JP2983279B2 - Composition for sludge dewatering agent - Google Patents
Composition for sludge dewatering agentInfo
- Publication number
- JP2983279B2 JP2983279B2 JP2294875A JP29487590A JP2983279B2 JP 2983279 B2 JP2983279 B2 JP 2983279B2 JP 2294875 A JP2294875 A JP 2294875A JP 29487590 A JP29487590 A JP 29487590A JP 2983279 B2 JP2983279 B2 JP 2983279B2
- Authority
- JP
- Japan
- Prior art keywords
- polymer compound
- amphoteric polymer
- sludge
- composition
- cationic
- 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 - Fee Related
Links
- 239000010802 sludge Substances 0.000 title claims description 41
- 239000000203 mixture Substances 0.000 title claims description 26
- 239000003795 chemical substances by application Substances 0.000 title claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 83
- 229920000642 polymer Polymers 0.000 claims description 68
- 229920006317 cationic polymer Polymers 0.000 claims description 25
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 13
- 125000000129 anionic group Chemical group 0.000 claims description 9
- 125000002091 cationic group Chemical group 0.000 claims description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 5
- 229910052700 potassium Inorganic materials 0.000 claims description 5
- 239000011591 potassium Substances 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- 150000001450 anions Chemical group 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- -1 for example Substances 0.000 description 19
- 239000012024 dehydrating agents Substances 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 9
- 229920001577 copolymer Polymers 0.000 description 9
- 229920001519 homopolymer Polymers 0.000 description 9
- 239000000178 monomer Substances 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 9
- 150000003839 salts Chemical class 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 230000018044 dehydration Effects 0.000 description 8
- 238000006297 dehydration reaction Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 7
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 7
- 239000011976 maleic acid Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 7
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 6
- 229940018557 citraconic acid Drugs 0.000 description 6
- 239000010865 sewage Substances 0.000 description 6
- 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 5
- 239000002253 acid Chemical class 0.000 description 5
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 5
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 5
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 5
- DYUWTXWIYMHBQS-UHFFFAOYSA-N n-prop-2-enylprop-2-en-1-amine Chemical compound C=CCNCC=C DYUWTXWIYMHBQS-UHFFFAOYSA-N 0.000 description 5
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 4
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 150000003863 ammonium salts Chemical class 0.000 description 4
- YIOJGTBNHQAVBO-UHFFFAOYSA-N dimethyl-bis(prop-2-enyl)azanium Chemical compound C=CC[N+](C)(C)CC=C YIOJGTBNHQAVBO-UHFFFAOYSA-N 0.000 description 4
- 239000004744 fabric Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- JZMJDSHXVKJFKW-UHFFFAOYSA-M methyl sulfate(1-) Chemical compound COS([O-])(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-M 0.000 description 4
- WGESLFUSXZBFQF-UHFFFAOYSA-N n-methyl-n-prop-2-enylprop-2-en-1-amine Chemical compound C=CCN(C)CC=C WGESLFUSXZBFQF-UHFFFAOYSA-N 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000001226 reprecipitation Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 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 3
- 229920006318 anionic polymer Polymers 0.000 description 3
- 230000015271 coagulation Effects 0.000 description 3
- 238000005345 coagulation Methods 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 239000010800 human waste Substances 0.000 description 3
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 3
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000739 chaotic effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- YRHAJIIKYFCUTG-UHFFFAOYSA-M dimethyl-bis(prop-2-enyl)azanium;bromide Chemical compound [Br-].C=CC[N+](C)(C)CC=C YRHAJIIKYFCUTG-UHFFFAOYSA-M 0.000 description 2
- 239000010840 domestic wastewater Substances 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000010842 industrial wastewater Substances 0.000 description 2
- GBCKRQRXNXQQPW-UHFFFAOYSA-N n,n-dimethylprop-2-en-1-amine Chemical compound CN(C)CC=C GBCKRQRXNXQQPW-UHFFFAOYSA-N 0.000 description 2
- IOXXVNYDGIXMIP-UHFFFAOYSA-N n-methylprop-2-en-1-amine Chemical compound CNCC=C IOXXVNYDGIXMIP-UHFFFAOYSA-N 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 229920002401 polyacrylamide Polymers 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 2
- HXVJQEGYAYABRY-UHFFFAOYSA-N 1-ethenyl-4,5-dihydroimidazole Chemical compound C=CN1CCN=C1 HXVJQEGYAYABRY-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- ZWAPMFBHEQZLGK-UHFFFAOYSA-N 5-(dimethylamino)-2-methylidenepentanamide Chemical compound CN(C)CCCC(=C)C(N)=O ZWAPMFBHEQZLGK-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 229940126062 Compound A Drugs 0.000 description 1
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 241001274216 Naso Species 0.000 description 1
- 206010067482 No adverse event Diseases 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- XXJLQQRZZGAIGT-UHFFFAOYSA-N benzyl(methyl)azanium;bromide Chemical compound [Br-].C[NH2+]CC1=CC=CC=C1 XXJLQQRZZGAIGT-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 125000004663 dialkyl amino group Chemical group 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- UYMKPFRHYYNDTL-UHFFFAOYSA-N ethenamine Chemical compound NC=C UYMKPFRHYYNDTL-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical group C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000010297 mechanical methods and process Methods 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Landscapes
- Separation Of Suspended Particles By Flocculating Agents (AREA)
- Treatment Of Sludge (AREA)
Description
【発明の詳細な説明】 [産業上の利用分野] 本発明は、下水処理、し尿処理、各種産業廃水、生活
廃水などの処理により生じる汚泥の凝集、脱水に有効な
脱水剤用組成物に関する。Description: TECHNICAL FIELD The present invention relates to a composition for a dehydrating agent that is effective for coagulation and dehydration of sludge generated by treatment of sewage treatment, human waste treatment, various industrial wastewaters, domestic wastewater, and the like.
[従来の技術] 従来より各種産業廃水、下水、し尿の処理などにより
生じる汚泥は、カチオン性高分子化合物を添加した後、
スクリューデカンター、フィルタープレス、ベルトプレ
スなどで脱水してから処理されている。[Prior art] Conventionally, sludge generated by treatment of various industrial wastewater, sewage, night soil, etc., after adding a cationic polymer compound,
It is treated after dehydration with a screw decanter, filter press, belt press, etc.
それらの汚泥は主に有機質よりなり、しばしばその一
部は腐敗している。そのため、汚泥は一般的に粘結性と
親水性、吸水性を有しており、加えて強度が低くかさば
っているため、そのままでは機械的に脱水処理をして廃
棄処分をすることはできない。このことが脱水前処理用
の薬剤の添加が必要な理由の一つである。These sludges are mainly composed of organic matter, often of which is spoiled. For this reason, sludge generally has caking properties, hydrophilicity, and water absorbability, and in addition, has low strength and is bulky, so that it is not possible to mechanically dewater it for disposal as it is. This is one of the reasons why it is necessary to add a chemical for pretreatment for dehydration.
脱水処理された汚泥(以下脱水ケーキという)は、埋
め立てなどに用いられることもあるが大部分は焼却処分
される。焼却において使用される燃料の大部分は脱水さ
れた汚泥中の水分蒸発に使用されるが、一般的に脱水ケ
ーキ中の水分が1%低下すると燃料を10%程度節約可能
とされている。そのため、焼却処分における燃料費用を
節減するために脱水ケーキの低含水率化が要望されてい
る。これもまた薬剤添加の理由であり、ケーキ含水率の
低さが添加する薬剤を選択する基準でもある。Dewatered sludge (hereinafter referred to as dewatered cake) is sometimes used for landfills, but is mostly incinerated. Most of the fuel used in incineration is used for evaporating water in dewatered sludge, but it is generally said that a 1% decrease in water in a dewatered cake can save about 10% of fuel. Therefore, there is a demand for reducing the water content of the dewatered cake in order to reduce fuel costs in incineration. This is also the reason for adding the drug, and the low water content of the cake is also a criterion for selecting the drug to be added.
このような汚泥の脱水には、これまで主に高分子量の
カチオン性高分子化合物、特にジメチルアミノエチルメ
タクリレートの第4級アンモニウム塩または酸塩を重合
成分として含む高分子脱水剤が広く用いられてきた。To dewater such sludge, a polymer dehydrating agent containing a high molecular weight cationic polymer compound, particularly a quaternary ammonium salt or an acid salt of dimethylaminoethyl methacrylate, as a polymerization component has been widely used. Was.
ところで、特に有機性の高い汚泥、例えば多量の生活
廃水を含む下水処理場より生ずる汚泥やし尿処理場より
生ずる汚泥などに対しては上記のような通常のカチオン
性高分子脱水剤を使用しても十分な脱水効果が得られな
いことが多く、そのような場合には脱水ケーキの含水率
が低くならないのみならず、脱水したフロックの強度も
弱く、懸濁質(以下SSという)の回収率も低い。By the way, especially for highly organic sludge, for example, sludge generated from a sewage treatment plant containing a large amount of domestic wastewater or sludge generated from a human waste treatment plant, the above-mentioned ordinary cationic polymer dehydrating agent is used. In many cases, a sufficient dewatering effect cannot be obtained. In such a case, not only does the water content of the dewatered cake not decrease, but also the strength of the dewatered floc is weak, and the recovery of suspended solids (hereinafter referred to as SS) Is also low.
このような汚泥の脱水に対しては、ポリアクリルアミ
ドをマンニッヒ変性したカチオン性高分子脱水剤とアニ
オン性高分子脱水剤の併用(特開昭58−139799号)、通
常のカチオン性高分子脱水剤とアニオン性高分子脱水剤
の併用(特開昭58−215454号)などが提案された。For the dehydration of such sludge, a combination of a cationic polymer dehydrating agent obtained by modifying polyacrylamide with Mannich and an anionic polymer dehydrating agent (JP-A-58-139799), a conventional cationic polymer dehydrating agent And an anionic polymer dehydrating agent (Japanese Patent Application Laid-Open No. 58-215454).
しかし、それらのようにカチオン性高分子脱水剤とア
ニオン性高分子脱水剤を併用する方法は、SS回収率、脱
水ケーキの含水率低下、ケーキの剥離性などにおいて改
善をなしたが、いずれの場合も各成分の混合比の設定や
混合操作の煩雑さが問題として残る。また、マンニッヒ
変性ポリマーは保存安定性が良好でなく、数か月程度の
保存によっても不溶性部分が生成するため脱水効果の低
下が起こりやすい。However, such methods using a combination of a cationic polymer dehydrating agent and an anionic polymer dehydrating agent have improved the SS recovery rate, the water content of the dehydrated cake, and the peelability of the cake. In this case, the setting of the mixing ratio of each component and the complexity of the mixing operation remain as problems. Further, the Mannich-modified polymer does not have good storage stability, and an insoluble portion is formed even after storage for several months, so that the dehydration effect tends to decrease.
このような問題をも解決するために、ジメチルアミノ
プロピルアクリルアミドの塩酸と(メタ)アクリル酸ま
たはその塩との共重合により得られる、カチオン基とア
ニオン基とを合せ持つ両性高分子化合物による脱水剤
(特開平2−14799号)も提案され、これにより、保存
安定性、脱水性能、pHの高い汚泥の処理能力を有する優
れた汚泥脱水剤が出現した。In order to solve such a problem, a dehydrating agent using an amphoteric polymer compound having both a cationic group and an anionic group, which is obtained by copolymerizing hydrochloric acid of dimethylaminopropylacrylamide with (meth) acrylic acid or a salt thereof. (JP-A-2-14799) has also been proposed, and as a result, an excellent sludge dewatering agent having storage stability, dewatering performance, and sludge treatment ability with high pH has appeared.
[発明が解決しようとする課題] しかしながら、残念なことにこの両性高分子化合物の
汚泥脱水剤をもってしても、添加後の凝集フロックにべ
とつきやくずれがあったり、フロックの大きさにばらつ
きがあり汚泥の再凝結が起こるなど、現状のままでは満
足し得ない点もまた見いだされている。[Problems to be Solved by the Invention] However, unfortunately, even with this amphoteric polymer sludge dehydrating agent, the flocculated floc after addition has stickiness or breakage, and the floc size varies. It has also been found that sludge re-condensation may not be satisfactory as it is.
[課題を解決するための手段] 本発明者らは、前記の課題を解決するために鋭意研究
を重ねた結果、カチオン性高分子化合物に対してある種
の両性高分子化合物を添加することによって、凝集脱水
性能並びに凝集フロックの性質を改善した脱水剤用組成
物が得られることを見出だし、これに基づいて本発明を
完成させた。[Means for Solving the Problems] The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, by adding a certain amphoteric polymer compound to the cationic polymer compound, The present inventors have found that a composition for a dehydrating agent having improved coagulation dewatering performance and cohesive floc properties can be obtained, and based on this, the present invention has been completed.
すなわち、本発明は、 カチオン性高分子化合物と、 下記の一般式(I)、(II)、(II′)、(III)お
よび(III′)で示されるカチオン系単位の少なくとも
1種と下記の一般式(IV)で示されるアニオン系単位と
を含む両性高分子化合物とを混合して調製される汚泥脱
水剤用組成物を要旨とするものである。That is, the present invention relates to a cationic polymer compound and at least one of cationic units represented by the following general formulas (I), (II), (II '), (III) and (III'). The present invention provides a composition for a sludge dewatering agent prepared by mixing an amphoteric polymer compound containing an anionic unit represented by the general formula (IV).
[ただし、上記式(I)、(II)、(II′)、(II
I)、(III′)および(IV)において、R1、R2はそれぞ
れ独立に水素原子、メチル基またはシクロヘキシル基で
あり、R3は水素原子またはメチル基であり、Rは水素原
子、メチル基またはベンジル基であり、R5、R6はそれぞ
れ独立にメチル基またはベンジル基であり、Xはアニオ
ン(例えばハロゲン、メチル硫酸等のアニオン)であ
り、Yは結合するカルボキシル基それぞれに対し独立に
水素、ナトリウム、カリウムまたはアンモニウムであ
る。] 本発明の汚泥脱水剤用組成物に用いられるカチオン性
高分子化合物はとくに限定されないが、例示すれば、ジ
アルキルアミノアルキルアクリレート、ジアルキルアミ
ノアルキルメタアクリレート、ジアルキルアミノアルキ
ルアクリルアミドもしくはジアルキルアミノアルキルメ
タアクリルアミドの4級化物または酸付加塩の単独重合
体、上記のモノマーとアクリルアミドまたはメタアクリ
ルアミドとの共重合体、ポリアクリルアミドのマンニッ
ヒ変性物またはホフマン分解物、ジアリルジメチルアン
モニウムクロリドの単独重合体または共重合体、ビニル
アミンの単独重合体または共重合体、ビニルイミダゾリ
ンの単独重合体または共重合体、ポリエチレンイミン、
エピハロヒドリン−アミン縮合物、ジシアンジアミド縮
合物、モノアルリアミンの単独重合体、ジアリルアミン
の単独重合体、N−アルキルジアリルアミンの単独重合
体などが可能である。 [However, the above formulas (I), (II), (II '), (II
In I), (III ′) and (IV), R 1 and R 2 are each independently a hydrogen atom, a methyl group or a cyclohexyl group, R 3 is a hydrogen atom or a methyl group, and R is a hydrogen atom, methyl R 5 and R 6 are each independently a methyl group or a benzyl group; X is an anion (for example, an anion such as halogen or methyl sulfate); and Y is independent of each of the carboxyl groups to be bonded. Hydrogen, sodium, potassium or ammonium. The cationic polymer compound used in the composition for a sludge dewatering agent of the present invention is not particularly limited. Examples thereof include dialkylaminoalkyl acrylate, dialkylaminoalkyl methacrylate, dialkylaminoalkyl acrylamide or dialkylaminoalkyl methacrylamide. A quaternary or acid addition salt homopolymer, a copolymer of the above monomers with acrylamide or methacrylamide, a Mannich-modified or Hoffman-decomposed product of polyacrylamide, a homopolymer or copolymer of diallyldimethylammonium chloride, Vinylamine homopolymer or copolymer, vinylimidazoline homopolymer or copolymer, polyethyleneimine,
Epihalohydrin-amine condensates, dicyandiamide condensates, homopolymers of monoarylamine, homopolymers of diallylamine, homopolymers of N-alkyldiallylamine and the like are possible.
これらのカチオン性高分子の分子量は10,000〜15,00
0,000の範囲が好ましい。The molecular weight of these cationic polymers is 10,000-15,000
A range of 0,000 is preferred.
以上にあげたカチオン性高分子化合物は、相互作用に
よる悪影響が見られない限りにおいて、それぞれいかな
る種類のいかなる比率での混合も可能である。The above-mentioned cationic polymer compounds can be mixed in any kind and in any ratio as long as no adverse effects due to the interaction are observed.
このうち特に好ましく用いられるものは、ジアルキル
アミノアルキルアクリレートもしくはジアルキルアミノ
アルキルメタアクリレートの第4級化物または酸付加塩
の単独重合体、上記のアクリレートモノマーとアクリル
アミドまたはメタアクリルアミドとの共重合体、ジアル
キルアミノアルキルアクリルアミドもしくはジアルキル
アミノアルキルメタアクリルアミドの第4級化物または
酸付加塩の単独重合体、またはジアルキルアミノアルキ
ルアクリルアミドもしくはジアルキルアミノアルキルメ
タアクリルアミドの第4級化物または酸付加塩とアクリ
ルアミドもしくはメタアクリルアミドとの共重合体であ
る。Of these, particularly preferably used are quaternized products of dialkylaminoalkyl acrylate or dialkylaminoalkyl methacrylate or homopolymers of acid addition salts, copolymers of the above acrylate monomers with acrylamide or methacrylamide, dialkylamino A homopolymer of a quaternized product of an alkylacrylamide or a dialkylaminoalkylmethacrylamide or an acid addition salt, or a copolymer of a quaternized product of a dialkylaminoalkylacrylamide or a dialkylaminoalkylmethacrylamide or an acid addition salt with acrylamide or methacrylamide It is a polymer.
その分子量は、1,000,000〜15,000,000の範囲である
ことがとくに好ましい。It is particularly preferred that the molecular weight is in the range from 1,000,000 to 15,000,000.
次に両性高分子化合物について説明する。 Next, the amphoteric polymer compound will be described.
この両性高分子化合物は、上記一般式(I)、(I
I)、(II′)、(III)および(III′)で示されるカ
チオン系単位の少なくとも1種と下記の一般式(IV)で
示されるアニオン系単位とを含むものであるが、好まし
い両性高分子化合物として下記のものが挙げられる。This amphoteric polymer compound has the general formula (I) or (I
It contains at least one of the cationic units represented by I), (II '), (III) and (III') and an anionic unit represented by the following general formula (IV). The compounds include the following.
これらの両性高分子化合物(A)、(B)、
(B′)、(C)および(C′)において、カチオン系
単位とアニオン系単位とは交互にまたはランダム状に結
合している。 These amphoteric polymer compounds (A), (B),
In (B ′), (C) and (C ′), the cationic unit and the anionic unit are bonded alternately or randomly.
上記両性高分子化合物は、カチオン性のモノマーとし
て、例えばモノアリルアミン、N−メチルアリルアミ
ン、N,N−ジメチルアリルアミン、N−シクロヘキシル
アリルアミン、N,N−(メチル)シクロヘキシルアリル
アミン、N,N−ジシクロヘキシルアリルアミン、ジアリ
ルアミン、N−メチルジアリルアミン、N−ベンジルジ
アリルアミン、塩化ジアリルジメチルアンモニウム、臭
化ジアリルジメチルアンモニウム、ヨウ化ジアリルジメ
チルアンモニウム、メチル硫酸ジアリルジメチルアンモ
ニウム、塩化ジアリルメチルベンジルアンモニウム、臭
化ジアリルメチルベンジルアンモニウム、ヨウ化ジアリ
ルメチルベンジルアンモニウム、メチル硫酸ジアリルメ
チルベンジルアンモニウム、塩化ジアリルジベンジルア
ンモニウム、臭化ジアリルジベンジルアンモニウム、ヨ
ウ化ジアリルジベンジルアンモニウム、メチル硫酸ジア
リルジベンジルアンモニウムなどを用い、アニオン性の
モノマーとして、例えばマレイン酸、シトラコン酸また
はそれらのナトリウム塩、カリウム塩、アンモニウム塩
などを用い、これらを共重合することにより得られる。The amphoteric polymer compound includes, as cationic monomers, for example, monoallylamine, N-methylallylamine, N, N-dimethylallylamine, N-cyclohexylallylamine, N, N- (methyl) cyclohexylallylamine, N, N-dicyclohexylallylamine , Diallylamine, N-methyldiallylamine, N-benzyldiallylamine, diallyldimethylammonium chloride, diallyldimethylammonium bromide, diallyldimethylammonium iodide, diallyldimethylammonium methylsulfate, diallylmethylbenzylammonium chloride, diallylmethylbenzylammonium bromide, iodine Diallyl methylbenzyl ammonium bromide, diallyl methyl benzyl ammonium methyl sulfate, diallyl dibenzyl ammonium chloride, diallyl dibromide Benzylammonium, diallyldibenzylammonium iodide, diallyldibenzylammonium methylsulfate, etc., and as anionic monomers, for example, maleic acid, citraconic acid or their sodium, potassium, ammonium salts, etc. It is obtained by copolymerization.
カチオン性のモノマーとしては、モノアリルアミン、
ジアリルアミン、メチルジアリルアミン、ジアリルジメ
チルアンモニウムクロリドなどを、アニオン性のモノマ
ーとしてはマレイン酸およびシトラコン酸などを用いる
のが特に好ましい。Monoallylamine, as the cationic monomer,
It is particularly preferable to use diallylamine, methyldiallylamine, diallyldimethylammonium chloride, and the like, and as the anionic monomer, maleic acid, citraconic acid, and the like.
上記のカチオン系単位およびアニオン系単位の共重合
後のポリマーにおけるモル存在比は、5:1から1:3、好ま
しくは3:1から1:2の範囲である。The molar abundance ratio of the cationic unit and the anionic unit in the polymer after copolymerization is in the range of 5: 1 to 1: 3, preferably 3: 1 to 1: 2.
両性高分子化合物の分子量は1,000〜10,000,000の範
囲であることが好ましい。The molecular weight of the amphoteric polymer compound is preferably in the range of 1,000 to 10,000,000.
両性高分子化合物の具体例を示すと、以下のものなど
があげられる。Specific examples of the amphoteric polymer compound include the following.
一般式(A)で示される両性高分子化合物には、モノ
アリルアミン、N−メチルアリルアミン、N,N−ジメチ
ルアリルアミン、N−シクロヘキシルアリルアミン、N,
N−(メチル)シクロヘキシルアリルアミンまたはN,N−
ジシクロヘキシルアリルアミンとマレイン酸、シトラコ
ン酸またはそれらのナトリウム塩、カリウム塩、アンモ
ニウム塩との共重合体などがあげられる。The amphoteric polymer compound represented by the general formula (A) includes monoallylamine, N-methylallylamine, N, N-dimethylallylamine, N-cyclohexylallylamine,
N- (methyl) cyclohexylallylamine or N, N-
And copolymers of dicyclohexylallylamine with maleic acid, citraconic acid or their sodium, potassium, and ammonium salts.
一般式(B)または(B′)で示される両性高分子化
合物には、ジアリルアミン、N−メチルジアリルアミン
またはN−ベンジルジアリルアミンとマレイン酸、シト
ラコン酸またはそれらのナトリウム塩、カリウム塩、ア
ンモニウム塩との共重合体などがあげられる。The amphoteric polymer compound represented by the general formula (B) or (B ') includes diallylamine, N-methyldiallylamine or N-benzyldiallylamine with maleic acid, citraconic acid or their sodium, potassium, and ammonium salts. And copolymers.
一般式(C)または(C′)で示される両性高分子化
合物には、塩化ジアリルジメチルアンモニウム、臭化ジ
アリルジメチルアンモニウム、ヨウ化ジアリルジメチル
アンモニウム、メチル硫酸ジアリルジメチルアンモニウ
ム、塩化ジアリルメチルベンジルアンモニウム、臭化ジ
アリルメチルベンジルアンモニウム、ヨウ化ジアリルメ
チルベンジルアンモニウム、メチル硫酸ジアリルメチル
ベンジルアンモニウム、塩化ジアリルジベンジルアンモ
ニウム、臭化ジアリルジベンジルアンモニウム、ヨウ化
ジアリルジベンジルアンモニウムまたはメチル硫酸ジア
リルジベンジルアンモニウムとマレイン酸、シトラコン
酸またはそれらのナトリウム塩、カリウム塩、アンモニ
ウム塩との共重合体などがあげられる。The amphoteric polymer compound represented by the general formula (C) or (C ′) includes diallyldimethylammonium chloride, diallyldimethylammonium bromide, diallyldimethylammonium iodide, diallyldimethylammonium methylsulfate, diallyldimethylbenzylammonium chloride, Diallyl methylbenzyl ammonium iodide, diallyl methyl benzyl ammonium iodide, diallyl methyl benzyl ammonium methyl sulfate, diallyl dibenzyl ammonium chloride, diallyl dibenzyl ammonium bromide, diallyl dibenzyl ammonium iodide or diallyl dibenzyl ammonium methyl sulfate and maleic acid, And citraconic acid or a copolymer thereof with a sodium salt, a potassium salt, or an ammonium salt.
これらの両性高分子化合物の重合は次の条件で行われ
る。The polymerization of these amphoteric polymer compounds is performed under the following conditions.
カチオン性モノマーとアニオン性モノマーをそれぞれ
水中で混合する。重合開始剤は、過硫酸アンモニウム、
過硫酸カリウム、過酸化水素、tert−ブチルハイドロパ
ーオキサイドなどの過酸化物、または過酸化物とFe++、
NaSO3、アスコルビン酸などの還元剤を組み合わせたレ
ドックス系触媒を用いることができる。重合反応は大気
圧のN2中で行われる。重合温度は10〜100℃、好ましく
は25〜65℃であり、反応時間は10〜120時間、通常は24
〜96時間である。反応終了後の両性高分子化合物は水溶
液として得られ、これは必要であれば、乾燥粉砕して粉
末にもできる。The cationic monomer and the anionic monomer are each mixed in water. The polymerization initiator is ammonium persulfate,
Peroxides such as potassium persulfate, hydrogen peroxide, tert-butyl hydroperoxide, or peroxides and Fe ++ ,
A redox catalyst combining a reducing agent such as NaSO 3 or ascorbic acid can be used. The polymerization reaction is carried out in N 2 at atmospheric pressure. The polymerization temperature is 10 to 100 ° C, preferably 25 to 65 ° C, and the reaction time is 10 to 120 hours, usually 24 hours.
~ 96 hours. After completion of the reaction, the amphoteric polymer compound is obtained as an aqueous solution, which can be dried and pulverized to a powder if necessary.
この両性高分子化合物は化学的に安定であるのでカチ
オン性高分子化合物も同様に化学的に安定な物を選択す
れば、その組成物は脱水剤として、広範なpH領域の汚泥
をpH変動の大きい方法によって処理する場合も用いるこ
とができる。Since this amphoteric polymer compound is chemically stable, if the cationic polymer compound is also chemically stable, the composition can be used as a dehydrating agent to remove sludge in a wide pH range and to control pH fluctuation. It can also be used when processing by a large method.
汚泥脱水剤用組成物は、カチオン性高分子化合物に、
上記両性高分子化合物を添加することによって得られ
る。カチオン性高分子化合物に両性高分子化合物を少量
添加することも本発明の特徴である。両性高分子化合物
の添加量は、全体の0.1〜15重量%であるのが好まし
い。両性高分子化合物が成分として、高分子化合物全体
の0.1重量%未満の場合はその性質を発揮できにくくな
る。15重量%を超えると、組成物の脱水性能が漸減して
いきかつ脱水ケーキの性質も添加割合に比べて改善率が
小さくなり、添加効率が低減することになる。The composition for sludge dewatering agent is a cationic polymer compound,
It is obtained by adding the amphoteric polymer compound. It is a feature of the present invention that a small amount of an amphoteric polymer compound is added to the cationic polymer compound. The added amount of the amphoteric polymer compound is preferably 0.1 to 15% by weight of the whole. When the amphoteric polymer compound is less than 0.1% by weight of the entire polymer compound as a component, it becomes difficult to exhibit its properties. If it exceeds 15% by weight, the dewatering performance of the composition will gradually decrease, and the improvement of the properties of the dewatered cake will be smaller than the ratio of addition, and the addition efficiency will decrease.
とくに好ましい添加量は、1〜10重量%である。 A particularly preferred addition amount is 1 to 10% by weight.
使用時には、2種の高分子化合物からなる汚泥脱水剤
用組成物を0.01〜1重量%の水溶液にして、処理対象の
汚泥、或いは廃水中の浮遊物に添加してフロックを形成
させる。このフロックは、通常機械的方法によって脱水
処理される。At the time of use, a composition for a sludge dehydrating agent composed of two kinds of polymer compounds is made into an aqueous solution of 0.01 to 1% by weight, and is added to sludge to be treated or suspended matter in wastewater to form flocs. This floc is usually dewatered by a mechanical method.
両性高分子化合物は、カチオン性高分子化合物とあら
かじめ混合して組成物として用いるほか、カチオン性高
分子化合物のみを添加した後の汚泥に最終的な混合比率
が好ましくは0.1〜15重量%となるように加えるといっ
たような用い方もできる。The amphoteric polymer compound is mixed with the cationic polymer compound in advance and used as a composition, and the final mixing ratio of the sludge after adding only the cationic polymer compound is preferably 0.1 to 15% by weight. It can also be used like adding.
[作用] カチオン性高分子化合物に両性高分子化合物を混合す
ることがなぜ汚泥の脱水性能を向上させるのかは正確に
は明らかでないが、以下のように推測される。カチオン
性高分子化合物は親水性と汚泥凝集性を有する。また、
両性高分子化合物は、分子内での正負両イオンの吸引反
発から立体的に安定な構造をとり、このことから粘着度
の強い汚泥と反応しても脱水性並びに濾布剥離性を良好
に維持する性質がある。本発明の汚泥脱水剤用組成物の
優れた効果は、これらの高分子化合物の機能が相互に補
完し合って発揮されると考えられる。[Action] Although it is not exactly clear why mixing the amphoteric polymer compound with the cationic polymer compound improves the sludge dewatering performance, it is speculated as follows. Cationic polymer compounds have hydrophilicity and sludge cohesion. Also,
The amphoteric polymer compound has a sterically stable structure due to the repulsion of both positive and negative ions in the molecule, and maintains good dewatering properties and filter cloth releasability even when it reacts with highly sticky sludge. There is a nature to do. It is considered that the excellent effects of the composition for a sludge dewatering agent of the present invention are exhibited by mutually complementing the functions of these polymer compounds.
[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、本発明はこれによって限定されるものではない。EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.
(参考例) 両性高分子化合物の合成 (1)モノアリルアミン107g(1.874モル)とマレイン
酸174g(1.899モル)を水110gに溶解し、過硫酸アンモ
ニウム13gを加えてN2中で55℃,96時間重合反応をさせ
た。反応を終了させた後メタノール再沈法で得られた両
性高分子化合物の収率は88%であった。1/10規定の塩化
ナトリウム水溶液を溶媒として、c=0.5g/dl、30℃で
測定した、この両性高分子化合物の固有粘度は0.31dl/g
であった。以下、本両性高分子化合物を両性高分子化合
物(イ)という(この両性高分子化合物(イ)は上記一
般式(A)の両性高分子化合物に包含される)。(Reference Example) amphoteric Synthesis of Polymer Compound (1) monoallylamine 107 g (1.874 mol) and 174g of maleic acid (1.899 mol) was dissolved in water 110g, 55 ° C. in N 2 was added of ammonium persulfate 13 g, 96 h The polymerization reaction was performed. After terminating the reaction, the yield of the amphoteric polymer compound obtained by the methanol reprecipitation method was 88%. Using a 1/10 normal sodium chloride aqueous solution as a solvent, c = 0.5 g / dl, measured at 30 ° C. The intrinsic viscosity of this amphoteric polymer compound is 0.31 dl / g
Met. Hereinafter, the amphoteric polymer compound is referred to as an amphoteric polymer compound (a) (the amphoteric polymer compound (a) is included in the amphoteric polymer compound of the general formula (A)).
(2)同様にジアリルアミン97g(0.998モル)とマレイ
ン酸58g(0.500モル)を水288gに溶解し、過硫酸アンモ
ニウム0.47gを加えてN2中で45℃,72時間重合反応をさせ
た。メタノール再沈法による両性高分子化合物の収率
は、99.5%であった。1/10規定の水酸化ナトリウム水溶
液を溶媒として、c=0.5g/dl、30℃で測定した、この
両性高分子化合物の固有粘度は1.48dl/gであった。以
下、本両性高分子化合物を両性高分子化合物(ロ)とい
う(この両性高分子化合物(ロ)は上記一般式(B)ま
たは(B′)の両性高分子化合物に包含される)。(2) Similarly, 97 g (0.998 mol) of diallylamine and 58 g (0.500 mol) of maleic acid were dissolved in 288 g of water, and 0.47 g of ammonium persulfate was added to carry out a polymerization reaction at 45 ° C. for 72 hours in N 2 . The yield of the amphoteric polymer compound by the methanol reprecipitation method was 99.5%. The intrinsic viscosity of the amphoteric polymer compound was 1.48 dl / g, measured at 30 ° C. using c / 10.5 g / dl aqueous sodium hydroxide as a solvent. Hereinafter, the amphoteric polymer compound is referred to as an amphoteric polymer compound (b) (the amphoteric polymer compound (b) is included in the amphoteric polymer compound of the general formula (B) or (B ')).
(3)同様にメチルジアリルアミン167g(1.502モル)
とシトラコン酸130g(0.999モル)を水445gに溶かし、
過硫酸アンモニウム2.9gを加えてN2中で55℃,48時間重
合反応をさせた。メタノール再沈法による両性高分子化
合物の収率は、76%であった。1/10規定の水酸化ナトリ
ウム水溶液を溶媒として、c=0.5g/dl、30℃で測定し
た、この両性高分子化合物の固有粘度は0.21dl/gであっ
た。以下、本両性高分子化合物を両性高分子化合物
(ハ)という(この両性高分子化合物(ハ)は上記一般
式(B)または(B′)の両性高分子化合物に包含され
る)。(3) Similarly, 167 g (1.502 mol) of methyldiallylamine
And 130 g (0.999 mol) of citraconic acid dissolved in 445 g of water,
2.9 g of ammonium persulfate was added, and a polymerization reaction was performed at 55 ° C. for 48 hours in N 2 . The yield of the amphoteric polymer compound by the methanol reprecipitation method was 76%. The intrinsic viscosity of this amphoteric polymer compound was 0.21 dl / g, measured at 30 ° C. using c / 10 gram aqueous sodium hydroxide as a solvent and c = 0.5 g / dl. Hereinafter, the amphoteric polymer compound is referred to as an amphoteric polymer compound (c) (the amphoteric polymer compound (c) is included in the amphoteric polymer compound of the general formula (B) or (B ')).
(4)同様にジアリルジメチルアンモニウムクロリド
(純度91.2%)176.6g(1モル)と40%NaOH100g(1モ
ル)を水124.9gに溶解し、この中に無水マレイン酸98.0
6g(1モル)を加えて溶解後、系を60−65℃に保持し、
過硫酸アンモニウム10.5g(モノマーに対して3.5重量
%)を2回に分けて添加した後、72時間重合させた。メ
タノール再沈法による両性高分子化合物の収率は98%で
あった。1/10規定の塩化ナトリウム水溶液を溶媒とし
て、C=0.5g/dl、30℃で測定した、この両性高分子化
合物の固有粘度は0.32dl/gであった。以下、本両性高分
子化合物を両性高分子化合物(ニ)という(この両性高
分子化合物(ニ)は上記一般式(C)または(C′)の
両性高分子化合物に包含される)。(4) Similarly, 176.6 g (1 mol) of diallyldimethylammonium chloride (purity: 91.2%) and 100 g (1 mol) of 40% NaOH were dissolved in 124.9 g of water, and 98.0 g of maleic anhydride was added thereto.
After adding and dissolving 6 g (1 mol), the system is kept at 60-65 ° C.
Ammonium persulfate (10.5 g, 3.5% by weight based on the monomer) was added in two portions, followed by polymerization for 72 hours. The yield of the amphoteric polymer compound by the methanol reprecipitation method was 98%. The intrinsic viscosity of the amphoteric polymer compound was 0.32 dl / g as measured at 30 ° C. using a 1/10 normal sodium chloride aqueous solution as a solvent and C = 0.5 g / dl. Hereinafter, the amphoteric polymer compound is referred to as an amphoteric polymer compound (d) (the amphoteric polymer compound (d) is included in the amphoteric polymer compound represented by the general formula (C) or (C ′)).
これら両性高分子化合物(イ)、(ロ)、(ハ)、
(ニ)は共に乾燥後粉砕して粉末としたものを用いた。These amphoteric polymer compounds (a), (b), (c),
(D) Both used after drying and pulverizing into powder.
カオチン性高分子化合物の合成 N,N−ジメチルアミノエチルメタアクリレートの塩化
メチル第4級塩を単独重合させてカチオン性高分子化合
物を得た。その1%水溶液の粘度は4000CPSであった。
以下、本カチオン性高分子化合物をカチオン性高分子化
合物(a)という。Synthesis of Chaotic Polymer Compound A cationic polymer compound was obtained by homopolymerizing methyl quaternary salt of N, N-dimethylaminoethyl methacrylate. The viscosity of the 1% aqueous solution was 4000 CPS.
Hereinafter, the present cationic polymer compound is referred to as a cationic polymer compound (a).
(実施例1〜16) 本発明の汚泥脱水剤用組成物の凝集効果の測定 本発明の汚泥脱水剤用組成物の性能について次の方法
と条件で測定を行った。(Examples 1 to 16) Measurement of Coagulation Effect of Sludge Dewatering Agent Composition of the Present Invention The performance of the sludge dewatering agent composition of the present invention was measured by the following method and conditions.
汚泥脱水剤用組成物は、参考例で得たカチオン性高分
子化合物(a)に、参考例で得た両性高分子化合物
(イ)、(ロ)、(ハ)、(ニ)を5%、10%となるよ
うに混合して得た。第1表に示すようにこれらの組成物
をそれぞれ組成物(i)、(ii)、(iii)、(iv)、
(v)、(vi)、(vii)、(viii)とする。The composition for a sludge dewatering agent was prepared by adding 5% of the cationic polymer compound (a) obtained in Reference Example to the amphoteric polymer compounds (A), (B), (C), and (D) obtained in Reference Example. , 10%. As shown in Table 1, these compositions were used as compositions (i), (ii), (iii), (iv),
(V), (vi), (vii), and (viii).
脱水作用の評価は以下のヌッチェテストによっておこ
なった。汚泥をビーカーに200ml取り、それに0.2重量%
の汚泥脱水剤用組成物を含む水溶液を所定量加えよく混
合する。それを100メッシュのナイロン瀘布上に注ぎ、3
0秒後の瀘液量を測定した。瀘布上の汚泥フロックにつ
いては、圧搾試験機を用いて1kg/cm2の加重を1分間与
えて脱水ケーキとし、そのケーキ含水率と瀘布剥離性を
求めた。The evaluation of the dehydration effect was performed by the following Nutsche test. Take 200ml of sludge into a beaker and add 0.2% by weight
A predetermined amount of an aqueous solution containing the composition for a sludge dewatering agent is added and mixed well. Pour it over 100 mesh nylon filter cloth and add 3
The filtrate volume after 0 seconds was measured. The sludge floc on the filter cloth was applied with a load of 1 kg / cm 2 for 1 minute using a compression tester to form a dewatered cake, and the water content of the cake and the releasability of the filter cloth were determined.
測定には、下水処理場の混合汚泥およびし尿処理場の
混合汚泥を試料に用いた。For the measurement, mixed sludge from a sewage treatment plant and mixed sludge from a human waste treatment plant were used as samples.
下水処理場の混合汚泥はpH6.0、SS2.6%であり、これ
に組成物(i)、(ii)、(iii)、(iv)、(v)、
(vi)、(vii)、(viii)をSSに対して0.8重量%とな
るよう添加した。ヌッチェテストの結果を第1表(実施
例1〜8)に示す。The mixed sludge of the sewage treatment plant has a pH of 6.0 and a SS of 2.6%, and contains the compositions (i), (ii), (iii), (iv), (v),
(Vi), (vii), and (viii) were added at 0.8% by weight based on SS. The results of the Nutsche test are shown in Table 1 (Examples 1 to 8).
し尿処理場の混合汚泥はpH6.8、SS1.8%であり、これ
に組成物(i)、(ii)、(iii)、(iv)、(v)、
(vi)、(vii)、(viii)をSSに対して1.6重量%とな
るよう添加した。ヌッチェテストの結果を第2表(実施
例9〜16)に示す。The mixed sludge of the night soil treatment plant has a pH of 6.8 and a SS of 1.8%, and the composition (i), (ii), (iii), (iv), (v),
(Vi), (vii) and (viii) were added at 1.6% by weight based on SS. The results of the Nutsche test are shown in Table 2 (Examples 9 to 16).
(比較例1〜4) 従来の高分子脱水剤の脱水効果の測定 上記実施例1〜16で両性高分子化合物と併用したカオ
チン性高分子化合物(a)のみを使用して、同様に脱水
性能を測定した(比較例1,2)。(Comparative Examples 1 to 4) Measurement of Dehydration Effect of Conventional Polymer Dehydrating Agent Similarly, the dehydration performance was similarly measured using only the chaotic polymer compound (a) used in combination with the amphoteric polymer compound in Examples 1 to 16 above. Was measured (Comparative Examples 1 and 2).
また、N,N−ジメチルアミノエチルアクリレートの塩
化メチル4級塩とアクリルアミドを80:20のモル比で重
合させて得たカチオン性高分子(b)(1%水溶液の粘
度は4000CPS)のみを使用して、同様に脱水性能を測定
した(比較例3,4)。Also, only the cationic polymer (b) (1% aqueous solution has a viscosity of 4000 CPS) obtained by polymerizing methyl quaternary salt of N, N-dimethylaminoethyl acrylate and acrylamide in a molar ratio of 80:20. Then, the dewatering performance was measured similarly (Comparative Examples 3 and 4).
これらの結果を第1表(比較例1,2)、第2表(比較
例3,4)に示す。The results are shown in Table 1 (Comparative Examples 1 and 2) and Table 2 (Comparative Examples 3 and 4).
(比較例5〜7) 本発明に含まれない汚泥脱水剤用組成物の凝集効果の測
定 N,N−ジメチルアミノエチルメタアクリレートの塩化
メチル4級塩とアクリル酸を50:50の成分重量組成比で
重合させて得た両性高分子化合物(c)(この両性高分
子化合物は本発明の両性高分子化合物に包含されないも
のであり、1%水溶液の粘度は1800CPS)の水溶液、お
よび両性高分子化合物(c)の乾燥粉末とカチオン性高
分子化合物(a)の乾燥粉末を重量比で5:95または10:9
0の割合で混合して水溶液にしたものを、実施例1〜8
および比較例1,2と同様の操作で下水処理場の混合汚泥
に添加しヌッチェテストを行った。(Comparative Examples 5 to 7) Measurement of agglomeration effect of composition for sludge dehydrating agent not included in the present invention 50:50 component weight composition of methyl quaternary salt of N, N-dimethylaminoethyl methacrylate and acrylic acid Amphoteric polymer compound (c) obtained by polymerization at a specific ratio (this amphoteric polymer compound is not included in the amphoteric polymer compound of the present invention, and a 1% aqueous solution has a viscosity of 1800 CPS); The dry powder of the compound (c) and the dry powder of the cationic polymer compound (a) are mixed in a weight ratio of 5:95 or 10: 9.
Examples 1 to 8 were prepared by mixing at a ratio of 0 to form an aqueous solution.
In addition, the same operation as in Comparative Examples 1 and 2 was performed, and the mixture was added to the mixed sludge in the sewage treatment plant to perform a Nutsche test.
得られた結果を第3表に示す。 Table 3 shows the obtained results.
[発明の効果] 上述の実施例および比較例からも示されるように、本
発明の汚泥脱水剤用組成物の脱水性能は、従来のカオチ
ン性高分子化合物からなる脱水剤およびカチオン性高分
子化合物に、本発明で用いられる両性高分子化合物に包
含されない両性高分子化合物を添加してなる脱水剤用組
成物に比較して優れている。加えて、脱水ケーキの強度
も高いため、ケーキのべとつきやくずれが少なく、剥離
性にも優れているため後処理も容易である。 [Effects of the Invention] As can be seen from the above Examples and Comparative Examples, the dewatering performance of the composition for a sludge dewatering agent of the present invention is as follows: Furthermore, it is superior to a composition for a dehydrating agent obtained by adding an amphoteric polymer compound not included in the amphoteric polymer compound used in the present invention. In addition, since the strength of the dewatered cake is high, the stickiness and breakage of the cake are small, and the cake is excellent in peelability, so that post-treatment is easy.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 平4−193308(JP,A) 特開 平2−31899(JP,A) 特開 昭64−4207(JP,A) 特開 昭61−245806(JP,A) 特開 昭52−95584(JP,A) (58)調査した分野(Int.Cl.6,DB名) C02F 11/00 - 11/20 B01D 21/01 ──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-4-193308 (JP, A) JP-A-2-31899 (JP, A) JP-A 64-4207 (JP, A) JP-A 61-1986 245806 (JP, A) JP-A-52-95584 (JP, A) (58) Fields investigated (Int. Cl. 6 , DB name) C02F 11/00-11/20 B01D 21/01
Claims (2)
び(III′)で示されるカチオン系単位の少なくとも1
種と下記の一般式(IV)で示されるアニオン系単位とを
含む両性高分子化合物とを混合して調製される汚泥脱水
剤用組成物。 [ただし、上記式(I)、(II)、(II′)、(II
I)、(III′)および(IV)において、R1、R2はそれぞ
れ独立に水素原子、メチル基またはシクロヘキシル基で
あり、R3は水素原子またはメチル基であり、Rは水素原
子、メチル基またはベンジル基であり、R5、R6はそれぞ
れ独立にメチル基またはベンジル基であり、Xはアニオ
ンであり、Yは結合するカルボキシル基それぞれに対し
独立に水素、ナトリウム、カリウムまたはアンモニウム
である。]1. A cationic polymer compound and at least one of cationic units represented by the following general formulas (I), (II), (II '), (III) and (III'):
A composition for a sludge dewatering agent prepared by mixing a seed with an amphoteric polymer compound containing an anionic unit represented by the following general formula (IV). [However, the above formulas (I), (II), (II '), (II
In I), (III ′) and (IV), R 1 and R 2 are each independently a hydrogen atom, a methyl group or a cyclohexyl group, R 3 is a hydrogen atom or a methyl group, and R is a hydrogen atom, methyl R 5 and R 6 are each independently a methyl group or a benzyl group, X is an anion, and Y is independently hydrogen, sodium, potassium or ammonium for each carboxyl group to be bonded. . ]
(A)、(B)、(B′)、(C)および(C′)より
選ばれる、請求項1に記載の汚泥脱水剤用組成物。 [ただし、上記式(A)、(B)、(B′)、(C)お
よび(C′)において、R1、R2、R3、R4、R5、R6、Xお
よびYは、請求項1において定義したのと同じ意味を有
する。〕2. The sludge dewatering agent according to claim 1, wherein the amphoteric polymer compound is selected from the following compounds (A), (B), (B '), (C) and (C'). Composition. [However, in the above formulas (A), (B), (B '), (C) and (C'), R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , X and Y are Has the same meaning as defined in claim 1. ]
Priority Applications (1)
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JP2294875A JP2983279B2 (en) | 1990-10-31 | 1990-10-31 | Composition for sludge dewatering agent |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2294875A JP2983279B2 (en) | 1990-10-31 | 1990-10-31 | Composition for sludge dewatering agent |
Publications (2)
Publication Number | Publication Date |
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JPH04166300A JPH04166300A (en) | 1992-06-12 |
JP2983279B2 true JP2983279B2 (en) | 1999-11-29 |
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ID=17813383
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JP4069163B2 (en) * | 2002-02-12 | 2008-04-02 | 友岡化研株式会社 | Organic sludge dewatering method and organic sludge dewatering flocculant |
JP2003245700A (en) * | 2002-02-26 | 2003-09-02 | Hymo Corp | Method for dehydrating organic sludge |
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