいはずであるが、架橋度が増加するに従い、Ｂ型粘度計（回転粘度計の一種）に測定した場合の粘度は大きくなる。この原因はＢ型粘度計のローター（測定時の回転子）と溶液との摩擦かあるいは絡み合いによるものと推定されるが正確には不明である。一方、架橋性のイオン性水溶性高分子の塩水中の粘度は、架橋度が増加するに従い低下していく。架橋によって分子が収縮しているので、塩水の多量のイオンによってその影響をより大きく受けるものと考えられる。従ってこれらの理由によって二つの粘度測定値の比、ＡＱＶ／ＳＬＶは、架橋度が高くなるに従い大きくなる（架橋がさらに進み水不溶性になった場合は、この関係は成り立たない）。本発明の架橋性の両性水溶性高分子では、この値は約３０〜１００程度になる。直鎖状の水溶性高分子、あるいは弱く架橋した水溶性高分子では、この値が１０から３０未満程度であることを考慮すると、本発明の架橋性の両性水溶性高分子は、高度に架橋した水溶性高分子であることが分かる。
The amphoteric water-soluble polymer of the present invention is a crosslinkable amphoteric water-soluble polymer in which 100 to 1,000 ppm of a chain transfer agent and 5 to 100 ppm of a crosslinking agent coexist in terms of mass with respect to the monomer mixture before polymerization. Polymers can also be synthesized. Assuming that the 0.2% by weight aqueous solution viscosity is AQV and the viscosity of the amphoteric water-soluble polymer in 0.5% by weight 1N saline solution is SLV, the ratio of both is
30 ≦ AQV / SLV ≦ 100 (at 25 ° C.)
It is preferable that This number can be used to represent the degree of crosslinking. Crosslinkable ionic water-soluble polymers are cross-linked in the molecule, and therefore have the property that molecules are difficult to spread in water, and should be less spread in water than linear polymers. However, as the degree of crosslinking increases, the viscosity when measured with a B-type viscometer (a type of rotational viscometer) increases. The cause is presumed to be due to friction or entanglement between the rotor of the B-type viscometer (rotor at the time of measurement) and the solution, but it is not exactly known. On the other hand, the viscosity of the crosslinkable ionic water-soluble polymer in salt water decreases as the degree of crosslinking increases. Since the molecules are contracted by the cross-linking, it is considered that the influence is greatly influenced by a large amount of ions of the salt water. Therefore, for these reasons, the ratio of the two viscosity measurements, AQV / SLV, increases as the degree of cross-linking increases (if the cross-linking progresses further and becomes water-insoluble, this relationship does not hold). In the crosslinkable amphoteric water-soluble polymer of the present invention, this value is about 30 to 100. In view of the fact that this value is about 10 to less than 30 for a linear water-soluble polymer or a weakly crosslinked water-soluble polymer, the crosslinkable amphoteric water-soluble polymer of the present invention is highly crosslinked. It can be seen that this is a water-soluble polymer.
また前述の電荷内包率に関しても説明する。電荷内包率は、以下のように定義される。すなわち
定義１）水溶性カチオン性高分子および両性でかつカチオン性単量体とアニオン性単量体共重合率の差が正である水溶性高分子の場合
電荷内包率[％]＝（１−α／β）×１００
αは酢酸にてｐＨ４．０に調整した水溶性カチオン性高分子あるいは両性水溶性高分子水溶液をポリビニルスルホン酸カリウム水溶液にて滴定した滴定量。βは酢酸にてｐＨ４．０に調整した水溶性カチオン性高分子あるいは両性水溶性高分子水溶液にポリビニルスルホン酸カリウム水溶液を前記水溶性カチオン性高分子あるいは両性水溶性高分子の電荷の中和を行うに十分な量加え、その後ポリジアリルジメチルアンモニウムクロライド水溶液にて滴定した滴定量をブランク値から差し引いた滴定量。ここでブランク値とは、水溶性カチオン性高分子あるいは両性水溶性高分子水溶液無添加時にポリビニルスルホン酸カリウム水溶液をポリジアリルジメチルアンモニウムクロライド水溶液にて滴定した滴定量である。
定義２）両性でかつカチオン性単量体とアニオン性単量体の共重合率の差が負である水溶性高分子の場合
電荷内包率[％]＝（１−α／β）×１００
αはアンモニアにてｐＨ１０．０に調整した水溶性両性高分子水溶液をポリジアリルジメチルアンモニウムクロライド水溶液にて滴定した滴定量。βはアンモニアにてｐＨ１０．０に調整した水溶性両性高分子水溶液にポリジアリルジメチルアンモニウムクロライド水溶液を前記水溶性両性高分子の電荷の中和を行うに十分な量加え、その後ポリビニルスルホン酸カリウム水溶液にて滴定した滴定量をブランク値から差し引いた滴定量。ここでブランク値とは、水溶性両性高分子水溶液無添加時にジアリルジメチルアンモニウムクロライド水溶液をポリビニルスルホン酸カリウム水溶液にて滴定した滴定量である。
Further, the above-described charge inclusion rate will be described. The charge inclusion rate is defined as follows. That is, definition 1) In the case of a water-soluble cationic polymer and an amphoteric and water-soluble polymer having a positive difference in the copolymerization rate between a cationic monomer and an anionic monomer, the charge inclusion rate [%] = (1− α / β) × 100
α is a titration amount obtained by titrating a water-soluble cationic polymer or an amphoteric water-soluble polymer aqueous solution adjusted to pH 4.0 with acetic acid with a potassium polyvinyl sulfonate aqueous solution. β is a water-soluble cationic polymer or an amphoteric water-soluble polymer aqueous solution adjusted to pH 4.0 with acetic acid, and an aqueous polyvinyl sulfonate potassium solution is used to neutralize the charge of the water-soluble cationic polymer or amphoteric water-soluble polymer. A titration amount obtained by adding a sufficient amount to perform, and then subtracting the titration amount titrated with an aqueous polydiallyldimethylammonium chloride solution from the blank value. Here, the blank value is a titration amount obtained by titrating a potassium polyvinylsulfonate aqueous solution with a polydiallyldimethylammonium chloride aqueous solution when no water-soluble cationic polymer or amphoteric water-soluble polymer aqueous solution was added.
Definition 2) Charge inclusion ratio [%] = (1−α / β) × 100 in the case of a water-soluble polymer that is amphoteric and has a negative difference in copolymerization rate between a cationic monomer and an anionic monomer
α is a titration amount obtained by titrating a water-soluble amphoteric polymer aqueous solution adjusted to pH 10.0 with ammonia with a polydiallyldimethylammonium chloride aqueous solution. β is a water-soluble amphoteric polymer aqueous solution adjusted to pH 10.0 with ammonia, and a polydiallyldimethylammonium chloride aqueous solution is added in an amount sufficient to neutralize the charge of the water-soluble amphoteric polymer, and then a potassium polyvinyl sulfonate aqueous solution Titration volume obtained by subtracting the titration volume titrated with the blank value. Here, the blank value is a titration amount obtained by titrating a diallyldimethylammonium chloride aqueous solution with a potassium polyvinyl sulfonate aqueous solution when no water-soluble amphoteric polymer aqueous solution was added.
すなわち電荷内包率の高い水溶性高分子は、架橋度が高まった水溶性高分子であり、電荷内包率の低い水溶性高分子は、架橋度が低い水溶性高分子であると言える。この理由は、以下の通りに説明される。直鎖状水溶性高分子は、希薄溶液中では、分子はほぼ「伸びきった」形状をしている。一方、架橋性水溶性高分子は、溶液中において粒子状の丸まった形状をしていて、粒子状の内部に存在するイオン性基は、外側には現われにくく、反対電荷との反応も緩慢に起こると考えられる。 That is, it can be said that a water-soluble polymer having a high charge encapsulation rate is a water-soluble polymer having a high degree of crosslinking, and a water-soluble polymer having a low charge encapsulation rate is a water-soluble polymer having a low crosslinking rate. The reason for this is explained as follows. A linear water-soluble polymer has a substantially “stretched” shape in a dilute solution. On the other hand, the crosslinkable water-soluble polymer has a rounded particle shape in the solution, and the ionic group present inside the particle is unlikely to appear on the outside and reacts slowly with the opposite charge. It is thought to happen.
ここで架橋性水溶性カチオン性高分子および、両性でかつカチオン性単量体とアニオン性単量体の共重合率の差が正である架橋性水溶性両性高分子に関しては、電荷内包率は以下のようになる。
電荷内包率[％]＝（１−α/β）×１００
滴定量αは、試料である架橋性カチオン性（両性）水溶性高分子に反対電荷を有するポリビニルスルホン酸カリウム水溶液を滴下して行き、水溶性カチオン性（両性）高分子の「表面」（粒子状の表面部）に存在するイオン性基にイオン的静電反応を行わせる操作を意味する。
For crosslinkable water-soluble cationic polymers and crosslinkable water-soluble amphoteric polymers that are amphoteric and have a positive difference in the copolymerization rate between the cationic monomer and the anionic monomer, the charge inclusion rate is It becomes as follows.
Charge inclusion rate [%] = (1−α / β) × 100
The titration amount α is obtained by dropping an aqueous solution of potassium polyvinyl sulfonate having an opposite charge onto a crosslinkable cationic (amphoteric) water-soluble polymer as a sample, and then “surface” (particles) of the water-soluble cationic (amphoteric) polymer. Meaning an ionic electrostatic reaction on an ionic group present on the surface portion.
次に架橋性カチオン性（両性）水溶性高分子の理論的な電荷量を中和するに十分な量以上の反対電荷を有するポリビニルスルホン酸カリウムを添加し、反応時間を十分取ったその後、余剰のポリビニルスルホン酸カリウムをジアリルジメチルアンモニウムクロライド水溶液により滴定する。また別に架橋性カチオン性（両性）水溶性高分子を添加しないでポリビニルスルホン酸カリウム溶液をジアリルジメチルアンモニウムクロライド水溶液により滴定し、ブランク値を出しておき、ブランク値より架橋性カチオン性（両性）水溶性高分子を添加した場合の滴定量を差し引き、この値がβとなる。β値は、架橋性カチオン性（両性）水溶性高分子の化学組成から計算される理論的な電荷量に相当すると考えられる。すなわち架橋性カチオン性（両性）水溶性高分子に対し、反対電荷が多量に存在するので、表面のカチオン性電荷だけでなく、内部の電荷まで静電的な中和反応が行われると考えられる。架橋度が高ければ、αはβに対し小さくなり、（１−α／β）値は、１に比べ大きくなり電荷内包率は大きい（すなわち架橋の度合いは高くなる）。 Next, potassium polyvinyl sulfonate having an opposite charge more than the amount sufficient to neutralize the theoretical charge amount of the crosslinkable cationic (amphoteric) water-soluble polymer was added, the reaction time was sufficient, and then the surplus Of polyvinyl sulfonate is titrated with an aqueous diallyldimethylammonium chloride solution. Separately, titrate the potassium polyvinyl sulfonate solution with diallyldimethylammonium chloride aqueous solution without adding a crosslinkable cationic (amphoteric) water-soluble polymer, and give a blank value. This value is β after subtracting the titration amount when the functional polymer is added. The β value is considered to correspond to the theoretical charge calculated from the chemical composition of the crosslinkable cationic (amphoteric) water-soluble polymer. In other words, the cross-linkable cationic (amphoteric) water-soluble polymer has a large amount of opposite charge, so it is considered that not only the surface cationic charge but also the internal charge is electrostatically neutralized. . If the degree of crosslinking is high, α is smaller than β, and the (1-α / β) value is larger than 1 and the charge inclusion rate is large (that is, the degree of crosslinking is high).
両性でかつカチオン性単量体とアニオン性単量体の共重合率の差が負である架橋性水溶性両性高分子の電荷内包率に関しても、上記とほぼ同じ内容で説明することができるが、アニオン性基を解離させるためアンモニアでｐＨをアルカリ性にするという違いだけがある。 The charge inclusion rate of the crosslinkable water-soluble amphoteric polymer that is amphoteric and has a negative difference in the copolymerization rate between the cationic monomer and the anionic monomer can be explained in the same manner as described above. The only difference is that the pH is made alkaline with ammonia to dissociate the anionic group.
ここでＡＱＶ／ＳＬＶと電荷内包率の数値の比較、また架橋した本発明のアニオン化度１から５モル％の両性水溶性高分子と従来のアニオン化度の高い両性水溶性高分子の架橋の程度に関して比較する。段落００００の実施例１で合成した表１に記載する試作品―３は、カチオン性単量体５０モル％、アニオン性単量体５モル％であり、ＡＱＶ／ＳＬＶ値は４０、電荷内包率は５０であり、比較的高度に架橋した水溶性高分子である。これに対し試作―１０は、イオン性は同様であり、架橋剤のない条件で重合したものでありＡＱＶ／ＳＬＶ値は１５、電荷内包率は１６％であり、ほぼ架橋のない水溶性高分子である。また比較例―３は、カチオン性単量体５０モル％で同じだが、アニオン化度が高く２０モル％である。ＡＱＶ／ＳＬＶ値と電荷内包率はそれぞれ２０と３０％であり、架橋の程度としては低い領域に入る。しかし架橋剤の量をみると単量体に対し質量比で４０ｐｐｍと試作―３に較べかなり多く添加しているが、架橋程度は低いことが示されている。すなわちアニオン化度あるいはイオン性を低下させることにより架橋度は、上がりやすくなることが分かる。原因は、架橋の掛かりやすいアクリルアミドが増えるためと推定はされるが、まだ確証はない。従って上記のことからも本発明の特徴を理解することができる。 Here, comparison of AQV / SLV and charge inclusion ratio values, and cross-linking of the crosslinked amphoteric water-soluble polymer of 1 to 5 mol% of the present invention and a conventional amphoteric water-soluble polymer having a high degree of anionization were carried out. Compare for degree. Prototype 3 described in Table 1 synthesized in Example 1 of paragraph 0000 is 50 mol% cationic monomer, 5 mol% anionic monomer, AQV / SLV value is 40, charge inclusion rate Is a relatively highly crosslinked water-soluble polymer. On the other hand, Prototype-10 has the same ionicity, polymerized under the condition without a crosslinking agent, has an AQV / SLV value of 15, a charge inclusion rate of 16%, and has almost no crosslinking. It is. Comparative Example 3 is the same at 50 mol% of the cationic monomer, but the degree of anionization is high and 20 mol%. The AQV / SLV value and the charge inclusion rate are 20 and 30%, respectively, and the degree of crosslinking falls into a low region. However, the amount of the crosslinking agent is 40 ppm by mass with respect to the monomer, which is considerably larger than that of Trial-3, but the degree of crosslinking is shown to be low. That is, it can be seen that the degree of crosslinking tends to increase by lowering the anionization degree or ionicity. The cause is presumed to be due to an increase in acrylamide, which is easily crosslinked, but there is no confirmation yet. Therefore, the features of the present invention can be understood from the above.
本発明における両性水溶性高分子の製品形態としては、粉末、油中水型エマルジョン、塩水溶液中分散液などどのような形態でも実施可能であるが、架橋性の水溶性高分子を重合する場合において、最も好ましい形態は油中水型エマルジョンである。 As the product form of the amphoteric water-soluble polymer in the present invention, any form such as a powder, a water-in-oil emulsion, or a dispersion in an aqueous salt solution can be used. However, when a crosslinkable water-soluble polymer is polymerized. The most preferred form is a water-in-oil emulsion.
粉末状の製品は、以下のようにして製造することができる。例えば塩水溶液中あるいは水に非混和性有機液体中にて分散重合した分散液、水溶液重合による粘性液体、あるいは単量体水溶液を高濃度で重合し流動性のない水性ゲル状物を得て、その後乾燥し造粒した粉末状とする。すなわち塩水中にて分散重合した分散液の場合は、直接乾燥機に入れ、一定時間乾燥し、塊状物を粉砕する方法がある。また水に非混和性有機液体中にて分散重合した分散液の場合は、非混和性有機液体を分離し、湿潤な重合粒子を乾燥機にて乾燥し粉末状とする。水溶液重合により生成した粘性液体は、水混和性有機液体により重合物を析出させ、それを乾燥し粉砕する。単量体を高濃度で水溶液重合した流動性のない水性ゲル状物の場合は、ミートチョッパーなどでゲル状物をミンチ化し、それを乾燥後、粉砕し粉末とする方法を採る。 The powdered product can be manufactured as follows. For example, a dispersion obtained by dispersion polymerization in a salt aqueous solution or water immiscible organic liquid, a viscous liquid obtained by aqueous solution polymerization, or a monomer aqueous solution is polymerized at a high concentration to obtain a non-flowable aqueous gel. Then, the powder is dried and granulated. That is, in the case of a dispersion polymerized by dispersion in salt water, there is a method in which the dispersion is directly put into a drier and dried for a certain time to crush the lump. In the case of a dispersion obtained by dispersion polymerization in water in an immiscible organic liquid, the immiscible organic liquid is separated, and wet polymer particles are dried in a dryer to form a powder. The viscous liquid produced by the aqueous solution polymerization precipitates a polymer with a water-miscible organic liquid, which is dried and pulverized. In the case of a non-flowable aqueous gel-like product obtained by polymerizing a monomer at a high concentration in water, the gel-like product is minced with a meat chopper, dried, pulverized and powdered.
油中水型エマルジョンの場合は、イオン性単量体、あるいはイオン性単量体、共重合可能な単量体及びこれら単量体に対し生成した重合体が水溶性を保つモル比で添加した架橋性単量体を含有する単量体混合物を水、少なくとも水と非混和性の炭化水素からなる油状物質、油中水型エマルジョンを形成するに有効な量とＨＬＢを有する少なくとも一種類の界面活性剤を混合し、強攪拌し油中水型エマルジョンを形成させ重合することにより合成する。 In the case of a water-in-oil emulsion, an ionic monomer, or an ionic monomer, a monomer that can be copolymerized, and a molar ratio that maintains a water-soluble polymer formed with these monomers are added. A monomer mixture containing a crosslinkable monomer is water, an oily substance comprising at least water-immiscible hydrocarbons, an amount effective to form a water-in-oil emulsion and at least one interface having an HLB It is synthesized by mixing the activator, stirring vigorously to form a water-in-oil emulsion and polymerizing.
また分散媒として使用する炭化水素からなる油状物質の例としては、パラフィン類あるいは灯油、軽油、中油などの鉱油、あるいはこれらと実質的に同じ範囲の沸点や粘度などの特性を有する炭化水素系合成油、あるいはこれらの混合物があげられる。含有量としては、油中水型エマルジョン全量に対して２０質量％〜５０質量％の範囲であり、好ましくは２０質量％〜３５質量％の範囲である。 Examples of oily substances composed of hydrocarbons used as dispersion media include paraffins, mineral oils such as kerosene, light oil, and middle oil, or hydrocarbon-based synthetics having characteristics such as boiling point and viscosity substantially in the same range as these. An oil or a mixture thereof may be mentioned. As content, it is the range of 20 mass%-50 mass% with respect to the water-in-oil type emulsion whole quantity, Preferably it is the range of 20 mass%-35 mass%.
油中水型エマルジョンを形成するに有効な量とＨＬＢを有する少なくとも一種類の界面活性剤の例としては、ＨＬＢ１〜１５のノニオン性界面活性剤であり、その具体例としては、ソルビタンモノオレ−ト、ソルビタンモノステアレ−ト、ソルビタンモノパルミテ−トなどがあげられる。これら界面活性剤の添加量としては、油中水型エマルジョン全量に対して０．５〜１０質量％であり、好ましくは１〜５質量％の範囲である。 Examples of at least one surfactant having an amount effective to form a water-in-oil emulsion and HLB are HLB 1-15 nonionic surfactants, specific examples of which include sorbitan monooleate Sorbitan monostearate, sorbitan monopalmitate and the like. The addition amount of these surfactants is 0.5 to 10% by mass, preferably 1 to 5% by mass, based on the total amount of the water-in-oil emulsion.
この場合、高ＨＬＢ界面活性剤により乳化させ、油中水型エマルジョンを成
させ重合したエマルジョンは、このままで水となじむので転相剤を添加する必
用がない。これら界面活性剤のＨＬＢは、９〜２０のもの、好ましくは１１〜
２０のものを使用する。高ＨＬＢ界面活性剤により乳化、重合した油中水型エ
マルジョンは、溶解が優れていて所謂フィッシュアイなどの未溶解粒子の発生
が少なく、ライン溶解し汚泥などの凝集処理対象物質に直接添加することがで
きる。そのような界面活性剤の例としては、カチオン性界面活性剤やＨＬＢ９
〜１５のノニオン性界面活性剤であり、ポリオキシエチレンポリオキシプロピ
レンアルキルエ−テル系、ポリオキシエチレンアルコールエ−テル系などであ
る。
In this case, an emulsion emulsified with a high HLB surfactant, formed into a water-in-oil emulsion and polymerized is compatible with water as it is, so there is no need to add a phase inversion agent. These surfactants have an HLB of 9-20, preferably 11-11.
20 things are used. A water-in-oil emulsion emulsified and polymerized with a high HLB surfactant is excellent in dissolution and generates less undissolved particles such as so-called fish eyes, and must be directly dissolved and added directly to substances subject to agglomeration such as sludge. Can do. Examples of such surfactants include cationic surfactants and HLB9
15 nonionic surfactants such as polyoxyethylene polyoxypropylene alkyl ether system, polyoxyethylene alcohol ether system and the like.
低ＨＬＢの界面活性剤により乳化、重合した場合は重合後転相剤と呼ばれる親水性界面化成剤を添加して油の膜で被われたエマルジョン粒子が水になじみ易くし、中の水溶性高分子が溶解しやすくする処理を行い、水で希釈しそれぞれの用途に用いる。親水性界面活性剤の例としては、カチオン性界面活性剤やＨＬＢ９〜１５のノニオン性界面活性剤であり、ポリオキシエチレンポリオキシプロピレンアルキルエ−テル系、ポリオキシエチレンアルコールエ−テル系などである。本発明に掛かる両性水溶性高分子は、高ＨＬＢ界面活性剤により乳化させ油中水型エマルジョンであることが好ましい。すなわち高ＨＬＢ界面活性剤を使用した場合、フィッシュアイなどを形成しにくく溶解性が良好であり、ライン溶解し、溶解液をそのまま汚泥に添加できるなどのメリットがある。添加量は油中水型エマルジョン液量に対し質量換算で０．５〜５％であり、好ましくは０．５〜２％である。 When emulsified and polymerized with a low-HLB surfactant, a hydrophilic interfacial modifier called a phase inversion agent is added after the polymerization to make the emulsion particles covered with the oil film easy to adapt to water, The molecule is treated so that it is easily dissolved, diluted with water and used for each application. Examples of hydrophilic surfactants are cationic surfactants and nonionic surfactants of HLB 9-15, such as polyoxyethylene polyoxypropylene alkyl ether systems and polyoxyethylene alcohol ether systems. is there. The amphoteric water-soluble polymer according to the present invention is preferably a water-in-oil emulsion emulsified with a high HLB surfactant. That is, when a high HLB surfactant is used, there is an advantage that it is difficult to form fish eyes and the like, the solubility is good, the line is dissolved, and the solution can be added to the sludge as it is. The addition amount is 0.5 to 5%, preferably 0.5 to 2% in terms of mass with respect to the amount of the water-in-oil emulsion.
塩水溶液中分散液の場合は、硫酸アンモニウムのような多価アニオン塩の水溶液を調製し、この中にカチオン性単量体、あるいは非イオン性単量体からなる混合物を仕込み、また、両性水溶性重合体の場合はアニオン性単量体をしこみ、分散剤として該塩水溶液に可溶な高分子分散剤を共存させ攪拌下、分散重合し合成することができる。 In the case of a dispersion in an aqueous salt solution, an aqueous solution of a polyvalent anion salt such as ammonium sulfate is prepared and charged with a mixture of a cationic monomer or a nonionic monomer. In the case of a polymer, an anionic monomer can be squeezed, and a polymer dispersant soluble in the aqueous salt solution can be used as a dispersant in the presence of stirring to carry out dispersion polymerization and synthesis.
高分子分散剤としては、非イオン性あるいはカチオン性高分子のいずれでも使用可能であるが、カチオン性高分子のほうがより好ましい。カチオン性高分子としては、アクリル系カチオン性単量体、たとえば、（メタ）アクリル酸ジメチルアミノエチルやジメチルアミノプロピル（メタ）アクリルアミドなどの無機酸や有機酸の塩、あるいは塩化メチルや塩化ベンジルによる四級アンモニウム塩とアクリルアミドとの共重合体である。例えば（メタ）アクリロイルオキシエチルトリメチルアンモニウム塩化物、（メタ）アクリロイルオキシ２−ヒドロキシプロピルトリメチルアンモニウム塩化物、（メタ）アクリロイルアミノプロピルトリメチルアンモニウム塩化物、（メタ）アクリロイルオキシエチルジメチルベンジルアンモニウム塩化物、（メタ）アクリロイルオキシ２−ヒドロキシプロピルジメチルベンジルアンモニウム塩化物、（メタ）アクリロイルアミノプロピルジメチルベンジルアンモニウム塩化物などがあげられ、これら単量体と非イオン性単量体との共重合体でも良い。またジメチルジアリルアンモニウム塩化物重合体などジアリルアミン系重合体でも使用できる。 As the polymer dispersant, either a nonionic or cationic polymer can be used, but a cationic polymer is more preferable. Cationic polymers include acrylic cationic monomers such as inorganic acid and organic acid salts such as dimethylaminoethyl (meth) acrylate and dimethylaminopropyl (meth) acrylamide, or methyl chloride and benzyl chloride. It is a copolymer of quaternary ammonium salt and acrylamide. For example, (meth) acryloyloxyethyltrimethylammonium chloride, (meth) acryloyloxy 2-hydroxypropyltrimethylammonium chloride, (meth) acryloylaminopropyltrimethylammonium chloride, (meth) acryloyloxyethyldimethylbenzylammonium chloride, ( Examples thereof include (meth) acryloyloxy 2-hydroxypropyldimethylbenzylammonium chloride, (meth) acryloylaminopropyldimethylbenzylammonium chloride, and a copolymer of these monomers and nonionic monomers may be used. Also, diallylamine polymers such as dimethyldiallylammonium chloride polymer can be used.
非イオン性高分子の例としては、上記非イオン性単量体の（共）重合体、ポリビニルアルコ−ル、スチレン／無水マレイン酸共重合物あるいはブテン／無水マレイン酸共重合物の完全アミド化物などである。 Examples of nonionic polymers include (co) polymers of the above nonionic monomers, polyvinyl alcohol, styrene / maleic anhydride copolymers or fully amidated products of butene / maleic anhydride copolymers. Etc.
上記イオン性高分子の分子量としては、５、０００から３００万、好ましくは５万から１５０万である。また、非イオン性高分子分の分子量としては、１，０００〜１００万であり、好ましくは１，０００〜５０万である。これら高分子分散剤の単量体に対する添加量は、１／１００〜１／１０であり、好ましくは２/１００〜５／１００である。 The molecular weight of the ionic polymer is 5,000 to 3 million, preferably 50,000 to 1.5 million. The molecular weight of the nonionic polymer is 1,000 to 1,000,000, preferably 1,000 to 500,000. The amount of these polymer dispersants added to the monomer is 1/100 to 1/10, preferably 2/100 to 5/100.
これら上記の種々重合は、重合は窒素雰囲気下にて、重合開始剤、例えば２、
２’−アゾビス（アミジノプロパン）二塩化水素化物または２、２’−アゾビ
ス〔２−（５−メチル−２−イミダゾリン−２−イル）プロパン〕二塩化水素
化物のような水溶性アゾ系重合開始剤、あるいは過硫酸アンモニウムおよび亜
硫酸水素ナトリウム併用のような水溶性レドックス系重合開始剤を添加し、撹
拌下あるいは無攪拌下ラジカル重合を行う。
These various polymerizations are carried out under a nitrogen atmosphere, with a polymerization initiator such as 2,
Initiation of water-soluble azo polymerization such as 2'-azobis (amidinopropane) dihydrochloride or 2,2'-azobis [2- (5-methyl-2-imidazolin-2-yl) propane] dihydrochloride A water-soluble redox polymerization initiator such as an agent or a combination of ammonium persulfate and sodium hydrogen sulfite is added, and radical polymerization is performed with or without stirring.
本発明の水溶性高分子組成物は、０．１質量％濃度の水溶液とした時の水溶液ｐＨが通常４．０以下、好ましくは３．０以下である。水溶液ｐＨが４．０を上回ると十分な性能が得られない。そのため酸性物質を配合する。この理由は二つある。すなわち両性水溶性高分子を配合するため溶液ｐＨが約５〜約９の範囲でイオンコンプレックスを形成し溶液が白濁する。このイオンコンプレックスが生成した状態で汚泥など処理対照に添加すると、性能が低下するためである。またｐＨが５付近より高い範囲では本発明で使用する（メタ）アクリル系水溶性高分子が加水分解を受け、劣化しやすくなる。０．１質量％濃度というのは、処理対象に添加する場合の下限に近い溶液濃度である。これら現象を防止するため水溶液のｐＨは４以下、１以上にすることが好ましい。 The water-soluble polymer composition of the present invention has an aqueous solution pH of usually 4.0 or less, preferably 3.0 or less when an aqueous solution having a concentration of 0.1% by mass is used. If the aqueous solution pH exceeds 4.0, sufficient performance cannot be obtained. Therefore, an acidic substance is blended. There are two reasons for this. That is, since an amphoteric water-soluble polymer is blended, an ion complex is formed in a solution pH range of about 5 to about 9, and the solution becomes cloudy. This is because when the ion complex is generated and added to a treatment control such as sludge, the performance decreases. In the range where the pH is higher than about 5, the (meth) acrylic water-soluble polymer used in the present invention is easily hydrolyzed and deteriorates. The 0.1 mass% concentration is a solution concentration close to the lower limit when added to the object to be treated. In order to prevent these phenomena, the pH of the aqueous solution is preferably 4 or less and 1 or more.
このような酸性物質の例として、無機あるいは有機の酸として塩酸、硫酸、酢酸、スルファミン酸、クエン酸、フマル酸、コハク酸、アジピン酸などである。これら酸性物質の添加量として水溶性高分子の固形分換算として、５〜２０質量％であり、好ましくは７〜１５質量％であり、０．１質量％濃度に溶解してもｐＨが４以下を確保できる。 Examples of such acidic substances include hydrochloric acid, sulfuric acid, acetic acid, sulfamic acid, citric acid, fumaric acid, succinic acid, adipic acid and the like as inorganic or organic acids. The addition amount of these acidic substances is 5 to 20% by mass, preferably 7 to 15% by mass in terms of solid content of the water-soluble polymer, and the pH is 4 or less even when dissolved in a concentration of 0.1% by mass. Can be secured.
本発明の架橋した両性水溶性高分子は、前述の理由によりアニオン化度を十分低下させてあることが特徴である。その結果アクリル酸などの連鎖移動の影響を受けずに架橋が進みやすく、同じ添加量の架橋性単量体により架橋の度合いが高まる。従来、両性水溶性高分子は、発明の詳細な説明中に「アニオン性単量体の共重合率として５から３０モル％が好ましく」（特開平７−２５６２９９号公報）、あるいは「アニオン性単量体構成単位５〜２０モル％」（特開２００２−２３３７０７号公報）、さらに「アニオン当量値（以下Ａｖと表す）が０．２〜２．５ｍｅｑ／ｇであることが好ましく、より好ましくは０．３〜１．８ｍｅｑ／ｇである。」（特開２００２−１７７７０６号公報）など一般的な記載は見られる（０．３ｍｅｑ／ｇでは２モル％共重合に相当する）。しかし実施例の検討では、こうした低アニオン性の両性水溶性高分子の記載は見当たらないのが現状である。本発明者等はこのような低アニオン性の領域の両性水溶性高分子の検討を詳細に行った。その結果、低アニオン性の両性水溶性高分子によって添加量の削減が達成でき、さらに従来、架橋性の水溶性高分子の欠点といわれる添加量の増加がなく、削減が達成できる場合もあり、優れた凝集性能が得られることが判明した。 The crosslinked amphoteric water-soluble polymer of the present invention is characterized in that the degree of anionization is sufficiently reduced for the reasons described above. As a result, the crosslinking easily proceeds without being affected by chain transfer such as acrylic acid, and the degree of crosslinking is increased by the same amount of the crosslinking monomer. Conventionally, the amphoteric water-soluble polymer is preferably expressed in the detailed description of the invention as “copolymerization ratio of anionic monomer is preferably 5 to 30 mol%” (Japanese Patent Laid-Open No. 7-256299) or “anionic monomer”. It is preferable that the monomer structural unit is 5 to 20 mol% (Japanese Patent Laid-Open No. 2002-233707), and that the anion equivalent value (hereinafter referred to as Av) is preferably 0.2 to 2.5 meq / g, more preferably General description such as “0.3 to 1.8 meq / g” (Japanese Patent Laid-Open No. 2002-177706) can be seen (corresponding to 2 mol% copolymerization at 0.3 meq / g). However, in the examination of the examples, there is no description of such a low anionic amphoteric water-soluble polymer. The present inventors have conducted a detailed study of amphoteric water-soluble polymers in such a low anionic region. As a result, the amount of addition can be reduced by the low anionic amphoteric water-soluble polymer, and further, there is no increase in the amount of addition, which is conventionally referred to as a disadvantage of the cross-linkable water-soluble polymer, and reduction may be achieved, It has been found that excellent agglomeration performance can be obtained.
本発明の両性水溶性高分子を含有するからなる汚泥脱水剤は、下水、し尿、産業排水の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）に通常０．１〜０．２質量％水溶液として添加される。対象とする汚泥に特に限定されないが、繊維分の少ない汚泥、有機分含有量（ＶＳＳ／ＳＳ）の高い汚泥、腐敗度の高い汚泥に対し特に有効であり好ましい。 The sludge dewatering agent comprising the amphoteric water-soluble polymer of the present invention is an organic sludge (so-called raw sludge, surplus sludge, mixed raw sludge, digested sludge, sedimentation sludge, floatation) generated by the treatment of sewage, human waste and industrial wastewater. Sludge and a mixture thereof) are usually added as 0.1 to 0.2 mass% aqueous solution. Although not particularly limited to the target sludge, it is particularly effective and preferable for sludge having a low fiber content, sludge having a high organic content (VSS / SS), and sludge having a high degree of spoilage.
また本発明の両性水溶性高分子を含有するからなる汚泥脱水剤は、単独で汚泥脱水に使用しても良いが、脱水効果がより好ましいのは、鉄塩、アルミ塩等の無機凝集剤と併用することができる。該無機凝集剤としては、塩鉄、硫鉄、ポリ鉄、ＰＡＣ、硫酸バンドなどが挙げられる。汚泥に対する添加量は、通常汚泥固形分に対し０．１〜２質量％、好ましくは０．３〜１．０質量％である。アニオン化度が低いために前に述べたように、無機凝集剤のカチオン電荷が無駄に消費されることなく効率よく作用する。その分無機凝集剤の効果が向上する。 Further, the sludge dewatering agent comprising the amphoteric water-soluble polymer of the present invention may be used alone for sludge dewatering, but the dewatering effect is more preferable with inorganic flocculants such as iron salts and aluminum salts. Can be used together. Examples of the inorganic flocculant include salt iron, iron sulfate, polyiron, PAC, and sulfuric acid band. The addition amount with respect to sludge is 0.1-2 mass% normally with respect to sludge solid content, Preferably it is 0.3-1.0 mass%. Since the degree of anionization is low, the cationic charge of the inorganic flocculant acts efficiently without being wasted as described above. Accordingly, the effect of the inorganic flocculant is improved.
使用する脱水機の種類は、デカンター、スクリュープレス、ベルトプレス、ロータリープレスなど通常の脱水機が可能である。 The type of dehydrator used can be a normal dehydrator such as a decanter, a screw press, a belt press, or a rotary press.
（実施例）以下、実施例により本発明をさらに詳細に説明するが、本発明はこれに限定されるものではない。 EXAMPLES The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.
攪拌機および温度制御装置を備えた反応槽に沸点１９０°Ｃないし２３０°Ｃのイソパラフィン１２６．０ｇにポリオキシエチレントリデシルエ−テル１２．５ｇ（対エマルジョン２．５質量％）を仕込み溶解させた。別に脱イオン水２９．８ｇとアクリル酸（ＡＡＣと略記）６０％水溶液４．９ｇ、アクリロイルオキシエチルトリメチルアンモニウム塩化物（以下ＤＡＭＱと略記）８０％水溶液７５．４ｇ、メタクリロイルオキシエチルトリメチルアンモニウム塩化物（以下ＤＭＭＱと略記）８０％水溶液２７．０ｇ、アクリルアミド（ＡＡＭと略記）５０％水溶液２３０．４ｇ及びメチレンビスアクリルアミド０．１質量％水溶液２．０ｇ（対単量体０．００１質量％）を各々採取し、各々を混合し完全に溶解させた。その後ｐＨを３．９５に調節し、油と水溶液を混合し、ホモジナイザーにて１０００ｒｐｍで１５分間攪拌乳化した。この時の単量体組成は、ＤＡＭＱ／ＤＭＭＱ／ＡＡＣ／ＡＡＭ＝１５／５／２／７８（モル％）である。 A reaction vessel equipped with a stirrer and a temperature controller was charged with 12.5 g of polyoxyethylene tridecyl ether (2.5% by mass of emulsion) and dissolved in 126.0 g of isoparaffin having a boiling point of 190 ° C. to 230 ° C. Separately, 29.8 g of deionized water, 4.9 g of 60% aqueous solution of acrylic acid (abbreviated as AAC), 75.4 g of 80% aqueous solution of acryloyloxyethyltrimethylammonium chloride (hereinafter abbreviated as DAMQ), methacryloyloxyethyltrimethylammonium chloride ( (Hereinafter abbreviated as DMMQ) 27.0 g of 80% aqueous solution, 230.4 g of 50% aqueous solution of acrylamide (abbreviated as AAM) and 2.0 g of methylenebisacrylamide 0.1% by mass aqueous solution (0.001% by mass of monomer). Collected and mixed to dissolve completely. Thereafter, the pH was adjusted to 3.95, the oil and the aqueous solution were mixed, and stirred and emulsified with a homogenizer at 1000 rpm for 15 minutes. The monomer composition at this time is DAMQ / DMMQ / AAC / AAM = 15/5/2/78 (mol%).
得られたエマルジョンにイソプロピルアルコール１０質量％水溶液１．０ｇ（対単量体０．０５質量％）を加え、単量体溶液の温度を３０〜３３℃に保ち、窒素置換を３０分行った後、２、２’−アゾビス〔２−（５−メチル−２−イミダゾリン−２−イル）プロパン〕二塩化水素化物の１質量％水溶液２．０ｇ（対単量体０．０１質量％）を加え、重合反応を開始させた。反応温度を３２±２℃で１２時間重合させ反応を完結させた。（試料−１）とする。試験に供する試料を、水溶性高分子濃度０．１質量％とした場合の粘度（ＡＱＶ）、０．１質量％で１Ｎ食塩水中の粘度（ＳＬＶ）を２５℃においてＢ型粘度計（回転粘度計の一種）により測定し、ミューテック社製ＰＣＤ滴定装置により電荷内包率を測定した。さらに光散乱法による重量平均分子量は約９００万であった。 After adding 1.0 g of isopropyl alcohol 10 mass% aqueous solution (0.05 mass% monomer) to the obtained emulsion, maintaining the temperature of the monomer solution at 30 to 33 ° C. and performing nitrogen substitution for 30 minutes 2,2'-azobis [2- (5-methyl-2-imidazolin-2-yl) propane] dihydrochloride 2.0 g (0.01% by weight monomer) was added. The polymerization reaction was started. The reaction was completed at a reaction temperature of 32 ± 2 ° C. for 12 hours to complete the reaction. (Sample-1). Viscosity (AQV) when water-soluble polymer concentration is 0.1% by mass for sample to be used for test, B-type viscometer (rotational viscosity at 25 ° C. with viscosity (SLV) in 1N saline solution at 0.1% by mass) The charge inclusion rate was measured with a PCD titration apparatus manufactured by Mutech. Furthermore, the weight average molecular weight by the light scattering method was about 9 million.
同様な操作によりＤＡＭＱ／ＤＭＭＱ／ＡＡＣ／ＡＡＭ＝３０／５／３／６２（試作−２）、ＤＡＭＱ／ＤＭＭＱ／ＡＡＣ／ＡＡＭ＝４５／５／５／４５（試作−３）、ＤＡＭＱ／ＤＭＭＱ／ＡＡＣ／ＡＡＭ＝４５／５／４／４６（試作−４）、ＤＡＭＱ／ＤＭＭＱ／ＡＡＣ／ＡＡＭ＝４５／５／２／４８（試作−５）、
ＤＡＭＱ／ＤＭＭＱ／ＡＡＣ／ＡＡＭ＝４５／５／１／４９（試作−６）、ＤＡＭＱ／ＤＭＭＱ／ＡＡＣ／ＡＡＭ＝５０／１０／５／３５（試作−７）、ＤＡＭＱ／ＤＭＭＱ／ＡＡＣ／ＡＡＭ＝７０／１０／５／１５（試作−８）からなる油中水型エマルジョンを合成した。結果を表１に示す。
By the same operation, DAMQ / DMMQ / AAC / AAM = 30/5/3/62 (prototype-2), DAMQ / DMMQ / AAC / AAM = 45/5/5/45 (prototype-3), DAMQ / DMMQ / AAC / AAM = 45/5/4/46 (prototype-4), DAMQ / DMMQ / AAC / AAM = 45/5/2/48 (prototype-5),
DAMQ / DMMQ / AAC / AAM = 45/5/1/49 (prototype-6), DAMQ / DMMQ / AAC / AAM = 50/10/5/35 (prototype-7), DAMQ / DMMQ / AAC / AAM = A water-in-oil emulsion consisting of 70/10/5/15 (prototype-8) was synthesized. The results are shown in Table 1.
（比較例１）
実施例１と同様な操作によりＤＡＭＱ／ＤＭＭＱ／ＡＡＣ／ＡＡＭ＝４５／５／１０／４０（比較−１）、ＤＡＭＱ／ＤＭＭＱ／ＡＡＣ／ＡＡＭ＝４５／５／１５／３５（比較−２）、ＤＡＭＱ／ＤＭＭＱ／ＡＡＣ／ＡＡＭ＝４５／５／２０／３０（比較−３）からなる油中水型エマルジョンを合成した。結果を表１に示す。
(Comparative Example 1)
DAMQ / DMMQ / AAC / AAM = 45/5/10/40 (Comparative-1), DAMQ / DMMQ / AAC / AAM = 45/5/15/35 (Comparative-2) by the same operation as Example 1. A water-in-oil emulsion consisting of DAMQ / DMMQ / AAC / AAM = 45/5/20/30 (Comparative-3) was synthesized. The results are shown in Table 1.
攪拌機および温度制御装置を備えた反応槽に沸点１９０°Ｃないし２３０°Ｃのイソパラフィン１２６．０ｇにポリオキシエチレントリデシルエ−テル１２．５ｇ（対エマルジョン２．５質量％）を仕込み溶解させた。別に脱イオン水３１．８ｇとアクリル酸（ＡＡＣと略記）６０％水溶液４．９ｇ、アクリロイルオキシエチルトリメチルアンモニウム塩化物（以下ＤＡＭＱと略記）８０％水溶液７５．４ｇ、メタクリロイルオキシエチルトリメチルアンモニウム塩化物（以下ＤＭＭＱと略記）８０％水溶液２７．０ｇ、アクリルアミド（ＡＡＭと略記）５０％水溶液２３０．４ｇを各々採取し、各々を混合し完全に溶解させた。その後ｐＨを３．９５に調節し、油と水溶液を混合し、ホモジナイザーにて１０００ｒｐｍで１５分間攪拌乳化した。この時の単量体組成は、ＤＡＭＱ／ＤＭＭＱ／ＡＡＣ／ＡＡＭ＝１５／５／２／７８（モル％）である。 A reaction vessel equipped with a stirrer and a temperature controller was charged with 12.5 g of polyoxyethylene tridecyl ether (2.5% by mass of emulsion) and dissolved in 126.0 g of isoparaffin having a boiling point of 190 ° C. to 230 ° C. Separately, 31.8 g of deionized water, 4.9 g of 60% aqueous solution of acrylic acid (abbreviated as AAC), 75.4 g of 80% aqueous solution of acryloyloxyethyltrimethylammonium chloride (hereinafter abbreviated as DAMQ), methacryloyloxyethyltrimethylammonium chloride ( Hereinafter, 27.0 g of 80% aqueous solution and 230.4 g of 50% aqueous solution of acrylamide (abbreviated as AAM) were sampled and mixed to dissolve completely. Thereafter, the pH was adjusted to 3.95, the oil and the aqueous solution were mixed, and stirred and emulsified with a homogenizer at 1000 rpm for 15 minutes. The monomer composition at this time is DAMQ / DMMQ / AAC / AAM = 15/5/2/78 (mol%).
得られたエマルジョンにイソプロピルアルコール１０質量％水溶液１．０ｇ（対単量体０．０５質量％）を加え、単量体溶液の温度を３０〜３３℃に保ち、窒素置換を３０分行った後、２、２’−アゾビス〔２−（５−メチル−２−イミダゾリン−２−イル）プロパン〕二塩化水素化物の１質量％水溶液２．０ｇ（対単量体０．０１質量％）を加え、重合反応を開始させた。反応温度を３２±２℃で１２時間重合させ反応を完結させた。（試料−９）とする。試験に供する試料を、水溶性高分子濃度０．１質量％とした場合の粘度（ＡＱＶ）、０．１質量％で１Ｎ食塩水中の粘度（ＳＬＶ）を２５℃においてＢ型粘度計（回転粘度計の一種）により測定し、ミューテック社製ＰＣＤ滴定装置により電荷内包率を測定した。さらに光散乱法による重量平均分子量は約７００万であった。 After adding 1.0 g of isopropyl alcohol 10 mass% aqueous solution (0.05 mass% monomer) to the obtained emulsion, maintaining the temperature of the monomer solution at 30 to 33 ° C. and performing nitrogen substitution for 30 minutes 2,2'-azobis [2- (5-methyl-2-imidazolin-2-yl) propane] dihydrochloride 2.0 g (0.01% by weight monomer) was added. The polymerization reaction was started. The reaction was completed at a reaction temperature of 32 ± 2 ° C. for 12 hours to complete the reaction. (Sample-9). Viscosity (AQV) when water-soluble polymer concentration is 0.1% by mass for sample to be used for test, B-type viscometer (rotational viscosity at 25 ° C. with viscosity (SLV) in 1N saline solution at 0.1% by mass) The charge inclusion rate was measured with a PCD titration apparatus manufactured by Mutech. Furthermore, the weight average molecular weight by the light scattering method was about 7 million.
（比較例２）
実施例２と同様な操作によりＤＡＭＱ／ＤＭＭＱ／ＡＡＣ／ＡＡＭ＝４５／５／１０／４０（比較−４）、ＤＡＭＱ／ＤＭＭＱ／ＡＡＣ／ＡＡＭ＝４５／５／２０／３０（比較−５）からなる油中水型エマルジョンを合成した。結果を表１に示す。
(Comparative Example 2)
From the same operation as in Example 2, DAMQ / DMMQ / AAC / AAM = 45/5/10/40 (Comparison-4), DAMQ / DMMQ / AAC / AAM = 45/5/20/30 (Comparison-5) A water-in-oil emulsion was synthesized. The results are shown in Table 1.
（表１）
ＤＡＭＱ；クリロイルオキシエチルトリメチルアンモニウム塩化物
ＤＭＭＱ；メタクリロイルオキシエチルトリメチルアンモニウム塩化物
ＡＡＭ；アクリルアミド、ＡＡＣ；アクリル酸、ＡＱＶ／ＳＬＶ；無次元
電荷内包率；％、架橋剤添加量；単量体に対する質量換算ｐｐｍ
( Table 1 )
DAMQ; acryloyloxyethyltrimethylammonium chloride DMMQ; methacryloyloxyethyltrimethylammonium chloride AAM; acrylamide, AAC; acrylic acid, AQV / SLV; dimensionless charge inclusion rate;%, amount of crosslinking agent added; mass relative to monomer Ppm conversion
下水消化汚泥（ｐＨ７．７５、ｓｓ分１６，８００ｍｇ／Ｌ）を用い、本発明の両性水溶性高分子を用い汚泥脱水試験を実施した。２００ｍＬをポリビ−カ−に採取し、表１の試作−１〜試作−８をそれぞれ対汚泥ＳＳ分０．７０％（懸濁粒子質量％）加え、ビ−カ−移し替え攪拌２０回行った後、Ｔ−１１７９Ｌの濾布（ナイロン製）により濾過し、１０秒後の濾液量の測定、及びフロック強度（大きさ）を目視により測定した。その後５０秒間濾過した汚泥をプレス圧３Ｋｇ／ｍ2で１分間脱水する。その後、濾布剥離性を目視によりチェックし、ケ−キ含水率（１０５℃で２０ｈｒ乾燥）を測定した。結果を表２に示す。 A sludge dewatering test was conducted using sewage digested sludge (pH 7.75, ss content 16,800 mg / L) using the amphoteric water-soluble polymer of the present invention. 200 mL was collected in a poly beaker, trial product-1 to trial product- 8 in Table 1 were added to each sludge SS content 0.70% (suspension particle mass%), the beaker was transferred and stirred 20 times. Then, it filtered with the T-1179L filter cloth (product made from nylon), measured the amount of filtrates 10 seconds later, and measured the floc intensity | strength (size) visually. Thereafter, the sludge filtered for 50 seconds is dehydrated at a press pressure of 3 kg / m 2 for 1 minute. Thereafter, the filter cloth peelability was visually checked, and the cake water content (dried at 105 ° C. for 20 hours) was measured. The results are shown in Table 2.
(比較例３)実施例３と同様な操作により、比較−１〜比較−５に関して試験を実施した。結果を表２に示す。 (Comparative Example 3) By the same operation as in Example 3, the tests for Comparative-1 to Comparative-5 were carried out. The results are shown in Table 2.
比較−１〜比較−５は、それぞれアニオン共重合率が１０〜２０モル％であり、
試料−１〜試料−８に較べ高い。その結果、試料−１〜試料−８に較べ添加量を増加させないと（試料−１〜試料−８に対し１５％増し）同等以上の効果を発揮しないことが分かる。
Comparative-1 to Comparative-5 have an anion copolymerization rate of 10 to 20 mol%,
Higher than Sample-1 to Sample- 8 . As a result, the sample -1 sample - it can be seen that exerts no - (8 to 15% widening sample -1 sample) equal or effect as not to increase the amount compared to 8.
（表２）
ケーキ含水率：質量％、添加量：対ｓｓ質量％、１０秒後濾液量：ｍＬ
フロック強度：ｍｍ
( Table 2 )
Moisture content of cake: mass%, added amount: ss mass%, 10 seconds later, filtrate amount: mL
Flock strength: mm
食品余剰汚泥（ｐＨ６．５０、ｓｓ分２１，３００ｍｇ／Ｌ）を用い、本発明の水溶性高分子組成物を用い汚泥脱水試験を実施した。２００ｍＬをポリビ−カ−に採取し、表１の試作−１〜試作−８をそれぞれ対汚泥ＳＳ分０．８５％（懸濁粒子質量％）加え、ビ−カ−移し替え攪拌２０回行った後、Ｔ−１１７９Ｌの濾布（ナイロン製）により濾過し、１０秒後の濾液量の測定、及びフロック強度（大きさ）を目視により測定した。その後５０秒間濾過した汚泥をプレス圧３Ｋｇ／ｍ2で１分間脱水する。その後、濾布剥離性を目視によりチェックし、ケ−キ含水率（１０５℃で２０ｈｒ乾燥）を測定した。結果を表３に示す。 A sludge dewatering test was carried out using food surplus sludge (pH 6.50, ss content 21,300 mg / L) using the water-soluble polymer composition of the present invention. 200 mL was collected in a poly beaker, and trial production-1 to trial production- 8 in Table 1 were added to each sludge SS content 0.85% (suspension particle mass%), and the beaker was transferred and stirred 20 times. Then, it filtered with the T-1179L filter cloth (product made from nylon), measured the amount of filtrates 10 seconds later, and measured the floc intensity | strength (size) visually. Thereafter, the sludge filtered for 50 seconds is dehydrated at a press pressure of 3 kg / m 2 for 1 minute. Thereafter, the filter cloth peelability was visually checked, and the cake water content (dried at 105 ° C. for 20 hours) was measured. The results are shown in Table 3.
(比較例４)実施例４と同様な操作により、比較−１〜比較−５に関して試験を実施した。結果を表３に示す。 (Comparative Example 4) By the same operation as in Example 4, tests were conducted for Comparative-1 to Comparative-5. The results are shown in Table 3.
比較−１〜比較−５は、それぞれアニオン共重合率が１０〜２０モル％であり、
試料−１〜試料−８に較べ高い。その結果、試料−１〜試料−８に較べ添加量を増加させないと（試料−１〜試料−８に対し１０％増し）同等以上の効果を発揮しないことが分かる。
Comparative-1 to Comparative-5 have an anion copolymerization rate of 10 to 20 mol%,
Higher than Sample-1 to Sample- 8 . As a result, the sample -1 sample - it can be seen that exerts no - (8 to 10% greater sample -1 sample) equal or effect as not to increase the amount compared to 8.
（表３）
ケーキ含水率：質量％、添加量：対ｓｓ質量％、１０秒後濾液量：ｍＬ
フロック強度：ｍｍ
( Table 3 )
Moisture content of cake: mass%, added amount: ss mass%, 10 seconds later, filtrate amount: mL
Flock strength: mm
Claims (5)
Ｒ１は水素又はメチル基、Ｒ２およびＲ３は炭素数１〜３のアルキル基、アルコキシ基あるいはベンジル基、Ｒ４は水素、炭素数１〜３のアルキル基、アルコキシル基あるいはベンジル基であり、同種でも異種でも良い。Ａは酸素またはＮＨ、Ｂは炭素数２〜４のアルキレン基またはアルコキシレン基、Ｘ１は陰イオンをそれぞれ表わす。
Ｒ４は水素又はメチル基、Ｒ５、Ｒ６は炭素数１〜３のアルキル基、あるいはベンジル基、Ｘ２ −は陰イオンをそれぞれ表す。
Ｒ８は水素またはＣＨ２ＣＯＯＹ２、ＱはＳＯ３、Ｃ６Ｈ５ＳＯ３、
ＣＯＮＨＣ（ＣＨ２）２ＣＨ２ＳＯ３、Ｃ６Ｈ５ＣＯＯあるいはＣＯＯ、Ｒ９は水素、メチル基またはＣＯＯＹ２であり、Ｙ１、Ｙ２は水素または陽イオンをそれぞれ表わす。 1 to 5 mol of a cationic monomer represented by the following general formula (1) and / or the following general formula (2), (meth) acrylamide, and an anionic monomer represented by the following general formula (3) % Of the monomer mixture is an amphoteric water-soluble polymer obtained by polymerizing 100 to 1,000 ppm of the chain transfer agent and 5 to 100 ppm of the crosslinking agent in terms of mass , When the 0.2% by mass aqueous solution of the amphoteric water-soluble polymer is AQV and the viscosity in the 0.5% by mass 1N saline solution is SLV, the ratio of both is 30 ≦ AQV / SLV ≦ 100 (at 25 ° C.), and the weight A sludge dewatering agent containing an amphoteric water-soluble polymer having an average molecular weight of 3 million to 10 million .
R 1 is hydrogen or a methyl group, R 2 and R 3 are an alkyl group having 1 to 3 carbon atoms, an alkoxy group or a benzyl group, and R 4 is hydrogen, an alkyl group having 1 to 3 carbon atoms, an alkoxyl group or a benzyl group. , Same or different. A represents oxygen or NH, B represents an alkylene group or alkoxylene group having 2 to 4 carbon atoms, and X 1 represents an anion.
R 4 represents hydrogen or a methyl group, R 5 and R 6 each represent an alkyl group having 1 to 3 carbon atoms, or a benzyl group, and X 2 − represents an anion.
R 8 is hydrogen or CH 2 COOY 2 , Q is SO 3 , C 6 H 5 SO 3 ,
CONHC (CH 2 ) 2 CH 2 SO 3 , C 6 H 5 COO or COO, R 9 is hydrogen, a methyl group or COOY 2 , and Y 1 and Y 2 each represent hydrogen or a cation.
Ｒ１は水素又はメチル基、Ｒ２およびＲ３は炭素数１〜３のアルキル基、アルコキシ基あるいはベンジル基、Ｒ４は水素、炭素数１〜３のアルキル基、アルコキシル基あるいはベンジル基であり、同種でも異種でも良い。Ａは酸素またはＮＨ、Ｂは炭素数２〜４のアルキレン基またはアルコキシレン基、Ｘ１は陰イオンをそれぞれ表わす。
Ｒ４は水素又はメチル基、Ｒ５、Ｒ６は炭素数１〜３のアルキル基、あるいはベンジル基、Ｘ２ −は陰イオンをそれぞれ表す。
Ｒ８は水素またはＣＨ２ＣＯＯＹ２、ＱはＳＯ３、Ｃ６Ｈ５ＳＯ３、
ＣＯＮＨＣ（ＣＨ２）２ＣＨ２ＳＯ３、Ｃ６Ｈ５ＣＯＯあるいはＣＯＯ、Ｒ９は水素、メチル基またはＣＯＯＹ２であり、Ｙ１、Ｙ２は水素または陽イオンをそれぞれ表わす。 1 to 5 mol of a cationic monomer represented by the following general formula (1) and / or the following general formula (2), (meth) acrylamide, and an anionic monomer represented by the following general formula (3) % Of the monomer mixture is an amphoteric water-soluble polymer obtained by polymerizing 100 to 1,000 ppm of the chain transfer agent and 5 to 100 ppm of the crosslinking agent in terms of mass , When the 0.2% by mass aqueous solution of the amphoteric water-soluble polymer is AQV and the viscosity in the 0.5% by mass 1N saline solution is SLV, the ratio of both is 30 ≦ AQV / SLV ≦ 100 (at 25 ° C.), and the weight A sludge dewatering method comprising adding a sludge dewatering agent containing an amphoteric water-soluble polymer having an average molecular weight of 3 million to 10 million to sludge and dehydrating it.
R 1 is hydrogen or a methyl group, R 2 and R 3 are an alkyl group having 1 to 3 carbon atoms, an alkoxy group or a benzyl group, and R 4 is hydrogen, an alkyl group having 1 to 3 carbon atoms, an alkoxyl group or a benzyl group. , Same or different. A represents oxygen or NH, B represents an alkylene group or alkoxylene group having 2 to 4 carbon atoms, and X 1 represents an anion.
R 4 represents hydrogen or a methyl group, R 5 and R 6 each represent an alkyl group having 1 to 3 carbon atoms, or a benzyl group, and X 2 − represents an anion.
R 8 is hydrogen or CH 2 COOY 2 , Q is SO 3 , C 6 H 5 SO 3 ,
CONHC (CH 2 ) 2 CH 2 SO 3 , C 6 H 5 COO or COO, R 9 is hydrogen, a methyl group or COOY 2 , and Y 1 and Y 2 each represent hydrogen or a cation.
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