JP2015057276A - Polymer flocculant - Google Patents
Polymer flocculant Download PDFInfo
- Publication number
- JP2015057276A JP2015057276A JP2014158515A JP2014158515A JP2015057276A JP 2015057276 A JP2015057276 A JP 2015057276A JP 2014158515 A JP2014158515 A JP 2014158515A JP 2014158515 A JP2014158515 A JP 2014158515A JP 2015057276 A JP2015057276 A JP 2015057276A
- Authority
- JP
- Japan
- Prior art keywords
- water
- polymer
- soluble
- acid
- parts
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 78
- 229920001577 copolymer Polymers 0.000 claims abstract description 71
- 239000000178 monomer Substances 0.000 claims abstract description 68
- 150000003839 salts Chemical class 0.000 claims abstract description 57
- 239000010802 sludge Substances 0.000 claims abstract description 42
- 238000000034 method Methods 0.000 claims abstract description 39
- 239000002351 wastewater Substances 0.000 claims abstract description 25
- 125000002091 cationic group Chemical group 0.000 claims abstract description 23
- 239000007788 liquid Substances 0.000 claims abstract description 6
- 238000000926 separation method Methods 0.000 claims abstract description 6
- 239000007864 aqueous solution Substances 0.000 claims description 74
- 239000002253 acid Substances 0.000 claims description 20
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 125000002947 alkylene group Chemical group 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 125000005842 heteroatom Chemical group 0.000 claims description 3
- 229910052727 yttrium Inorganic materials 0.000 claims description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 57
- -1 wastewater treatment Substances 0.000 description 53
- 238000006116 polymerization reaction Methods 0.000 description 38
- 239000007787 solid Substances 0.000 description 31
- 238000003756 stirring Methods 0.000 description 31
- 239000002245 particle Substances 0.000 description 26
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 24
- 238000004519 manufacturing process Methods 0.000 description 24
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 23
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 22
- 235000012970 cakes Nutrition 0.000 description 22
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 21
- 239000000701 coagulant Substances 0.000 description 20
- 230000002776 aggregation Effects 0.000 description 19
- 238000004220 aggregation Methods 0.000 description 15
- 239000004744 fabric Substances 0.000 description 14
- 239000000203 mixture Substances 0.000 description 14
- 235000014113 dietary fatty acids Nutrition 0.000 description 13
- 239000000194 fatty acid Substances 0.000 description 13
- 229930195729 fatty acid Natural products 0.000 description 13
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 12
- 238000005259 measurement Methods 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- 150000001412 amines Chemical class 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 11
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 239000000654 additive Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 229920001451 polypropylene glycol Polymers 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 8
- 239000002270 dispersing agent Substances 0.000 description 8
- 229940098779 methanesulfonic acid Drugs 0.000 description 8
- 230000002441 reversible effect Effects 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 125000000217 alkyl group Chemical group 0.000 description 7
- 239000002612 dispersion medium Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000000706 filtrate Substances 0.000 description 7
- 150000007522 mineralic acids Chemical class 0.000 description 7
- QLIBJPGWWSHWBF-UHFFFAOYSA-N 2-aminoethyl methacrylate Chemical compound CC(=C)C(=O)OCCN QLIBJPGWWSHWBF-UHFFFAOYSA-N 0.000 description 6
- USDJHFHQDMHVEW-UHFFFAOYSA-N 2-hydroxyethylazanium;methanesulfonate Chemical compound NCCO.CS(O)(=O)=O USDJHFHQDMHVEW-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 208000005156 Dehydration Diseases 0.000 description 6
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000000996 additive effect Effects 0.000 description 6
- 229910052783 alkali metal Inorganic materials 0.000 description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 6
- 125000000129 anionic group Chemical group 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 6
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 6
- 230000018044 dehydration Effects 0.000 description 6
- 238000006297 dehydration reaction Methods 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 238000005227 gel permeation chromatography Methods 0.000 description 6
- 239000011261 inert gas Substances 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 229910017604 nitric acid Inorganic materials 0.000 description 6
- 229920001223 polyethylene glycol Polymers 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- SSOLNOMRVKKSON-UHFFFAOYSA-N proguanil Chemical compound CC(C)\N=C(/N)N=C(N)NC1=CC=C(Cl)C=C1 SSOLNOMRVKKSON-UHFFFAOYSA-N 0.000 description 6
- 238000010557 suspension polymerization reaction Methods 0.000 description 6
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 6
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 6
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 5
- 125000002723 alicyclic group Chemical group 0.000 description 5
- 125000001931 aliphatic group Chemical group 0.000 description 5
- 239000012986 chain transfer agent Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000010779 crude oil Substances 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- 239000008394 flocculating agent Substances 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 230000002209 hydrophobic effect Effects 0.000 description 5
- 239000011976 maleic acid Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 125000004433 nitrogen atom Chemical group N* 0.000 description 5
- 239000010865 sewage Substances 0.000 description 5
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 238000005054 agglomeration Methods 0.000 description 4
- 150000001340 alkali metals Chemical class 0.000 description 4
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 4
- 239000000084 colloidal system Substances 0.000 description 4
- YKGMKSIHIVVYKY-UHFFFAOYSA-N dabrafenib mesylate Chemical compound CS(O)(=O)=O.S1C(C(C)(C)C)=NC(C=2C(=C(NS(=O)(=O)C=3C(=CC=CC=3F)F)C=CC=2)F)=C1C1=CC=NC(N)=N1 YKGMKSIHIVVYKY-UHFFFAOYSA-N 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- ATWDUWYFCBVNET-UHFFFAOYSA-N ethylammonium methanesulfonate Chemical compound CC[NH3+].CS([O-])(=O)=O ATWDUWYFCBVNET-UHFFFAOYSA-N 0.000 description 4
- 150000004665 fatty acids Chemical class 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000005342 ion exchange Methods 0.000 description 4
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 4
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 4
- PJUIMOJAAPLTRJ-UHFFFAOYSA-N monothioglycerol Chemical compound OCC(O)CS PJUIMOJAAPLTRJ-UHFFFAOYSA-N 0.000 description 4
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 4
- 150000003141 primary amines Chemical class 0.000 description 4
- 239000007870 radical polymerization initiator Substances 0.000 description 4
- 238000010526 radical polymerization reaction Methods 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 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 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical class ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 3
- 238000005345 coagulation Methods 0.000 description 3
- 230000015271 coagulation Effects 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 150000004662 dithiols Chemical class 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000003623 enhancer Substances 0.000 description 3
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 238000005189 flocculation Methods 0.000 description 3
- 230000016615 flocculation Effects 0.000 description 3
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical group 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 230000001771 impaired effect Effects 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- YACKEPLHDIMKIO-UHFFFAOYSA-N methylphosphonic acid Chemical compound CP(O)(O)=O YACKEPLHDIMKIO-UHFFFAOYSA-N 0.000 description 3
- ZQXSMRAEXCEDJD-UHFFFAOYSA-N n-ethenylformamide Chemical compound C=CNC=O ZQXSMRAEXCEDJD-UHFFFAOYSA-N 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- 150000007524 organic acids Chemical class 0.000 description 3
- 150000002978 peroxides Chemical class 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- UMSVPCYSAUKCAZ-UHFFFAOYSA-N propane;hydrochloride Chemical compound Cl.CCC UMSVPCYSAUKCAZ-UHFFFAOYSA-N 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- 239000010801 sewage sludge Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000002562 thickening agent Substances 0.000 description 3
- 125000003396 thiol group Chemical group [H]S* 0.000 description 3
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 3
- 238000004065 wastewater treatment Methods 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N 1-nonene Chemical compound CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- BLOQISMXYPADKL-UHFFFAOYSA-N 1-prop-2-enoyloxypropane-1-sulfonic acid Chemical compound CCC(S(O)(=O)=O)OC(=O)C=C BLOQISMXYPADKL-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 2
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 2
- SDNXQWUJWNTDCC-UHFFFAOYSA-N 2-methylsulfonylethanamine Chemical compound CS(=O)(=O)CCN SDNXQWUJWNTDCC-UHFFFAOYSA-N 0.000 description 2
- SNCMCDMEYCLVBO-UHFFFAOYSA-N 3-aminopropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCN SNCMCDMEYCLVBO-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 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
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- YYLLIJHXUHJATK-UHFFFAOYSA-N Cyclohexyl acetate Chemical compound CC(=O)OC1CCCCC1 YYLLIJHXUHJATK-UHFFFAOYSA-N 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- QLZHNIAADXEJJP-UHFFFAOYSA-N Phenylphosphonic acid Chemical compound OP(O)(=O)C1=CC=CC=C1 QLZHNIAADXEJJP-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 229930006000 Sucrose Natural products 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
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- HVAMZGADVCBITI-UHFFFAOYSA-N pent-4-enoic acid Chemical compound OC(=O)CCC=C HVAMZGADVCBITI-UHFFFAOYSA-N 0.000 description 1
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- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
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- 150000003109 potassium Chemical class 0.000 description 1
- DJEHXEMURTVAOE-UHFFFAOYSA-M potassium bisulfite Chemical compound [K+].OS([O-])=O DJEHXEMURTVAOE-UHFFFAOYSA-M 0.000 description 1
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- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
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- NCNISYUOWMIOPI-UHFFFAOYSA-N propane-1,1-dithiol Chemical compound CCC(S)S NCNISYUOWMIOPI-UHFFFAOYSA-N 0.000 description 1
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- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
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- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
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- 238000010992 reflux Methods 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 230000011218 segmentation Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
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- 125000004964 sulfoalkyl group Chemical group 0.000 description 1
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- 239000006228 supernatant Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
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- 238000003786 synthesis reaction Methods 0.000 description 1
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 description 1
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- 238000010998 test method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- NBOMNTLFRHMDEZ-UHFFFAOYSA-N thiosalicylic acid Chemical compound OC(=O)C1=CC=CC=C1S NBOMNTLFRHMDEZ-UHFFFAOYSA-N 0.000 description 1
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- 229910052723 transition metal Inorganic materials 0.000 description 1
- IEKWPPTXWFKANS-UHFFFAOYSA-K trichlorocobalt Chemical compound Cl[Co](Cl)Cl IEKWPPTXWFKANS-UHFFFAOYSA-K 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 239000007762 w/o emulsion Substances 0.000 description 1
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- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Separation Of Suspended Particles By Flocculating Agents (AREA)
- Treatment Of Sludge (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
本発明は、高分子凝集剤に関する。さらに詳しくは、脱水性に優れる汚泥または廃水処理用等の高分子凝集剤に関する。 The present invention relates to a polymer flocculant. More specifically, the present invention relates to a polymer flocculant for sludge or wastewater treatment having excellent dewaterability.
従来、下水等の汚泥処理、廃水処理、あるいは土木現場での泥水処理、浚渫埋め立て時の泥水の沈降分離促進用等の処理剤として、さらには製紙用脱水剤や紙力増強剤等として水溶性高分子からなる高分子凝集剤が広く使用されている。とくに近年、発生する汚泥量等の増加から、脱水処理速度向上のニーズが高まってきていることや、有機性汚泥の性状の難脱水化に伴う、脱水ケーキの焼却処分費用の増大、並びに脱水ケーキをそのまま埋め立て処分する際の埋め立て地の逼迫した状況等から、より強固で、粗大なフロックを形成させ、脱水ケーキの含水率を大幅に低減することができる高分子凝集剤が強く望まれている。より強固で、粗大なフロックを形成させるために、例えば架橋型ポリマー(例えば特許文献1、2参照)が提案されている。 Conventionally, it is water-soluble as a treatment agent for sludge treatment such as sewage, wastewater treatment, mud treatment at civil engineering sites, and for promoting sedimentation and separation of muddy water at the time of reclamation, and also as a paper-making dehydrating agent and paper strength enhancer. Polymer flocculants made of polymers are widely used. Especially in recent years, the need to improve the speed of dewatering treatment has increased due to an increase in the amount of sludge generated, etc., and the cost of incineration of dewatered cake has increased due to the difficulty of dewatering the properties of organic sludge. From the tight situation of the landfill site when the landfill is disposed of as it is, there is a strong demand for a polymer flocculant capable of forming a stronger, coarser floc and greatly reducing the moisture content of the dehydrated cake. . In order to form stronger and coarser flocs, for example, cross-linked polymers (see, for example, Patent Documents 1 and 2) have been proposed.
しかしながら、特許文献1、2に記載の高分子凝集剤は、多少、形成されたフロックは強固になったものの、ケーキの含水率が不十分であり、さらなる脱水ケーキ含水率の低下が望まれていた。
本発明の目的は、脱水ケーキの含水率が低くなるフロックを形成する高分子凝集剤を提供することにある。
However, in the polymer flocculants described in Patent Documents 1 and 2, although the floc formed is somewhat strong, the moisture content of the cake is insufficient, and further reduction of the moisture content of the dehydrated cake is desired. It was.
An object of the present invention is to provide a polymer flocculant that forms flocs that reduce the water content of a dehydrated cake.
本発明者らは、上記課題を解決するため鋭意検討した結果、本発明に到達した。すなわち、本発明は、下記一般式(1)で表される水溶性カチオンモノマー(a1)を含有する水溶性不飽和モノマー(a)を構成単位とする水溶性(共)重合体(A)と、下記一般式(2)で表される塩(B)とを含有してなり、該(A)の重量に基づく該(B)の含有量が1〜20%である高分子凝集剤(P)である。
CH2=C(CH3)−CO−X1−Q−N+R1R2R3・Z- (1)
[式中、R1〜R3はH、X1はOまたはNH、Qは炭素数1〜4のアルキレン基、Z-はプロトン酸のH+を除く残基を表す。]
X2−N+R4R5R6・Y- (2)
[式中、X2はヘテロ原子を有していてもよい炭素数1〜5の1価の炭化水素基、R4〜R6はH、Y-はプロトン酸のH+を除く残基を表す。]
As a result of intensive studies to solve the above-mentioned problems, the present inventors have reached the present invention. That is, the present invention relates to a water-soluble (co) polymer (A) having a water-soluble unsaturated monomer (a) containing a water-soluble cationic monomer (a1) represented by the following general formula (1) as a structural unit: A polymer flocculant (P) comprising a salt (B) represented by the following general formula (2), wherein the content of (B) based on the weight of (A) is 1 to 20% ).
CH 2 = C (CH 3) -CO-X 1 -Q-N + R 1 R 2 R 3 · Z - (1)
[Wherein R 1 to R 3 are H, X 1 is O or NH, Q is an alkylene group having 1 to 4 carbon atoms, and Z − represents a residue other than H + of a protonic acid. ]
X 2 −N + R 4 R 5 R 6 · Y − (2)
[Wherein X 2 is a monovalent hydrocarbon group having 1 to 5 carbon atoms which may have a hetero atom, R 4 to R 6 are H, and Y − is a residue other than H + of a protonic acid. Represent. ]
本発明の高分子凝集剤(P)は下記の効果を奏する。
(1)粗大かつ強固なフロックを形成する
(2)凝集性能がよく、ろ液量が増大することから、脱水処理速度を向上できる。
(3)脱水ケーキ含水率が低いことから、発生する廃棄物量および焼却処理コストを大幅に削減できる。
The polymer flocculant (P) of the present invention has the following effects.
(1) Form coarse and strong flocs (2) Good flocculation performance and increase in the amount of filtrate, thus improving the dehydration speed.
(3) Since the moisture content of the dehydrated cake is low, the amount of generated waste and incineration costs can be greatly reduced.
[水溶性(共)重合体(A)]
本発明における水溶性(共)重合体(A)は、下記一般式(1)で表される水溶性カチオンモノマー(a1)を含有する水溶性不飽和モノマー(a)を構成単位とする水溶性(共)重合体である。
ここにおいて、水溶性とは、水に対する溶解度が1g以上/水100g(20℃)であることを意味する。
CH2=C(CH3)−CO−X1−Q−N+R1R2R3・Z- (1)
[Water-soluble (co) polymer (A)]
The water-soluble (co) polymer (A) in the present invention has a water-soluble unsaturated monomer (a) containing a water-soluble cationic monomer (a1) represented by the following general formula (1) as a structural unit. (Co) polymer.
Here, water-soluble means that the solubility in water is 1 g or more / 100 g of water (20 ° C.).
CH 2 = C (CH 3) -CO-X 1 -Q-N + R 1 R 2 R 3 · Z - (1)
一般式(1)中、R1〜R3はH、X1はOまたはNH、Qは炭素数1〜4のアルキレン基(メチレン、エチレンおよびプロピレン基等)を表す。アルキレン基の炭素数(以下、Cと略記することがある。)が4を超えると水への溶解性が悪くなる。
Z-はプロトン酸のH+を除く残基を表す。プロトン酸とはプロトンを与える酸と定義されるもので、該プロトン酸としては、無機酸(塩酸、硫酸、リン酸、硝酸等)、および有機酸[スルホン酸(パラトルエンスルホン酸、メタンスルホン酸、ドデシルベンゼンスルホン酸、ナフタレンスルホン酸等)、カルボン酸(シュウ酸、 酢酸、マレイン酸等)、ホスホン酸(メチルホスホン酸、フェニルホスホン酸等)等]が挙げられる。これらのうち、凝集性能の観点から好ましいのは無機酸および有機酸のうちのスルホン酸、さらに好ましいのは塩酸、硫酸、メタンスルホン酸、とくに好ましいのは硫酸、メタンスルホン酸である。
In the general formula (1), R 1 to R 3 are H, X 1 is O or NH, and Q is an alkylene group having 1 to 4 carbon atoms (such as methylene, ethylene, and propylene groups). If the number of carbon atoms of the alkylene group (hereinafter sometimes abbreviated as C) exceeds 4, the solubility in water becomes poor.
Z − represents a residue other than H + of the protonic acid. A proton acid is defined as an acid that gives a proton, and as the proton acid, an inorganic acid (hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, etc.) and an organic acid [sulfonic acid (paratoluenesulfonic acid, methanesulfonic acid) , Dodecylbenzenesulfonic acid, naphthalenesulfonic acid, etc.), carboxylic acids (oxalic acid, acetic acid, maleic acid, etc.), phosphonic acids (methylphosphonic acid, phenylphosphonic acid, etc.) and the like. Of these, sulfonic acid among inorganic acids and organic acids is preferable from the viewpoint of aggregating performance, hydrochloric acid, sulfuric acid and methanesulfonic acid are more preferable, and sulfuric acid and methanesulfonic acid are particularly preferable.
[水溶性不飽和モノマー(a)]
水溶性不飽和モノマー(a)には、前記一般式(1)で表される水溶性カチオンモノマー(a1)が含まれる。
(a1)としては、以下の塩[無機酸(塩酸、硫酸、リン酸、硝酸等)塩、有機酸[スルホン酸(パラトルエンスルホン酸、メタンスルホン酸、ドデシルベンゼンスルホン酸、ナフタレンスルホン酸等)、カルボン酸(シュウ酸、 酢酸、マレイン酸等)、ホスホン酸(メチルホスホン酸、フェニルホスホン酸等)塩等]、およびこれらの混合物等が挙げられる。
(a11)窒素原子含有メタアクリレート
窒素原子含有メタアクリレートとしては、C5〜8のもの、例えばアミノメチルメタアクリレート、アミノエチルメタアクリレート、アミノプロピルメタアクリレート、アミノブチルメタアクリレート;
[Water-soluble unsaturated monomer (a)]
The water-soluble unsaturated monomer (a) includes the water-soluble cationic monomer (a1) represented by the general formula (1).
Examples of (a1) include the following salts [inorganic acids (hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, etc.) salts, organic acids [sulfonic acids (paratoluenesulfonic acid, methanesulfonic acid, dodecylbenzenesulfonic acid, naphthalenesulfonic acid, etc.) Carboxylic acid (oxalic acid, acetic acid, maleic acid, etc.), phosphonic acid (methylphosphonic acid, phenylphosphonic acid etc.) salt, etc.], and mixtures thereof.
(A11) Nitrogen atom-containing methacrylate As the nitrogen atom-containing methacrylate, those having C5-8, such as aminomethyl methacrylate, aminoethyl methacrylate, aminopropyl methacrylate, aminobutyl methacrylate;
(a12)窒素原子含有メタアクリルアミド
窒素原子含有メタアクリルアミドとしては、C5〜8のもの、例えばアミノメチルメタアクリルアミド、アミノエチルメタアクリルアミド、アミノプロピルメタアクリルアミド、アミノブチルメタアクリルアミド。
(A12) Nitrogen atom-containing methacrylamide As nitrogen atom-containing methacrylamide, C5-8, for example, aminomethyl methacrylamide, aminoethyl methacrylamide, aminopropyl methacrylamide, aminobutyl methacrylamide.
これらの(a11)の塩、(a12)の塩のうち、後述の高分子凝集剤(P)の凝集性能および重合性の観点から好ましいのは(a11)の塩、さらに好ましいのはアミノエチルメタアクリレートおよびアミノプロピルメタアクリレートの塩、とくに好ましいのはアミノエチルメタアクリレートの塩である。さらに、これらの塩のうち好ましいのは塩酸塩、硫酸塩、メタンスルホン酸塩、さらに好ましいのは硫酸塩、メタンスルホン酸塩、とくに好ましいのは硫酸塩である。 Of these salts (a11) and (a12), the salt of (a11) is preferred from the viewpoint of the aggregation performance and polymerizability of the polymer flocculant (P) described later, and more preferred is aminoethylmeta Acrylate and aminopropyl methacrylate salts, particularly preferred are aminoethyl methacrylate salts. Further, among these salts, preferred are hydrochloride, sulfate and methanesulfonate, more preferred are sulfate and methanesulfonate, and particularly preferred is sulfate.
水溶性不飽和モノマー(a)には、前記水溶性カチオンモノマー(a1)以外に、その他の水溶性不飽和モノマー(a2)を含有させることができる。 The water-soluble unsaturated monomer (a) can contain other water-soluble unsaturated monomer (a2) in addition to the water-soluble cationic monomer (a1).
その他の水溶性不飽和モノマー(a2)としては、下記のカチオン性モノマー(a21)、ノニオン性モノマー(a22)、アニオン性モノマー(a23)、およびこれらの混合物が挙げられる。 Examples of the other water-soluble unsaturated monomer (a2) include the following cationic monomer (a21), nonionic monomer (a22), anionic monomer (a23), and mixtures thereof.
(a21)カチオン性モノマー
下記のもの、これらの塩[例えば無機酸(塩酸、硫酸、リン酸および硝酸等)塩、メチルクロライド塩、ジメチル硫酸塩およびベンジルクロライド塩]、およびこれらの混合物が挙げられる。
(A21) Cationic monomer The following are included, and salts thereof [for example, inorganic acid (hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, etc.) salts, methyl chloride salts, dimethyl sulfate salts and benzyl chloride salts], and mixtures thereof. .
(a211)前記(a1)以外の窒素原子含有(メタ)アクリレート
C5〜30のもの、例えばN,N−ジアルキル(アルキル基はC1〜2)アミノアルキル(C2〜3)(メタ)アクリレート[N,N−ジメチルアミノ−エチルおよび−プロピル(メタ)アクリレート、N,N−ジエチルアミノ−エチルおよび−プロピル(メタ)アクリレート等]、複素環含有(メタ)アクリレート[N−モルホリノエチル(メタ)アクリレート等];なお、本発明において(メタ)アクリレートはメタアクリレートおよびアクリレートを意味する。
(A211) Nitrogen atom-containing (meth) acrylates other than (a1) C5-30, such as N, N-dialkyl (alkyl group is C1-2) aminoalkyl (C2-3) (meth) acrylate [N, N-dimethylamino-ethyl and -propyl (meth) acrylate, N, N-diethylamino-ethyl and -propyl (meth) acrylate and the like], heterocyclic-containing (meth) acrylate [N-morpholinoethyl (meth) acrylate and the like]; In the present invention, (meth) acrylate means methacrylate and acrylate.
(a212)アミノ基を有するエチレン性不飽和化合物
C2〜21のもの、例えばビニルアミン、ビニルアニリン、(メタ)アリルアミン、p−アミノスチレン;
(a213)アミンイミド基を有する化合物
C6〜21のもの、例えば1,1,1−トリメチルアミン(メタ)アクリルイミド、1,1−ジメチル−1−エチルアミン(メタ)アクリルイミド。
(A212) ethylenically unsaturated compound having an amino group C2-21, such as vinylamine, vinylaniline, (meth) allylamine, p-aminostyrene;
(A213) Compound having an amine imide group C6-21, such as 1,1,1-trimethylamine (meth) acrylimide, 1,1-dimethyl-1-ethylamine (meth) acrylimide.
(a22)ノニオン性モノマー
下記のもの、およびこれらの混合物が挙げられる。
(a221)(メタ)アクリレート
C4以上かつ数平均分子量[以下Mnと略記。測定は後述の測定条件でのゲルパーミエイションクロマトグラフィー(GPC)法による。]5,000以下のもの、例えば水酸基含有(メタ)アクリレート[ヒドロキシエチル、ジエチレングリコールモノ、ポリエチレングリコール(重合度3〜50)、モノおよび(ポリ)グリセロール(重合度1〜10)モノ(メタ)アクリレート]およびアクリル酸アルキル(アルキル基はC1〜2)エステル(C4〜5のもの、例えばアクリル酸メチル、アクリル酸エチル);
(A22) Nonionic monomer The following are mentioned, and these mixtures.
(A221) (Meth) acrylate C4 or more and number average molecular weight [hereinafter abbreviated as Mn. The measurement is based on a gel permeation chromatography (GPC) method under the measurement conditions described later. ] 5,000 or less, for example, hydroxyl group-containing (meth) acrylate [hydroxyethyl, diethylene glycol mono, polyethylene glycol (degree of polymerization 3 to 50), mono and (poly) glycerol (degree of polymerization 1 to 10) mono (meth) acrylate And alkyl acrylate (alkyl group is C1-2) ester (C4-5, such as methyl acrylate, ethyl acrylate);
(a222)(メタ)アクリルアミドおよびその誘導体
C3〜30のもの、例えば(メタ)アクリルアミド、N−アルキル(C1〜3)(メタ)アクリルアミド[N−メチルおよびイソプロピル(メタ)アクリルアミド等]、N−アルキロール(メタ)アクリルアミド[N−メチロール(メタ)アクリルアミド等]、N−アルキロール(C1〜2)(メタ)アクリルアミドのアルキレンオキシド(C2〜3、以下AOと略記。)1〜8モル付加物;
(A222) (meth) acrylamide and its derivatives C3-30, such as (meth) acrylamide, N-alkyl (C1-3) (meth) acrylamide [N-methyl and isopropyl (meth) acrylamide etc.], N-alkyl Roll (meth) acrylamide [N-methylol (meth) acrylamide etc.], N-alkylol (C1-2) (meth) acrylamide alkylene oxide (C2-3, hereinafter abbreviated as AO) 1-8 mol adduct;
(a223)前記(a1)、(a21)および(a222)以外の窒素原子含有エチレン性不飽和化合物
C3〜30のもの、例えばアクリロニトリル、N−ビニルホルムアミド、N−ビニル−2−ピロリドン、N−ビニルイミダゾール、N−ビニルスクシンイミド、N−カルバゾールアルキル(C1〜3)(メタ)アクリレート、2−シアノエチル(メタ)アクリレート、ヒドロキシエチルマレイミドのAO2〜10モル付加物。
(A223) Nitrogen-containing ethylenically unsaturated compounds other than the above (a1), (a21) and (a222) C3-30, such as acrylonitrile, N-vinylformamide, N-vinyl-2-pyrrolidone, N-vinyl AO2 to 10 mol adduct of imidazole, N-vinylsuccinimide, N-carbazole alkyl (C1-3) (meth) acrylate, 2-cyanoethyl (meth) acrylate, and hydroxyethylmaleimide.
(a23)アニオン性モノマー
下記のもの、これらの塩[アルカリ金属(リチウム、ナトリウム、カリウム等、以下同じ。)塩、アルカリ土類金属(マグネシウム、カルシウム等、以下同じ。)塩、アンモニウム塩およびアミン(C1〜20)塩等]、およびこれらの混合物が挙げられる。
(A23) Anionic monomer The following, these salts [alkali metal (lithium, sodium, potassium, etc., the same shall apply hereinafter) salt, alkaline earth metal (magnesium, calcium, etc., the same shall apply hereinafter) salt, ammonium salt and amine (C1-20) salts and the like], and mixtures thereof.
(a231)不飽和カルボン酸
C3〜30のもの、例えば(メタ)アクリル酸、(無水)マレイン酸、フマル酸、(無水)イタコン酸、ビニル安息香酸、アリル酢酸;
(a232)不飽和スルホン酸
脂肪族不飽和スルホン酸(C2〜20、例えばビニルスルホン酸)、芳香族不飽和スルホン酸(C6〜20、例えばスチレンスルホン酸)、スルホ基含有(メタ)アクリレート[C2〜24、例えばスルホアルキル(C2〜20)(メタ)アクリレート[2−(メタ)アクリロイルオキシエタン、−プロパンおよび−ブタンスルホン酸、3−(メタ)アクリロイルオキシプロパンスルホン酸、4−(メタ)アクリロイルオキシブタンスルホン酸、2−(メタ)アクリロイルオキシ−2,2−ジメチルエタンスルホン酸、p−(メタ)アクリロイルオキシメチルベンゼンスルホン酸等]、スルホ基含有(メタ)アクリルアミド[2−(メタ)アクリロイルアミノエタンスルホン酸、2−および3−(メタ)アクリロイルアミノプロパンスルホン酸、2−および4−(メタ)アクリロイルアミノブタンスルホン酸、2−(メタ)アクリロイルアミノ−2,2−ジメチルエタンスルホン酸、p−(メタ)アクリロイルアミノメチルベンゼンスルホン酸等]、アルキル(C1〜20)(メタ)アリルスルホコハク酸エステル[メチル(メタ)アリルスルホコハク酸エステル等]等;
(A231) unsaturated carboxylic acids of C3-30, such as (meth) acrylic acid, (anhydrous) maleic acid, fumaric acid, (anhydrous) itaconic acid, vinylbenzoic acid, allyl acetic acid;
(A232) Unsaturated sulfonic acid Aliphatic unsaturated sulfonic acid (C2-20, for example, vinylsulfonic acid), aromatic unsaturated sulfonic acid (C6-20, for example, styrenesulfonic acid), sulfo group-containing (meth) acrylate [C2 To 24, such as sulfoalkyl (C2-20) (meth) acrylate [2- (meth) acryloyloxyethane, -propane and -butanesulfonic acid, 3- (meth) acryloyloxypropanesulfonic acid, 4- (meth) acryloyl Oxybutanesulfonic acid, 2- (meth) acryloyloxy-2,2-dimethylethanesulfonic acid, p- (meth) acryloyloxymethylbenzenesulfonic acid, etc.], sulfo group-containing (meth) acrylamide [2- (meth) acryloyl Aminoethanesulfonic acid, 2- and 3- (meth) acrylic Roylaminopropanesulfonic acid, 2- and 4- (meth) acryloylaminobutanesulfonic acid, 2- (meth) acryloylamino-2,2-dimethylethanesulfonic acid, p- (meth) acryloylaminomethylbenzenesulfonic acid, etc.] Alkyl (C1-20) (meth) allylsulfosuccinate [methyl (meth) allylsulfosuccinate and the like] and the like;
(a233)(メタ)アクリロイルポリオキシアルキレン(アルキレン基はC1〜3)硫酸エステル
(メタ)アクリロイルポリオキシエチレン[エチレンオキシド(以下EOと略記)付加モル数2〜50]硫酸エステル等。
(A233) (Meth) acryloyl polyoxyalkylene (alkylene group is C1-3) sulfate ester (meth) acryloyl polyoxyethylene [ethylene oxide (hereinafter abbreviated as EO) added mole number 2-50] sulfate ester and the like.
本発明におけるMnおよび後述の重量平均分子量(Mw)のGPC測定は次の測定条件に従うものとする。
<GPC測定条件>
GPC機種:HLC−8120GPC、東ソー(株)製
カラム :TSKgel GMHXL2本+TSKgel
Multipore HXL−M、東ソー(株)製
溶媒 :テトラヒドロフラン(THF)
検出装置 :屈折率検出器
基準物質 :標準ポリスチレン(TSKstandard
POLYSTYRENE)、東ソー(株)製
The GPC measurement of Mn and the weight average molecular weight (Mw) described later in the present invention shall conform to the following measurement conditions.
<GPC measurement conditions>
GPC model: HLC-8120GPC, manufactured by Tosoh Corporation Column: TSKgel 2 GMHXL + TSKgel
Multipore HXL-M, manufactured by Tosoh Corporation Solvent: Tetrahydrofuran (THF)
Detection device: Refractive index detector Reference material: Standard polystyrene (TSKstandard
POLYSTYRENE), manufactured by Tosoh Corporation
上記の水溶性不飽和モノマー(a2)のうち水溶性(共)重合体(A)の共重合性の観点から好ましいのは、(a211)、(a22)、(a231)、(a232)、さらに好ましいのは(a211)、(a222)、(a223)、(a231)、および(a232)のうちスルホ基含有(メタ)アクリレート、スルホ基含有(メタ)アクリルアミド、最も好ましいのは(a211)のうちのN,N−ジメチルアミノエチル(メタ)アクリレートの塩、(a222)のうちの(メタ)アクリルアミド、(a223)のうちのアクリロニトリル、N−ビニルホルムアミド、(a231)のうちの(メタ)アクリル酸、(無水)マレイン酸、(無水)イタコン酸およびこれらのアルカリ金属塩、(a232)のうちの2−(メタ)アクリロイルオキシエタンスルホン酸、2−および3−(メタ)アクリロイルオキシプロパンスルホン酸、2−(メタ)アクリロイルアミノ−2,2−ジメチルエタンスルホン酸およびこれらのアルカリ金属塩である。また、これらの(a2)は、任意に混合して共重合させることができる。 Among the water-soluble unsaturated monomers (a2), from the viewpoint of copolymerization of the water-soluble (co) polymer (A), (a211), (a22), (a231), (a232), Preferred among (a211), (a222), (a223), (a231), and (a232) is a sulfo group-containing (meth) acrylate, a sulfo group-containing (meth) acrylamide, and most preferred is (a211) N, N-dimethylaminoethyl (meth) acrylate salt, (meth) acrylamide in (a222), acrylonitrile in (a223), N-vinylformamide, (meth) acrylic acid in (a231) 2- (meth) acryloyl of (a232), (anhydrous) maleic acid, (anhydrous) itaconic acid and alkali metal salts thereof Oxy ethanesulfonic acid, 2- and 3- (meth) acryloyloxy-propanesulfonic acid, 2- (meth) acryloyl-2,2-dimethyl-ethane sulfonic acid and alkali metal salts thereof. Moreover, these (a2) can be arbitrarily mixed and copolymerized.
[水溶性不飽和モノマー(a)以外のその他のモノマー]
水溶性(共)重合体(A)を構成するモノマーとしては、前記水溶性不飽和モノマー(a)以外に、本発明の効果を阻害しない範囲で必要により水不溶性不飽和モノマー(x)を併用することができる。
水不溶性不飽和モノマー(x)としては、以下の(x1)〜(x5)、およびこれらの混合物が挙げられる。
[Other monomers other than the water-soluble unsaturated monomer (a)]
As a monomer constituting the water-soluble (co) polymer (A), in addition to the water-soluble unsaturated monomer (a), a water-insoluble unsaturated monomer (x) may be used in combination as long as the effects of the present invention are not impaired. can do.
Examples of the water-insoluble unsaturated monomer (x) include the following (x1) to (x5) and mixtures thereof.
(x1)C6〜23の(メタ)アクリレート
脂肪族または脂環式アルコール(C3〜20)の(メタ)アクリレート[プロピル−、ブチル−、ラウリル−、オクタデシル−およびシクロヘキシル(メタ)アクリレート等]およびエポキシ基(C4〜20)含有(メタ)アクリレート[グリシジル(メタ)アクリレート等];
(X1) C6-23 (meth) acrylate (meth) acrylate of aliphatic or cycloaliphatic alcohol (C3-20) [propyl-, butyl-, lauryl-, octadecyl- and cyclohexyl (meth) acrylate etc.] and epoxy Group (C4-20) -containing (meth) acrylate [glycidyl (meth) acrylate and the like];
(x2)[モノアルコキシ(C1〜20)、モノシクロアルコキシ(C3〜12)およびモノフェノキシ]ポリプロピレングリコール(ポリプロピレングリコールは以下、PPGと略記)[プロピレンオキシド(以下POと略記)付加モル数2〜50]の不飽和カルボン酸モノエステル
モノオール(C1〜20)もしくは1価フェノール(C6〜20)のPO付加物の(メタ)アクリル酸エステル[ω−メトキシPPG、ω−エトキシPPG、ω−プロポキシ、ω−ブトキシPPG、ω−シクロヘキソキシPPGおよびω−フェノキシPPGモノ(メタ)アクリレート等]、および2価アルコール(C2〜20)もしくは2価フェノール(C6〜20)のPO付加物の(メタ)アクリル酸エステル[ω−ヒドロキシエチル(ポリ)オキシプロピレンモノ(メタ)アクリレート等]等;
(X2) [monoalkoxy (C1-20), monocycloalkoxy (C3-12) and monophenoxy] polypropylene glycol (polypropylene glycol is hereinafter abbreviated as PPG) [propylene oxide (hereinafter abbreviated as PO) added mole number 2 50] Unsaturated carboxylic acid monoester monool (C1-20) or monohydric phenol (C6-20) PO adduct (meth) acrylic acid ester [ω-methoxy PPG, ω-ethoxy PPG, ω-propoxy , Ω-butoxy PPG, ω-cyclohexoxy PPG and ω-phenoxy PPG mono (meth) acrylate, etc.], and (meth) of PO adducts of dihydric alcohol (C2-20) or dihydric phenol (C6-20) Acrylic ester [ω-hydroxyethyl (poly) oxypropylene Mono (meth) acrylate, etc.] or the like;
(x3)C2〜30の不飽和炭化水素
エチレン、ノネン、スチレン、α−メチルスチレン等;
(x4)不飽和アルコール[C2〜4、例えばビニルアルコール、(メタ)アリルアルコール]のカルボン酸(C2〜30)エステル(プロピオン酸ビニル等);
(x5)ハロゲン含有モノマー(C2〜30、例えば塩化ビニル)。
(X3) C2-30 unsaturated hydrocarbon ethylene, nonene, styrene, α-methylstyrene and the like;
(X4) carboxylic acid (C2-30) ester of unsaturated alcohol [C2-4, for example, vinyl alcohol, (meth) allyl alcohol] (vinyl propionate, etc.);
(X5) A halogen-containing monomer (C2-30, such as vinyl chloride).
水溶性(共)重合体(A)を構成するモノマーの合計モル数に基づく前記各モノマーの含有量は、水溶性カチオンモノマー(a1)は、凝集性能の観点から好ましくは90%以上、さらに好ましくは95モル%以上;水溶性不飽和モノマー(a2)は、凝集性能および高分子量化の観点から好ましくは10モル%以下、さらに好ましくは5モル%以下;水不溶性不飽和モノマー(x)は、通常5モル%以下、凝集性能および高分子凝集剤の水への溶解性の観点から好ましくは1モル%以下である。 The content of each monomer based on the total number of moles of monomers constituting the water-soluble (co) polymer (A) is preferably 90% or more, more preferably water-soluble cationic monomer (a1) from the viewpoint of aggregation performance. 95 mol% or more; the water-soluble unsaturated monomer (a2) is preferably 10 mol% or less, more preferably 5 mol% or less from the viewpoint of aggregation performance and high molecular weight; the water-insoluble unsaturated monomer (x) is The amount is usually 5 mol% or less, and preferably 1 mol% or less from the viewpoint of aggregation performance and solubility of the polymer flocculant in water.
水溶性(共)重合体(A)は、ラジカル重合開始剤(d)、必要によりラジカル重合用連鎖移動剤(c)を用いて、上記モノマーを、公知の水溶液重合(例えば、特開昭55−133413号公報に記載の断熱重合、薄膜重合、噴霧重合等)や、公知の逆相懸濁重合(例えば特公昭54−30710号公報、特開昭56−26909号公報、特開平1−5808号公報に記載のもの)を含む種々の重合法[光重合(例えば特公平6−804公報に記載のもの)、沈澱重合(例えば特開昭61−123610公報に記載のもの)、逆相乳化重合(例えば特開昭58−197398号、特開平9−276605号に記載のもの)等]で、製造することができる。
該重合法のうち、工業上の観点から好ましいのは水溶液重合、逆相懸濁重合、光重合および逆相乳化重合、さらに好ましいのは水溶液重合および逆相懸濁重合である。
The water-soluble (co) polymer (A) is prepared by using a radical polymerization initiator (d) and, if necessary, a chain transfer agent for radical polymerization (c), the above monomers to form a known aqueous solution (for example, JP-A-55). Adiabatic polymerization, thin film polymerization, spray polymerization and the like described in JP-A-133413) and known reversed-phase suspension polymerization (for example, JP-B-54-30710, JP-A-56-26909, JP-A-1-5808). Various polymerization methods (including those described in Japanese Patent Publication No. 6-804), precipitation polymerization (such as those described in JP-A-61-123610), reverse phase emulsification And the like (for example, those described in JP-A-58-197398 and JP-A-9-276605).
Among the polymerization methods, aqueous solution polymerization, reverse phase suspension polymerization, photopolymerization and reverse phase emulsion polymerization are preferable from an industrial viewpoint, and aqueous solution polymerization and reverse phase suspension polymerization are more preferable.
ラジカル重合開始剤(d)としては、種々のもの、例えばアゾ化合物〔水溶性のもの[アゾビスアミジノプロパン(塩)、アゾビスシアノ吉草酸(塩)等]および油溶性のもの[アゾビスジメチルバレロニトリル、アゾビスイソブチロニトリル、アゾビスシクロヘキサンカルボニトリル等]〕および過酸化物〔水溶性のもの[過酢酸、t−ブチルパーオキサイド、過酸化水素、過硫酸アンモニウム、過硫酸ナトリウム、過硫酸カリウム等]および油溶性のもの[ベンゾイルパーオキシド、クメンヒドロキシパーオキシド等]〕が挙げられる。 Examples of the radical polymerization initiator (d) include various compounds such as azo compounds [water-soluble compounds [azobisamidinopropane (salt), azobiscyanovaleric acid (salt), etc.]] and oil-soluble compounds (azobisdimethylvaleronitrile). , Azobisisobutyronitrile, azobiscyclohexanecarbonitrile, etc.]] and peroxides [water soluble [peracetic acid, t-butyl peroxide, hydrogen peroxide, ammonium persulfate, sodium persulfate, potassium persulfate, etc.] And oil-soluble ones [benzoyl peroxide, cumene hydroxy peroxide, etc.].
上記アゾ化合物における塩としては、無機酸(塩酸、硫酸、リン酸、硝酸等)塩およびアルカリ金属(リチウム、ナトリウム、カリウム等)塩等が挙げられる。
上記過酸化物は還元剤と組み合わせてレドックス開始剤として用いてもよく、還元剤としては重亜硫酸塩(重亜硫酸ナトリウム、重亜硫酸カリウム、重亜硫酸アンモニウム等)、還元性金属塩[硫酸鉄(II)等]、遷移金属塩のアミン錯体[塩化コバルト(III)のペンタメチレンヘキサミン錯体、塩化銅(II)のジエチレントリアミン錯体等]、有機性還元剤〔アスコルビン酸、3級アミン[ジメチルアミノ安息香酸(塩)、ジメチルアミノエタノール等]等〕が挙げられる。
また、アゾ化合物、過酸化物およびレドックス開始剤はそれぞれ単独で用いてもよいし、2種以上を併用してもいずれでもよい。
Examples of the salt in the azo compound include inorganic acid (hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, etc.) salts and alkali metal (lithium, sodium, potassium, etc.) salts.
The above peroxide may be used as a redox initiator in combination with a reducing agent. Examples of the reducing agent include bisulfites (sodium bisulfite, potassium bisulfite, ammonium bisulfite, etc.), reducing metal salts [iron sulfate (II ), Etc.], amine complexes of transition metal salts [pentamethylenehexamine complexes of cobalt (III) chloride, diethylenetriamine complexes of copper (II) chloride, etc.], organic reducing agents [ascorbic acid, tertiary amine [dimethylaminobenzoic acid ( Salt), dimethylaminoethanol and the like].
Further, the azo compound, peroxide and redox initiator may be used alone or in combination of two or more.
上記ラジカル重合開始剤(d)のうち、得られる水溶性(共)重合体(A)の水不溶解分低減の観点からアゾ化合物が好ましい。
また、(d)の使用量は(A)の最適な分子量を得るとの観点から、(A)を構成するモノマーの全重量に基づいて、好ましい下限は0.001重量%、さらに好ましくは0.005重量%、とくに好ましくは0.01重量%、好ましい上限は1重量%、さらに好ましくは0.5重量%、とくに好ましくは0.1重量%、最も好ましくは0.05重量%である。
Of the radical polymerization initiator (d), an azo compound is preferable from the viewpoint of reducing the water-insoluble content of the water-soluble (co) polymer (A) to be obtained.
From the viewpoint of obtaining the optimum molecular weight of (A), the preferred lower limit is 0.001% by weight, more preferably 0, based on the total weight of the monomers constituting (A). 0.005% by weight, particularly preferably 0.01% by weight, and a preferred upper limit is 1% by weight, more preferably 0.5% by weight, particularly preferably 0.1% by weight, and most preferably 0.05% by weight.
ラジカル重合用連鎖移動剤(c)としては特に限定なく、例えば分子内に1つまたは2つ以上の水酸基を有する化合物[分子量32以上かつMn50,000以下、例えばメタノール、エタノール、イソプロピルアルコール、エチレングリコール、プロピレングリコール、ポリエチレングリコール(分子量100以上かつMn50,000以下)およびポリエチレンポリプロピレングリコール(分子量100以上かつMn50,000以下)]、アンモニア、分子内に1つまたは2つ以上のアミノ基を有する化合物[例えばアミン(C1〜30、例えばメチルアミン、ジメチルアミン、トリエチルアミンおよびプロパノールアミン)]、分子内に1つまたは2つ以上のチオール基を有する化合物(後述)、および(次)亜リン酸化合物〔亜リン酸、次亜リン酸、およびこれらの塩[アルカリ金属(Na、K等)塩等]、並びにこれらの誘導体等〕が挙げられる。
これらのうちで(A)の分子量制御の観点から好ましいのは、分子内に1つまたは2つ以上のチオール基を有する化合物である。
The chain transfer agent (c) for radical polymerization is not particularly limited. For example, a compound having one or more hydroxyl groups in the molecule [molecular weight of 32 or more and Mn of 50,000 or less, such as methanol, ethanol, isopropyl alcohol, ethylene glycol , Propylene glycol, polyethylene glycol (molecular weight of 100 or more and Mn 50,000 or less) and polyethylene polypropylene glycol (molecular weight of 100 or more and Mn 50,000 or less)], ammonia, a compound having one or more amino groups in the molecule [ For example, amines (C1-30, such as methylamine, dimethylamine, triethylamine and propanolamine)], compounds having one or more thiol groups in the molecule (described later), and (hypo) phosphite compounds [suboxides Re Acid, hypophosphorous acid, and salts thereof [alkali metal (Na, K, etc.) salts, and derivatives, etc.] and the like.
Among these, a compound having one or two or more thiol groups in the molecule is preferable from the viewpoint of controlling the molecular weight of (A).
分子内にチオール基を有する化合物には、以下の(1)、(2)、これらの混合物およびこれらの塩[アルカリ金属(例えばリチウム、ナトリウムおよびカリウム)塩、アルカリ土類金属(例えばマグネシウムおよびカルシウム)塩、アンモニウム塩、アミン(C1〜20)塩および無機酸(例えば塩酸、硫酸、硝酸およびリン酸)塩]が含まれる。 The compounds having a thiol group in the molecule include the following (1), (2), mixtures thereof and salts thereof [alkali metal (for example, lithium, sodium and potassium) salts, alkaline earth metals (for example, magnesium and calcium) Salt), ammonium salt, amine (C1-20) salt and inorganic acid (eg hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid) salt].
(1)1価チオール
脂肪族チオール[C1〜20、例えばメタンチオール、エタンチオール、プロパンチオール、n−オクタンチオール、n−ドデカンチオール、ヘキサデカンチオール、n−オクタデカンチオール、2−メルカプトエタノール、メルカプト酢酸、3−メルカプトプロピオン酸、1−チオグリセロール、チオグリコール酸モノエタノールアミン)、1−チオグリセロール、チオグリコール酸モノエタノールアミン、チオマレイン酸、システインおよび2−メルカプトエチルアミン]、脂環式チオール(C5〜20、例えばシクロペンタンチオールおよびシクロヘキサンチオール)および芳香(脂肪)族チオール(C6〜12、例えばベンゼンチオールおよびベンジルメルカプタンおよびチオサリチル酸)が挙げられる。
(1) Monovalent thiol Aliphatic thiol [C1-20, such as methanethiol, ethanethiol, propanethiol, n-octanethiol, n-dodecanethiol, hexadecanethiol, n-octadecanethiol, 2-mercaptoethanol, mercaptoacetic acid, 3-mercaptopropionic acid, 1-thioglycerol, thioglycolic acid monoethanolamine), 1-thioglycerol, thioglycolic acid monoethanolamine, thiomaleic acid, cysteine and 2-mercaptoethylamine], alicyclic thiols (C5-20) For example, cyclopentanethiol and cyclohexanethiol) and aromatic (aliphatic) thiols (C6-12, such as benzenethiol and benzyl mercaptan and thiosalicylic acid).
(2)多価チオール
ジチオール[脂肪族(C2〜40)ジチオール(例えばエタンジチオール、ジエチレングリコールジメルカプタン、トリエチレングリコールジメルカプタン、プロパンジチオール、1,3−および1,4−ブタンジチオール、1,6−ヘキサンジチオール、ネオペンタンジチオール等)、脂環式(C5〜20)ジチオール(例えばシクロペンタンジチオールおよびシクロヘキサンジチオール)および芳香族(C6〜16)ジチオール(例えばベンジルメルカプタン、ビフェニルジチオール)、トリチオール(C3〜20、例えばチオグリセリン)が挙げられる。
(2) polyvalent thiol dithiol [aliphatic (C2-40) dithiol (eg ethane dithiol, diethylene glycol dimercaptan, triethylene glycol dimercaptan, propanedithiol, 1,3- and 1,4-butanedithiol, 1,6- Hexanedithiol, neopentanedithiol, etc.), alicyclic (C5-20) dithiol (eg cyclopentanedithiol and cyclohexanedithiol) and aromatic (C6-16) dithiol (eg benzyl mercaptan, biphenyldithiol), trithiol (C3-20) For example, thioglycerin).
ラジカル重合用連鎖移動剤(c)の使用量は、(A)を構成する重合性モノマーの合計重量に基づいて、通常15重量%以下、高分子凝集剤の水への溶解性、凝集性能および(A)として最適な分子量を得るとの観点から、好ましい下限は0.0001%、さらに好ましくは0.0005%、とくに好ましくは0.001%、最も好ましくは0.005%、好ましい上限は10%、さらに好ましくは5%、とくに好ましくは3%、最も好ましくは1%である。 The amount of the chain transfer agent for radical polymerization (c) used is usually 15% by weight or less based on the total weight of the polymerizable monomers constituting (A), the solubility of the polymer flocculant in water, the aggregation performance and From the viewpoint of obtaining an optimal molecular weight as (A), the preferred lower limit is 0.0001%, more preferably 0.0005%, particularly preferably 0.001%, most preferably 0.005%, and the preferred upper limit is 10%. %, More preferably 5%, particularly preferably 3%, most preferably 1%.
水溶性(共)重合体(A)の製造方法のうち逆相懸濁重合法としては、例えば次の方法が挙げられる。
疎水性分散媒(e)および分散剤(f)を重合槽に仕込み、必要に応じて加熱しながら所定の重合温度(通常20〜100℃、好ましくは30〜80℃)に調整した後、槽内を不活性ガス(例えば窒素)で十分置換する。
一方、前記水溶性カチオンモノマー(a1)を含有する水溶性不飽和モノマー(a)、ラジカル重合開始剤(d)、および必要によりラジカル重合用連鎖移動剤(c)、並びに水不溶性不飽和モノマー(x)を加えたモノマー水溶液を調製し、不活性ガスで十分置換した後、撹拌下で重合槽内に投入し、懸濁させながら重合させる。
モノマー水溶液の投入方法としては、一括投入または滴下のいずれでもよい。また、その際モノマー水溶液としては、(a)、(d)および必要により加える(c)、および/または(x)の均一水溶液としてもよいし、別々の水溶液とした上で、滴下直前で混合してもよいし、別々に同時滴下してもよい。モノマー水溶液等を不活性ガスで置換する方法としては、モノマー水溶液等に不活性ガスをバブリング供給する方法、滴下ライン中でスタティックミキサー等により不活性ガスをブレンドする方法等が挙げられ、重合の均一性の観点からスタティックミキサーで不活性ガスをブレンドする方法が好ましい。
Among the production methods of the water-soluble (co) polymer (A), examples of the reverse phase suspension polymerization method include the following methods.
After the hydrophobic dispersion medium (e) and the dispersant (f) are charged into a polymerization tank and adjusted to a predetermined polymerization temperature (usually 20 to 100 ° C., preferably 30 to 80 ° C.) while heating as necessary, the tank The inside is sufficiently replaced with an inert gas (for example, nitrogen).
On the other hand, the water-soluble unsaturated monomer (a) containing the water-soluble cationic monomer (a1), the radical polymerization initiator (d), and optionally the radical transfer chain transfer agent (c), and the water-insoluble unsaturated monomer ( An aqueous monomer solution to which x) is added is prepared and sufficiently substituted with an inert gas, and then charged into a polymerization vessel under stirring and polymerized while being suspended.
The method for charging the monomer aqueous solution may be either batch charging or dropping. In this case, the monomer aqueous solution may be a uniform aqueous solution of (a), (d) and (c) and / or (x) added as necessary, or a separate aqueous solution, which is mixed immediately before dropping. Alternatively, they may be dropped simultaneously at the same time. Examples of the method of replacing the monomer aqueous solution with an inert gas include a method of bubbling and supplying an inert gas to the monomer aqueous solution, a method of blending an inert gas with a static mixer or the like in a dropping line, and the like. From the viewpoint of properties, a method of blending an inert gas with a static mixer is preferred.
疎水性分散媒(e)とは、水に対する溶解度(20℃)が1g未満/水100gである分散媒を意味し、下記のものが挙げられる。
(1)炭化水素
脂肪族(C5〜12、例えばn−ヘキサン、n−ヘプタン、n−オクタン、n−ノナン、n−デカン)、脂環含有(C5〜12、例えばシクロペンタン、シクロヘキサン、シクロヘプタン、メチルシクロヘキサン、シクロオクタン、デカリン)および芳香環含有炭化水素(C6〜12、例えばベンゼン、トルエン、キシレン、エチルベンゼン)等;
(2)ケトン
脂肪族(C3〜10、例えばメチル−n−プロピルケトン、ジエチルケトン、メチルイソブチルケトン)、脂環含有(C5〜10、例えばシクロペンタノン、シクロヘキサノン)および芳香環含有ケトン(C8〜13、例えばアセトフェノン、ベンゾフェノン)等;
(3)エーテル
脂肪族(C4〜8、例えばジ−n−プロピルエーテル、ジ−n−ブチルエーテル、ジエチレングリコールジメチルエーテル)、環状(C4〜18、例えばテトラヒドロピラン)および芳香環含有エーテル(C7〜12、例えばアニソール)等;
(4)エステル
脂肪族(C3〜10、例えば酢酸n−ブチル、酢酸イソブチル)、脂環含有(C7〜12、例えば酢酸シクロヘキシル、シクロヘキサンカルボン酸メチル)および芳香環含有エステル(C8〜13、例えば安息香酸メチル、安息香酸エチル、安息香酸n−ブチル、酢酸ベンジル、ジメチルフタレート、ジエチルフタレート、ジ−n−ブチルフタレート)等。
これらのうち、製造時の取り扱い性、および重合時の温度制御の観点から、好ましいのは脂肪族および脂環含有炭化水素、脂肪族および脂環含有エステル、さらに好ましいのはn−ヘキサン、n−ヘプタン、n−オクタン、n−ノナン、n−デカン、シクロヘキサン、メチルシクロヘキサン、酢酸n−ブチル、酢酸イソブチルおよび酢酸シクロヘキシルである。
The hydrophobic dispersion medium (e) means a dispersion medium having a solubility in water (20 ° C.) of less than 1 g / 100 g of water, and includes the following.
(1) Hydrocarbon aliphatic (C5-12, such as n-hexane, n-heptane, n-octane, n-nonane, n-decane), alicyclic ring (C5-12, such as cyclopentane, cyclohexane, cycloheptane) , Methylcyclohexane, cyclooctane, decalin) and aromatic ring-containing hydrocarbons (C6-12, such as benzene, toluene, xylene, ethylbenzene) and the like;
(2) Ketone Aliphatic (C3-10, such as methyl-n-propylketone, diethylketone, methylisobutylketone), alicyclic ring-containing (C5-10, such as cyclopentanone, cyclohexanone) and aromatic ring-containing ketone (C8- 13, for example, acetophenone, benzophenone) and the like;
(3) Ethers Aliphatic (C4-8, eg di-n-propyl ether, di-n-butyl ether, diethylene glycol dimethyl ether), cyclic (C4-18, eg tetrahydropyran) and aromatic ring-containing ethers (C7-12, eg Anisole) and the like;
(4) Esters Aliphatic (C3-10, eg n-butyl acetate, isobutyl acetate), alicyclic (C7-12, eg cyclohexyl acetate, methyl cyclohexanecarboxylate) and aromatic ring containing esters (C8-13, eg benzoic) Acid methyl, ethyl benzoate, n-butyl benzoate, benzyl acetate, dimethyl phthalate, diethyl phthalate, di-n-butyl phthalate) and the like.
Among these, from the viewpoints of handling during production and temperature control during polymerization, aliphatic and alicyclic hydrocarbons, aliphatic and alicyclic esters are preferable, and n-hexane, n-hexane are more preferable. Heptane, n-octane, n-nonane, n-decane, cyclohexane, methylcyclohexane, n-butyl acetate, isobutyl acetate and cyclohexyl acetate.
疎水性分散媒(e)の使用量は、分散系の安定性の観点からモノマー水溶液の全重量に基づいて、好ましい下限は25%、さらに好ましくは40%、とくに好ましくは65%、生産性の観点から好ましい上限は1,000%、さらに好ましくは400%、とくに好ましくは200%である。 The amount of the hydrophobic dispersion medium (e) used is preferably 25%, more preferably 40%, particularly preferably 65% based on the total weight of the aqueous monomer solution from the viewpoint of the stability of the dispersion. From the viewpoint, the upper limit is preferably 1,000%, more preferably 400%, and particularly preferably 200%.
分散剤(f)としては、逆相懸濁粒子の分散安定性、および得られる高分子凝集剤の粉体流動性を制御する観点から、好ましくはHLB(Hydrophile−Lipophile Balance)が1〜8、さらに好ましくは2〜7、とくに好ましくは3〜5の、種々の油溶性物質が挙げられる。ここにおいてHLBとは親水性と親油性とのつり合いを表し、下記の式から求められる(「界面活性剤の合成と其応用」、501頁、1957年槇書店刊;「界面活性剤入門」、212−213頁、2007年三洋化成工業刊、等参照)。
HLB=10×(無機性/有機性)
上記式中、( )内は有機化合物の無機性と有機性の比率を表し、該比率は上記文献に記載されている値から計算することができる。
As the dispersant (f), from the viewpoint of controlling the dispersion stability of the reversed-phase suspended particles and the powder flowability of the resulting polymer flocculant, preferably HLB (Hydrophile-Lipophile Balance) is 1 to 8, More preferably, various oil-soluble substances of 2 to 7, particularly preferably 3 to 5, are mentioned. Here, HLB represents a balance between hydrophilicity and lipophilicity, and is determined from the following formula ("Surfactant Synthesis and Its Application", page 501, published by Tsuji Shoten in 1957; "Introduction to Surfactants", 212-213, 2007, published by Sanyo Kasei Kogyo, etc.).
HLB = 10 × (inorganic / organic)
In the above formula, the value in () represents the inorganic to organic ratio of the organic compound, and the ratio can be calculated from the values described in the above documents.
(f)には、重量平均分子量[以下Mwと略記。測定は前記条件でのGPC法による。]が5,000未満(さらに好ましくは100〜3,000、とくに好ましくは100〜1,000)の低分子分散剤(f1)、およびMwが5,000以上(さらに好ましくは7,000〜1,000,000、とくに好ましくは10,000〜100,000)の高分子分散剤(f2)が含まれる。 In (f), weight average molecular weight [hereinafter abbreviated as Mw. The measurement is based on the GPC method under the above conditions. ] Is less than 5,000 (more preferably from 100 to 3,000, particularly preferably from 100 to 1,000), and a low molecular dispersant (f1), and Mw is 5,000 or more (more preferably from 7,000 to 1). , 1,000,000, particularly preferably 10,000 to 100,000) of the polymer dispersant (f2).
(f1)には、多価(2〜8またはそれ以上)アルコールの脂肪酸(C10〜30)エステル〔ショ糖脂肪酸エステル(C22〜120、例えばショ糖ジステアレート、ショ糖トリステアレート)、ソルビタン脂肪酸エステル(C16〜120、例えばソルビタンモノステアレート、ソルビタンモノオレート)、(ポリ)グリセリン脂肪酸エステル(C12〜120、例えばグリセリンモノステアレート)、PEG脂肪酸エステル[Mw100〜5,000未満、例えばPEGのモノステアレート]等〕、アルキル(C1〜30)アリルエーテル等が含まれる。 (F1) includes fatty acid (C10-30) esters of polyhydric (2-8 or more) alcohols [sucrose fatty acid esters (C22-120, such as sucrose distearate, sucrose tristearate), sorbitan fatty acid esters (C16-120, eg sorbitan monostearate, sorbitan monooleate), (poly) glycerin fatty acid ester (C12-120, eg glycerin monostearate), PEG fatty acid ester [Mw 100-less than 5000, eg monostearate of PEG Rate] and the like, and alkyl (C1-30) allyl ether and the like.
上記(f1)のうち、製造時における装置への重合粒子付着防止および高分子凝集剤の粉体流動性の観点から好ましいのは、多価アルコールの脂肪酸エステル、さらに好ましいのは、ショ糖脂肪酸エステル、ソルビタン脂肪酸エステル、PEG脂肪酸エステルである。 Of the above (f1), from the viewpoints of preventing polymer particle adhesion to the apparatus during production and the powder flowability of the polymer flocculant, fatty acid esters of polyhydric alcohols are preferred, and sucrose fatty acid esters are more preferred. Sorbitan fatty acid ester and PEG fatty acid ester.
(f2)には、アルケンとα,β−不飽和多価カルボン酸(無水物)との共重合体またはその誘導体[例えば1−オレフィン(C11〜100)/(無水)マレイン酸共重合体、およびそのアミン反応物]、長鎖アルキル基(C12〜50)含有(メタ)アクリレート(共)重合体、変性(アミノ、カルボキシ、エポキシ、ヒドロキシ、メルカプト、脂肪酸エステル、脂肪酸アミド変性等)オルガノポリシロキサン、セルロースエーテル(例えばエチルセルロース、エチルヒドロキシエチルセルロース)、エチレン・酢酸ビニル共重合体、および無水マレイン酸変性された、エチレン・酢酸ビニル共重合体等が含まれる。 (F2) includes a copolymer of alkene and α, β-unsaturated polyvalent carboxylic acid (anhydride) or a derivative thereof [for example, 1-olefin (C11-100) / (anhydrous) maleic acid copolymer, And its amine reaction product], long-chain alkyl group (C12-50) -containing (meth) acrylate (co) polymer, modified (amino, carboxy, epoxy, hydroxy, mercapto, fatty acid ester, fatty acid amide modified, etc.) organopolysiloxane , Cellulose ethers (for example, ethyl cellulose, ethyl hydroxyethyl cellulose), ethylene / vinyl acetate copolymers, and ethylene / vinyl acetate copolymers modified with maleic anhydride.
分散剤(f)の使用に当たっては、逆相懸濁粒子の分散安定性および高分子凝集剤の粉体流動性、粒度分布の観点から(f1)と(f2)を併用することが好ましく、併用する際の重量比[(f1)/(f2)]は、同様の観点から好ましくは70/30〜1/99、さらに好ましくは50/50〜5/95である。
(f1)と(f2)を併用する場合、粒度分布の観点から好ましい組合せは、多価アルコールの脂肪酸エステルと無水マレイン酸変性されたエチレン・酢酸ビニル共重合体の組合せ、さらに好ましいのはPEG脂肪酸エステルと無水マレイン酸変性されたエチレン・酢酸ビニル共重合体の組み合わせである。
In using the dispersant (f), it is preferable to use (f1) and (f2) in combination from the viewpoints of dispersion stability of the reversed-phase suspended particles, powder flowability of the polymer flocculant, and particle size distribution. From the same viewpoint, the weight ratio [(f1) / (f2)] is preferably 70/30 to 1/99, more preferably 50/50 to 5/95.
When (f1) and (f2) are used in combination, a preferred combination from the viewpoint of particle size distribution is a combination of a fatty acid ester of a polyhydric alcohol and a maleic anhydride-modified ethylene / vinyl acetate copolymer, more preferably a PEG fatty acid. This is a combination of an ester and a maleic anhydride-modified ethylene / vinyl acetate copolymer.
(f)の使用量は、疎水性分散媒(e)の重量に基づいて、通常20重量%以下、逆相懸濁粒子の安定性、高分子凝集剤の粉体流動性および粒子径制御の観点から、好ましくは0.01〜10重量%、さらに好ましくは0.05〜5重量%である。 The amount of (f) used is usually 20% by weight or less based on the weight of the hydrophobic dispersion medium (e), the stability of the reversed phase suspension particles, the powder flowability of the polymer flocculant and the particle size control. From the viewpoint, it is preferably 0.01 to 10% by weight, more preferably 0.05 to 5% by weight.
重合性モノマー水溶液中のモノマー濃度(重量%)は、下限は通常30%、高分子量化の観点から好ましくは40%、さらに好ましくは45%、とくに好ましくは50%、最も好ましくは55%、上限は通常90%、重合温度制御の観点から好ましくは85%、さらに好ましくは80%、とくに好ましくは75%、最も好ましくは70%である。 The lower limit of the monomer concentration (% by weight) in the aqueous polymerizable monomer solution is usually 30%, preferably 40%, more preferably 45%, particularly preferably 50%, most preferably 55%, and the upper limit. Is usually 90%, preferably 85%, more preferably 80%, particularly preferably 75%, most preferably 70% from the viewpoint of polymerization temperature control.
重合温度は、下限は通常10℃、重合速度の観点から好ましくは20℃、より好ましくは30℃、とくに好ましくは40℃、最も好ましくは50℃、上限は通常95℃、ポリマーの熱劣化防止の観点から好ましくは90℃、さらに好ましくは80℃、とくに好ましくは70℃、最も好ましくは60℃である。
また、重合中は所定重合温度を一定(例えば所定重合温度±5℃)に保つよう、適宜加熱、冷却して調節することが好ましい。重合温度を一定に保つために、予め所定重合温度に温調した分散媒に撹拌下でモノマーを随時滴下してもよい。その際の滴下時間は、モノマー濃度、および重合反応発熱量により異なるが、通常0.5〜20時間、生産性および温度制御の観点から好ましくは1〜10時間である。
The lower limit of the polymerization temperature is usually 10 ° C., preferably 20 ° C. from the viewpoint of the polymerization rate, more preferably 30 ° C., particularly preferably 40 ° C., most preferably 50 ° C., and the upper limit is usually 95 ° C. to prevent thermal degradation of the polymer. From the viewpoint, it is preferably 90 ° C, more preferably 80 ° C, particularly preferably 70 ° C, and most preferably 60 ° C.
Further, during polymerization, it is preferable to adjust by appropriately heating and cooling so that the predetermined polymerization temperature is kept constant (for example, predetermined polymerization temperature ± 5 ° C.). In order to keep the polymerization temperature constant, the monomer may be added dropwise to the dispersion medium that has been previously adjusted to a predetermined polymerization temperature under stirring. The dropping time at that time varies depending on the monomer concentration and the calorific value of the polymerization reaction, but is usually 0.5 to 20 hours, and preferably 1 to 10 hours from the viewpoint of productivity and temperature control.
重合時間は重合による発熱がなくなった時点で終了が確認できるが、通常発熱により重合開始を確認した時点から1〜24時間、工業的観点および重合を完結し、残存モノマーを減少させるとの観点から、好ましくは2〜12時間である。逆相懸濁重合の場合のように、モノマーを随時滴下する場合は滴下終了後から上記時間重合することが好ましい。
上記のモノマー濃度、重合温度および重合時間は、モノマー組成、および開始剤種類等によって適宜調整することができる。
The polymerization time can be confirmed to end when the exotherm is eliminated by polymerization, but from the viewpoint of completing the polymerization from 1 to 24 hours from the point of confirming the start of polymerization by normal exotherm, and reducing the residual monomer. , Preferably 2 to 12 hours. As in the case of reverse phase suspension polymerization, when the monomer is dropped at any time, it is preferable to carry out the polymerization for the above time after completion of the dropping.
The monomer concentration, polymerization temperature, and polymerization time can be appropriately adjusted depending on the monomer composition, the initiator type, and the like.
重合時の圧力(単位はkPa、以下絶対圧力を示す。)は、特に限定されないが、逆相懸濁重合の場合、重合時の温度調節が容易である点から、好ましくは重合温度において、分散媒が沸騰する圧力または疎水性分散媒と水とが共沸する圧力が好ましい。具体的には、好ましい下限は5kPa、さらに好ましくは12kPa、とくに好ましくは25kPa、好ましい上限は95kPa、さらに好ましくは80kPa、とくに好ましくは65kPaである。 The pressure at the time of polymerization (unit: kPa, hereinafter referred to as absolute pressure) is not particularly limited, but in the case of reverse phase suspension polymerization, it is preferable that the dispersion is preferably performed at the polymerization temperature from the viewpoint of easy temperature control during the polymerization. A pressure at which the medium boils or a pressure at which the hydrophobic dispersion medium and water azeotrope is preferable. Specifically, the preferred lower limit is 5 kPa, more preferably 12 kPa, particularly preferably 25 kPa, and the preferred upper limit is 95 kPa, more preferably 80 kPa, and particularly preferably 65 kPa.
重合時のモノマー水溶液のpHは、特に限定されないが、重合速度、得られる水溶性重合体の溶解性の観点から、好ましくは0.5〜7、さらに好ましくは1〜6、とくに好ましくは1.5〜5である。 The pH of the aqueous monomer solution at the time of polymerization is not particularly limited, but is preferably 0.5 to 7, more preferably 1 to 6, particularly preferably 1. from the viewpoint of the polymerization rate and the solubility of the resulting water-soluble polymer. 5-5.
また、(A)は予め上記の方法による製造の後、ポリマー変性反応させたものでもよい。ポリマー変性反応としては、例えばアクリルアミド等の加水分解性官能基を分子内に有する水溶性不飽和モノマーを使用した場合に、重合時または重合後に苛性アルカリ(水酸化ナトリウム、水酸化カリウム等)または炭酸アルカリ(炭酸ナトリウム、炭酸カリウム等)を添加して、モノマーのアミド基を部分的に加水分解(加水分解率は全モノマーの合計モル数に基づいて約1〜60モル%)してカルボキシル基を導入する方法(例えば、特開昭56−16505号公報)、ホルムアルデヒド、ジアルキル(C1〜12)アミンおよびハロゲン化(例えば塩化、臭化およびヨウ化)アルキル(C1〜12)(例えばメチルクロライドおよびエチルクロライド)を加え、マンニッヒ反応によって部分的にカチオン性基を導入する方法、およびアクリロニトリル等のニトリル基と、ビニルホルムアミド等の加水分解により得られるアミノ基との閉環反応により分子内にアミジン環を形成させる方法(例えば特開平5−192513号公報)が挙げられる。 In addition, (A) may be prepared by the above-described method, followed by polymer modification reaction. As the polymer modification reaction, for example, when a water-soluble unsaturated monomer having a hydrolyzable functional group in the molecule such as acrylamide is used, caustic alkali (sodium hydroxide, potassium hydroxide, etc.) or carbonic acid is used during or after the polymerization. Alkali (sodium carbonate, potassium carbonate, etc.) is added, and the amide group of the monomer is partially hydrolyzed (the hydrolysis rate is about 1 to 60 mol% based on the total number of moles of all monomers) to form a carboxyl group. Methods of introduction (for example, JP-A-56-16505), formaldehyde, dialkyl (C1-12) amine and halogenated (for example, chloride, bromide and iodide) alkyl (C1-12) (for example, methyl chloride and ethyl) Chloride) and partially introducing a cationic group by the Mannich reaction, and And nitrile group such as acrylonitrile, and a method of forming an amidine ring in a molecule by ring closure reaction of an amino group obtained by the hydrolysis of vinyl formamide (for example, Japanese Unexamined 5-192513 JP) is.
また、(A)として2種以上の水溶性(共)重合体を用いる場合、予めそれぞれを製造した後に混合してもよいし、一方を予め製造しておき、他方の製造時のモノマーに加えて製造してもよい。 Moreover, when using 2 or more types of water-soluble (co) polymers as (A), you may mix after manufacturing each beforehand, and it manufactures one beforehand and adds to the monomer at the time of the other manufacture. May be manufactured.
水溶性(共)重合体(A)の0.2重量%水溶液の粘度(単位:mPa・s、25℃、以下Vwと表記)の、(A)の0.5重量%塩水溶液の粘度(単位:mPa・s、25℃、以下 Vsと表記)に対する比[Vw/Vs]は、後述するフロック強度およびケーキ含水率低減の観点から、好ましくは6〜35、さらに好ましくは9〜25、とくに好ましくは12〜20である。 Viscosity of 0.5% by weight aqueous salt solution of (A) of 0.2% by weight aqueous solution of water-soluble (co) polymer (A) (unit: mPa · s, 25 ° C., hereinafter referred to as Vw) ( The ratio [Vw / Vs] to the unit: mPa · s, 25 ° C., hereinafter referred to as Vs) is preferably 6 to 35, more preferably 9 to 25, particularly from the viewpoint of reducing floc strength and cake moisture content described later. Preferably it is 12-20.
Vw/Vsと凝集性能との関係について次のような仮説を立てた。すなわち、Vw/Vsは塩水中での分子の縮こまりを示し、ポリマー鎖が過剰に縮まっている場合には、汚泥粒子表面の電荷を中和しにくく、強度の弱いフロックが形成されて含水率が高くなり、また、ポリマー鎖が過剰に拡がっている場合には、汚泥粒子表面の電荷は中和されるものの、凝集に際しては水を多く含んだフロックが形成されて含水率が高くなると推定されることから、ポリマー鎖が適度な拡がりを有する場合が凝集性能に優れるとの仮説である。 The following hypothesis was made about the relationship between Vw / Vs and aggregation performance. That is, Vw / Vs indicates molecular shrinkage in salt water, and when the polymer chain is excessively shrunk, it is difficult to neutralize the charge on the sludge particle surface, and flocs with low strength are formed and the water content is low. When the polymer chain is excessively spread, the charge on the sludge particle surface is neutralized, but it is presumed that a floc containing a lot of water is formed at the time of agglomeration and the water content becomes high. Therefore, it is a hypothesis that the polymer chain has an appropriate spread when the polymer chain has an appropriate spread.
本発明における水溶性(共)重合体(A)のVwは以下の方法によって測定される。なお、該測定は室温下(約25℃)で行う。
(1)測定試料(0.2重量%水溶液)の調製
あらかじめ試料0.4g(固形分含量換算したもの)を精秤し、別途500mlのガラス製ビーカーにイオン交換水を約199gとり、ジャーテスター[型式「JMD−6HS−A」、宮本理研工業(株)製、以下同じ。]に板状の塩ビ製撹拌羽根(直径5cm、高さ2cm、厚さ0.2cm)2枚を十字になるように上下に連続して撹拌棒に取り付けた撹拌装置を用い、200rpmの速度で撹拌する。試料を加え、全体の重量(試料とイオン交換水の合計重量)が200gとなるようにイオン交換水を加えた後、3時間撹拌して完全に溶解し、0.2重量%の水溶性(共)重合体(A)溶液を調製する。
なお、水溶性(共)重合体(A)の固形分含量は、試料約1.0gをシャーレ(内径105mm、深さ20mm)に秤量(W1)して、循風乾燥機中105±5℃で90分間乾燥させた後の残存重量を(W2)として、次式から算出した値である。
固形分含量(重量%)=(W2)×100/(W1)
Vw of the water-soluble (co) polymer (A) in the present invention is measured by the following method. The measurement is performed at room temperature (about 25 ° C.).
(1) Preparation of measurement sample (0.2% by weight aqueous solution) In advance, 0.4 g (sample converted to solid content) of sample was precisely weighed, and about 199 g of ion-exchanged water was separately taken in a 500 ml glass beaker. [Model “JMD-6HS-A” manufactured by Miyamoto Riken Kogyo Co., Ltd., and so on. ] Using a stirring device in which two plate-like stirring blades made of PVC (diameter: 5 cm, height: 2 cm, thickness: 0.2 cm) are attached to the stirring rod in a vertical manner in a cross shape at a speed of 200 rpm. Stir. Add sample, add ion exchange water so that the total weight (total weight of sample and ion exchange water) is 200 g, then stir for 3 hours to completely dissolve, 0.2 wt% water-soluble ( A (co) polymer (A) solution is prepared.
The solid content of the water-soluble (co) polymer (A) was determined by weighing about 1.0 g of a sample into a petri dish (inner diameter 105 mm, depth 20 mm) (W1) and circulating in a circulating dryer at 105 ± 5 ° C. This is a value calculated from the following equation, where (W2) is the residual weight after drying for 90 minutes.
Solid content (% by weight) = (W2) × 100 / (W1)
(2)粘度の測定
(1)で調製した水溶液を200mlトールビーカーに全量移し、水浴中で25℃に温度調整し、ローターガードを付けたブルックフィールド粘度計[型式「TV−10M」、東機産業(株)製、以下同じ。]で、30rpmでローターを回転し、回転開始から5分後の粘度を測定する。使用するローター番号は機器の測定可能な粘度範囲に従って、付け替える。
(2) Viscosity measurement The entire amount of the aqueous solution prepared in (1) was transferred to a 200 ml tall beaker, the temperature was adjusted to 25 ° C. in a water bath, and a Brookfield viscometer with a rotor guard [model “TV-10M”, Toki The same applies to Sangyo Co., Ltd. ], Rotate the rotor at 30 rpm, and measure the viscosity 5 minutes after the start of rotation. The rotor number used is changed according to the measurable viscosity range of the instrument.
本発明における水溶性(共)重合体(A)のVsは0.5重量%水溶性(共)重合体(A)塩水溶液(塩水は4重量%塩化ナトリウム水溶液)の粘度を示し、以下の方法によって測定される。
(1)測定試料(0.5重量%塩水溶液)の調製
あらかじめ試料2.5g(固形分含量換算したもの)を精秤し、別途500mlのガラス製ビーカーにイオン交換水を約470gとり、上記と同じ撹拌装置で200rpmの速度で撹拌する。試料を加え、全体の重量(試料とイオン交換水の合計重量)が480gとなるようにイオン交換水を加えた後、4時間撹拌する。4時間撹拌した時点で、塩化ナトリウム20gを加え、さらに30分間撹拌し、0.5重量%塩水溶液を調製する。
なお、水溶性(共)重合体(A)の固形分含量の求め方は、上記Vwの場合と同じである。
The Vs of the water-soluble (co) polymer (A) in the present invention indicates the viscosity of a 0.5 wt% water-soluble (co) polymer (A) salt aqueous solution (the salt water is 4 wt% sodium chloride aqueous solution). Measured by method.
(1) Preparation of measurement sample (0.5 wt% salt aqueous solution) Preliminarily weigh 2.5 g of sample (converted to solid content), and take about 470 g of ion-exchanged water in a 500 ml glass beaker. Stir at the speed of 200 rpm with the same stirrer. A sample is added, and ion-exchange water is added so that the total weight (total weight of the sample and ion-exchange water) is 480 g, followed by stirring for 4 hours. When the mixture is stirred for 4 hours, 20 g of sodium chloride is added, and the mixture is further stirred for 30 minutes to prepare a 0.5 wt% salt aqueous solution.
The method for obtaining the solid content of the water-soluble (co) polymer (A) is the same as in the case of Vw.
(2)粘度の測定
(1)で調製した水溶液の一部を200mlトールビーカーに移し、水浴中で25℃に温度調整し、ローターガードを付けたブルックフィールド粘度計で60rpmでローターを回転し、回転開始から5分後の粘度を測定する。使用するローター番号は機器の測定可能な粘度範囲に従って、付け替える。
(2) Measurement of viscosity Transfer a part of the aqueous solution prepared in (1) to a 200 ml tall beaker, adjust the temperature to 25 ° C. in a water bath, rotate the rotor at 60 rpm with a Brookfield viscometer with a rotor guard, The viscosity is measured 5 minutes after the start of rotation. The rotor number used is changed according to the measurable viscosity range of the instrument.
上記Vsは、(A)を構成する全モノマーの重量に対する、重合時に用いるラジカル重合用連鎖移動剤(c)の重量比で制御され、(c)の重量比が増えるほどVsは小さくなる。従って、前記Vw/Vsを大きくするには、(c)を増やすことで制御でき、逆にVw/Vsを小さくする場合は、(c)を減らすことで制御できる。 The above Vs is controlled by the weight ratio of the chain transfer agent for radical polymerization (c) used at the time of polymerization to the weight of all monomers constituting (A), and Vs decreases as the weight ratio of (c) increases. Therefore, increasing Vw / Vs can be controlled by increasing (c), and conversely, decreasing Vw / Vs can be controlled by decreasing (c).
水溶性(共)重合体(A)のVwは、凝集性能および汚泥等の中の懸濁粒子との反応速度の観点から好ましくは50〜2,500、さらに好ましくは100〜2,000、とくに好ましくは150〜1,500である。 The Vw of the water-soluble (co) polymer (A) is preferably 50 to 2,500, more preferably 100 to 2,000, particularly from the viewpoint of agglomeration performance and reaction rate with suspended particles in sludge and the like. Preferably it is 150-1,500.
水溶性(共)重合体(A)のVsは、凝集性能および汚泥等の中の懸濁粒子との反応性の観点から好ましくは1〜100、さらに好ましくは3〜30、とくに好ましくは5〜14である。 Vs of the water-soluble (co) polymer (A) is preferably 1 to 100, more preferably 3 to 30, particularly preferably 5 to 5 from the viewpoints of aggregation performance and reactivity with suspended particles in sludge and the like. 14.
水溶性(共)重合体(A)の塩水不溶解分は、好ましくは50g以下、さらに好ましくは30g以下である。
本発明において(A)の塩水不溶解分は、0.5重量%塩水溶液を目開き180μmの金網で濾過した後に、金網上に残る固形分の重量(g)を示し、下記方法で測定される。
(1)塩水不溶解分(単位:g)[水への溶解性の評価]
上記、Vsの測定用に調製した液(約500g)全量を、あらかじめ空重量(W1)を測った目開き180μmのステンレス製篩上に移し入れ、篩上の残留物を3分間流水(5000cm3/分)で洗浄し、篩に付着した水滴を拭き取り、全体(篩+篩上の固形分)の重量(W2)を測定し、下記式より不溶解分を算出する。
塩水不溶解分(g)=(W2)−(W1)
The salt water insoluble content of the water-soluble (co) polymer (A) is preferably 50 g or less, more preferably 30 g or less.
In the present invention, the salt water insoluble matter of (A) indicates the weight (g) of the solid content remaining on the wire mesh after filtering the 0.5 wt% salt aqueous solution with a wire mesh of 180 μm, and is measured by the following method. The
(1) Salt water insoluble matter (unit: g) [Evaluation of solubility in water]
The total amount of the liquid (about 500 g) prepared for the measurement of Vs was transferred onto a stainless steel sieve having an opening of 180 μm whose empty weight (W1) was measured in advance, and the residue on the sieve was washed with running water (5000 cm 3). / Min), water droplets adhering to the sieve are wiped off, the weight (W2) of the whole (the sieve + solid content on the sieve) is measured, and the insoluble matter is calculated from the following formula.
Salt water insoluble matter (g) = (W2)-(W1)
[塩(B)]
本発明における塩(B)は下記一般式(2)で表される。
X2−N+R4R5R6・Y- (2)
[Salt (B)]
The salt (B) in the present invention is represented by the following general formula (2).
X 2 −N + R 4 R 5 R 6 · Y − (2)
一般式(2)中、X2はヘテロ原子を有していてもよいC1〜5(好ましくはC2〜3)の1価の炭化水素基、R4〜R6はH、Y-はプロトン酸のH+を除く残基を表す。X2がC1未満では、ケーキ含水率(脱水性)に劣り、C5を超えると親水性が低下し、凝集性能が劣る。 In the general formula (2), X 2 is a C1-5 (preferably C2-3) monovalent hydrocarbon group which may have a hetero atom, R 4 to R 6 are H, and Y − is a protonic acid. Represents a residue excluding H + of The X 2 is less than C1, poor cake moisture content (dewatering), greater than C5 When hydrophilicity is lowered, aggregation ability is poor.
前記塩(B)は、とくに限定されないが、後述の高分子凝集剤(P)の凝集性能の観点から、X2を有する1級アミン(b1)とプロトン酸(b2)から構成される1級アミンプロトン酸塩が好ましい。 The salt (B) is not particularly limited, but from the viewpoint of the aggregation performance of the polymer flocculant (P) described later, a primary composed of a primary amine (b1) having X 2 and a protonic acid (b2). Amine protonic acid salts are preferred.
X2を有する1級アミン(b1)としては、下記の(b11)〜(b14)が挙げられる。 Examples of the primary amine (b1) having X 2 include the following (b11) to (b14).
(b11)アルキルアミン
例えばメチルアミン、エチルアミン;
(b12)ヒドロキシアルキルアミン
例えばモノエタノールアミン、モノプロパノールアミン、モノイソプロパノールアミン;
(b13)アルコキシアルキルアミン
例えばメトキシエチルアミン;
(b14)アルキルチオエーテルアルキルアミン
例えばメチルチオエチルアミン。
(B11) alkylamines such as methylamine, ethylamine;
(B12) hydroxyalkylamines such as monoethanolamine, monopropanolamine, monoisopropanolamine;
(B13) alkoxyalkylamines such as methoxyethylamine;
(B14) Alkylthioether alkylamine For example, methylthioethylamine.
上記(b1)のうち、(P)の凝集性能の観点から、好ましいのは(b11)、(b12)、さらに好ましいのは(b12)、とくに好ましいのはモノエタノールアミンである。 Of the above (b1), from the viewpoint of the aggregation performance of (P), (b11) and (b12) are preferable, (b12) is more preferable, and monoethanolamine is particularly preferable.
前記一般式(2)中のY-は、プロトン酸(b2)からプロトン酸のH+を除く残基であり、該プロトン酸(b2)としては、下記の(b21)〜(b26)が挙げられる。 Y − in the general formula (2) is a residue obtained by removing H + of the protonic acid from the protonic acid (b2). Examples of the protonic acid (b2) include the following (b21) to (b26). It is done.
(b21)無機酸
例えばハロゲン化水素(例えば、HF、HCl、HBrおよびHI)、硫酸、硝酸およびリン酸;
(b22)硫酸エステル
例えばC1〜3のアルキルもしくはアルケニル硫酸エステル(例えばメチル硫酸、エチル硫酸、プロピル硫酸);
(b23)スルホン酸
例えばC1〜3のアルキルもしくはアルケニルスルホン酸(例えばメタンスルホン酸、エタンスルホン酸、プロパンスルホン酸);
(B21) inorganic acids such as hydrogen halides (eg HF, HCl, HBr and HI), sulfuric acid, nitric acid and phosphoric acid;
(B22) sulfate ester, for example, C1-3 alkyl or alkenyl sulfate esters (eg, methyl sulfate, ethyl sulfate, propyl sulfate);
(B23) Sulfonic acid, for example, C1-3 alkyl or alkenyl sulfonic acids (for example, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid);
(b24)リン酸エステル
例えばC1〜3のアルキルもしくはアルケニルリン酸エステル(例えばメチルリン酸エステル、エチルリン酸エステル、プロピルリン酸エステル);
(b25)ホスホン酸
例えばC1〜3のアルキルもしくはアルケニルホスホン酸(例えばメチルホスホン酸、エチルホスホン酸、プロピルホスホン酸);
(b26)カルボン酸
例えばC1〜3のアルキルもしくはアルケニルカルボン酸(例えば酢酸、プロピオン酸)。
(B24) Phosphate ester For example, C1-3 alkyl or alkenyl phosphate ester (eg, methyl phosphate ester, ethyl phosphate ester, propyl phosphate ester);
(B25) Phosphonic acid, for example C1-3 alkyl or alkenyl phosphonic acids (for example methylphosphonic acid, ethylphosphonic acid, propylphosphonic acid);
(B26) Carboxylic acid For example, C1-3 alkyl or alkenyl carboxylic acid (for example, acetic acid, propionic acid).
上記(b2)のうち、(P)の凝集性能の観点から、好ましいのは(b21)、(b23)、さらに好ましいのは硫酸、スルホン酸、とくに好ましいのはメタンスルホン酸である。 Of the above (b2), from the viewpoint of the aggregation performance of (P), (b21) and (b23) are preferable, sulfuric acid and sulfonic acid are more preferable, and methanesulfonic acid is particularly preferable.
塩(B)のうち、(P)の凝集性能の観点から、好ましいのはエチルアミン硫酸塩、エチルアミンメタンスルホン酸塩、モノエタノールアミン硫酸塩、モノプロパノールアミン硫酸塩、モノエタノールアミンメタンスルホン酸塩、モノプロパノールアミンメタンスルホン酸塩、さらに好ましいのはモノエタノールアミンメタンスルホン酸塩である。 Among the salts (B), from the viewpoint of the aggregation performance of (P), ethylamine sulfate, ethylamine methanesulfonate, monoethanolamine sulfate, monopropanolamine sulfate, monoethanolamine methanesulfonate, Monopropanolamine methanesulfonate, more preferably monoethanolamine methanesulfonate.
[高分子凝集剤(P)]
本発明の高分子凝集剤(P)は、前記水溶性(共)重合体(A)、前記塩(B)を含有してなる。該(A)の重量に基づく該塩(B)の含有量は、1〜20%、好ましくは3〜15%、さらに好ましくは5〜9%である。1%未満では脱水ケーキの含水率に劣り、20%を超えると水溶性(共)重合体(A)による凝集性能が劣り、フロックが崩れやすくなる。
高分子凝集剤(P)が顕著な凝集性能を発揮するのは、仮説ではあるが、特定量の塩(B)が汚泥または廃水の懸濁粒子と相互作用することに起因するものと考えられる。
また、特定量の塩(B)の存在下で水溶性不飽和モノマー(a)を重合させることにより、高分子凝集剤(P)中の水溶性(共)重合体(A)の分子量分布、ポリマー鎖の拡がりがさらに好適になっているものと推定される。
[Polymer flocculant (P)]
The polymer flocculant (P) of the present invention comprises the water-soluble (co) polymer (A) and the salt (B). The content of the salt (B) based on the weight of the (A) is 1 to 20%, preferably 3 to 15%, more preferably 5 to 9%. If it is less than 1%, the moisture content of the dehydrated cake is inferior, and if it exceeds 20%, the agglomeration performance by the water-soluble (co) polymer (A) is inferior, and the flocs are liable to collapse.
Although it is a hypothesis that the polymer flocculant (P) exhibits remarkable flocculation performance, it is considered that the specific amount of salt (B) interacts with sludge or waste water suspended particles. .
Further, by polymerizing the water-soluble unsaturated monomer (a) in the presence of a specific amount of the salt (B), the molecular weight distribution of the water-soluble (co) polymer (A) in the polymer flocculant (P), It is presumed that the polymer chain spread is more suitable.
塩(B)は、水溶性(共)重合体(A)の製造時(例えば、モノマー水溶液)に含有させても、(A)の製造後に含有させても、いずれの方法でもよい。工業的な観点および(P)の凝集性能の観点から好ましいのは(A)の製造時に含有させる方法である。 The salt (B) may be contained either during production of the water-soluble (co) polymer (A) (for example, an aqueous monomer solution) or after production of (A). From the industrial viewpoint and the viewpoint of the cohesive performance of (P), the method of incorporating (A) is preferable.
前記(A)の重量に基づく塩(B)の含有量(α)は、例えば以下の方法で求められる。
[1]500mLのガラス製容器に高分子凝集剤(P)5.0gにメチルエチルケトン250gを加えて、マグネティックスターラー[マイティ・スターラーパワータイプHE−16GB、小池精密機器製作所製]を用いて室温で30分間、500rpmの条件で撹拌する。
[2]内容物の全量を加圧ろ過し、ろ過ケーキ(β)、ろ液(γ)を得る。
[3]ろ過ケーキ(β)の全量をステンレス製容器に移す。次に循風乾燥機で100℃、5時間乾燥させて(A)を単離し、(P)中の(A)の重量(Wβ)を精秤する。
[4]ろ液(γ)の全量をステンレス製容器に移す。次に循風乾燥機で100℃、5時間乾燥させて塩(B)を単離し、(P)中の塩(B)の重量(Wγ)を精秤する。
[5]次式により、(A)の重量に基づく塩(B)の含有量(α)を算出する(単位:重量%)。
(α)=(Wγ)×100/(Wβ)
The content (α) of the salt (B) based on the weight of (A) can be determined, for example, by the following method.
[1] In a 500 mL glass container, 250 g of methyl ethyl ketone is added to 5.0 g of the polymer flocculant (P), and a magnetic stirrer [Mighty Stirrer Power Type HE-16GB, manufactured by Koike Seimitsu Seisakusho] is used at room temperature for 30. Stir for 5 minutes at 500 rpm.
[2] The entire content is pressure filtered to obtain a filter cake (β) and a filtrate (γ).
[3] Transfer the entire amount of the filter cake (β) to a stainless steel container. Next, (A) is isolated by drying at 100 ° C. for 5 hours with a circulating drier, and the weight (Wβ) of (A) in (P) is precisely weighed.
[4] Transfer the entire amount of the filtrate (γ) to a stainless steel container. Next, the salt (B) is isolated by drying at 100 ° C. for 5 hours with a circulating dryer, and the weight (Wγ) of the salt (B) in (P) is precisely weighed.
[5] The content (α) of the salt (B) based on the weight of (A) is calculated according to the following formula (unit: wt%).
(Α) = (Wγ) × 100 / (Wβ)
前記(P)には(A)、(B)以外に、必要に応じ、本発明の効果を阻害しない範囲で、高分子凝集剤に通常用いられる、消泡剤、キレート化剤、pH調整剤、界面活性剤、ブロッキング防止剤、酸化防止剤、紫外線吸収剤および防腐剤からなる群から選ばれる添加剤を含有させることができる。添加剤を含有させる方法としては特に限定はなく、(A)、(B)とこれらの添加剤を、常温または加熱下、撹拌混合する方法等が挙げられる。 In addition to (A) and (B), the anti-foaming agent, chelating agent, and pH adjuster that are usually used for the polymer flocculant as long as the effects of the present invention are not impaired as necessary. An additive selected from the group consisting of a surfactant, an anti-blocking agent, an antioxidant, an ultraviolet absorber and a preservative can be contained. The method for containing the additive is not particularly limited, and examples thereof include a method in which (A) and (B) and these additives are stirred and mixed at room temperature or under heating.
上記添加剤の使用量は、(A)の重量に基づいて、消泡剤は通常5%以下、好ましくは1〜3%、キレート化剤は通常30%以下、好ましくは2〜10%、pH調整剤は通常10%以下、好ましくは1〜5%、界面活性剤およびブロッキング防止剤はそれぞれ通常5%以下、好ましくは1〜3%、酸化防止剤、紫外線吸収剤および防腐剤はそれぞれ通常5%以下、好ましくは0.1〜2%である。
なお、(P)中の(A)の含有量は、好ましくは50重量%以上、さらに好ましくは80重量%以上である。
The amount of the additive used is usually 5% or less, preferably 1 to 3%, and the chelating agent is usually 30% or less, preferably 2 to 10%, based on the weight of (A). The regulator is usually 10% or less, preferably 1 to 5%, the surfactant and the anti-blocking agent are each usually 5% or less, preferably 1 to 3%, and the antioxidant, the ultraviolet absorber and the preservative are each usually 5%. % Or less, preferably 0.1 to 2%.
The content of (A) in (P) is preferably 50% by weight or more, and more preferably 80% by weight or more.
本発明の高分子凝集剤(P)は、従来にない特異的な凝集効果を示すことから、下水等の汚泥、工場廃水の処理で生じた有機性汚泥、無機性汚泥の脱水処理用高分子凝集剤として用いることができ、とくに有機性汚泥の脱水処理用として好適に用いられる。
有機性汚泥の場合は、懸濁粒子の大きさが比較的大きく、また水中において懸濁粒子表面がマイナスに帯電しているとの観点から、本発明の高分子凝集剤(P)に用いる水溶性(共)重合体(A)としては、カチオン性水溶性(共)重合体および/または両性水溶性(共)重合体で構成されることが好ましく、本発明の特徴である上記効果をより一層発揮できるとの観点から、さらに好ましいのはカチオン水溶性(共)重合体で構成されるものである。
ここでカチオン性水溶性(共)重合体とは、分子内にカチオン性基を有する水溶性(共)重合体、すなわち水に溶解した際にカチオン性を示す水溶性(共)重合体であり、また両性水溶性(共)重合体とは、分子内にカチオン性基およびアニオン性基を有する水溶性(共)重合体または分子内にカチオン性基を有する水溶性(共)重合体と分子内にアニオン性基を有する水溶性(共)重合体の混合物、すなわち水に溶解した際にカチオン性およびアニオン性を示す水溶性(共)重合体である。これらの水溶性(共)重合体の水中におけるカチオン性またはアニオン性は、コロイド当量値(meq/g)を目安として評価することができる。即ち、カチオン性水溶性(共)重合体中のカチオン性基当量値はカチオンコロイド当量値として求めることができ、両性水溶性(共)重合体中のカチオン性基当量値およびアニオン性基当量値は、それぞれカチオンコロイド当量値およびアニオンコロイド当量値として求めることができる。
Since the polymer flocculant (P) of the present invention exhibits a specific agglomeration effect that has not existed in the past, it is a polymer for dewatering treatment of sludge such as sewage, organic sludge generated by treatment of factory wastewater, and inorganic sludge. It can be used as a flocculant and is particularly preferably used for dewatering treatment of organic sludge.
In the case of organic sludge, the aqueous particles used in the polymer flocculant (P) of the present invention are from the viewpoint that the size of the suspended particles is relatively large and the surface of the suspended particles is negatively charged in water. The hydrophilic (co) polymer (A) is preferably composed of a cationic water-soluble (co) polymer and / or an amphoteric water-soluble (co) polymer. From the viewpoint that it can be further exerted, a cationic water-soluble (co) polymer is more preferable.
Here, the cationic water-soluble (co) polymer is a water-soluble (co) polymer having a cationic group in the molecule, that is, a water-soluble (co) polymer that exhibits cationic properties when dissolved in water. The amphoteric water-soluble (co) polymer is a water-soluble (co) polymer having a cationic group and an anionic group in the molecule, or a water-soluble (co) polymer having a cationic group in the molecule and a molecule. It is a mixture of water-soluble (co) polymers having an anionic group therein, that is, a water-soluble (co) polymer that exhibits cationic and anionic properties when dissolved in water. The cationicity or anionicity of these water-soluble (co) polymers in water can be evaluated using the colloid equivalent value (meq / g) as a guide. That is, the cationic group equivalent value in the cationic water-soluble (co) polymer can be determined as the cationic colloid equivalent value, and the cationic group equivalent value and the anionic group equivalent value in the amphoteric water-soluble (co) polymer. Can be determined as a cation colloid equivalent value and an anion colloid equivalent value, respectively.
本発明の高分子凝集剤(P)の形態は、粉末状(例えば破砕状、真球状および葡萄房状)、フィルム状、水溶液状、油中水型(w/o)エマルション状および懸濁液状等、公知の任意形態でよい。 The form of the polymer flocculant (P) of the present invention is in the form of powder (for example, crushed, true spherical and kitchen), film, aqueous solution, water-in-oil (w / o) emulsion and suspension. Or any other known form.
本発明の、汚泥または廃水の処理方法は、本発明の高分子凝集剤(P)を汚泥または廃水に添加、混合してフロックを形成させ、固液分離を行う方法であれば特に限定されることはない。
上記処理方法のうち、本発明の効果(凝集性能、すなわち高フロック強度、フロックの粗大化、脱水ケーキの低含水率化)発揮の観点から好ましいのは、高分子凝集剤を汚泥または廃水に添加、混合してフロックを形成させ、固液分離を行う方法である。なお、高分子凝集剤を汚泥または廃水に添加するに際してはこれらは予め水溶液の形態としておくことが均一混合の観点から好ましい。
The method for treating sludge or wastewater of the present invention is particularly limited as long as the polymer flocculant (P) of the present invention is added to and mixed with sludge or wastewater to form a floc and perform solid-liquid separation. There is nothing.
Among the above treatment methods, the polymer flocculant is preferably added to sludge or wastewater from the viewpoint of the effects of the present invention (flocculation performance, that is, high floc strength, coarse floc, low water content of dehydrated cake). , Mixing to form flocs and performing solid-liquid separation. In addition, when adding a polymer flocculent to sludge or wastewater, it is preferable to make these into the form of aqueous solution previously from a uniform mixing viewpoint.
また、高分子凝集剤(P)を汚泥または廃水に適用する際には、本発明の効果を阻害しない範囲で公知の無機凝結剤や有機凝結剤を1種または2種以上併用してもよい。これらを併用する場合は、
(i)(P)に予め添加しておく方法、
(ii)汚泥または廃水への(P)の添加時に同時に添加する方法、
(iii)無機凝結剤および/または有機凝結剤を、(P)とは別にその添加の前および/または後に順序不同で汚泥または廃水に添加する方法
のいずれを採用してもよい。
これらのうち凝集性能の観点から好ましいのは、(iii)のうち(P)の添加の前に無機凝結剤および/または有機凝結剤をまず初めに汚泥または廃水に添加する方法である。
Further, when the polymer flocculant (P) is applied to sludge or wastewater, one or more known inorganic coagulants and organic coagulants may be used in combination as long as the effects of the present invention are not impaired. . When using these together,
(I) a method of previously adding to (P),
(Ii) a method of adding simultaneously with the addition of (P) to sludge or wastewater,
(Iii) Either an inorganic coagulant and / or an organic coagulant may be added to sludge or wastewater in any order before and / or after addition of (P).
Among these, the method of adding an inorganic coagulant and / or an organic coagulant to sludge or waste water is preferable from the viewpoint of coagulation performance before adding (P) of (iii).
無機凝結剤としては、例えば硫酸バンド、ポリ塩化アルミニウム、塩化第二鉄、硫酸第二鉄、ポリ硫酸鉄および消石灰が挙げられる。
有機凝結剤としては、例えばエピハロヒドリンとアミンとの重縮合体(もしくはその塩酸塩、以下塩酸塩と略記)、エピハロヒドリンとアルキレンジアミンとの重縮合体(塩酸塩)、ポリエチレンイミン(塩酸塩)、アルキレンジハライド−アルキレンポリアミン重縮合体(塩酸塩)、アニリン−ホルムアルデヒド重縮合体(塩酸塩)、ポリビニルベンジルトリメチルアンモニウムクロライド、ポリビニルピリジン(塩酸塩)、(ジ)メチルジ(メタ)アリルアンモニウムクロライドおよびポリビニルイミダゾリン(塩酸塩)が挙げられる。これらの無機凝結剤および有機凝結剤はそれぞれの1種または2種以上用いても、あるいは両者を併用してもいずれでもよい。
Examples of the inorganic coagulant include sulfate band, polyaluminum chloride, ferric chloride, ferric sulfate, polyiron sulfate and slaked lime.
Examples of organic coagulants include polycondensates of epihalohydrin and amine (or its hydrochloride, hereinafter abbreviated as hydrochloride), polycondensates of epihalohydrin and alkylenediamine (hydrochloride), polyethyleneimine (hydrochloride), alkyl, and the like. Range halide-alkylene polyamine polycondensate (hydrochloride), aniline-formaldehyde polycondensate (hydrochloride), polyvinylbenzyltrimethylammonium chloride, polyvinylpyridine (hydrochloride), (di) methyldi (meth) allylammonium chloride and polyvinylimidazoline (Hydrochloride). These inorganic coagulants and organic coagulants may be used singly or in combination, or both may be used in combination.
該凝結剤を予め(P)に添加しておく場合の使用量は、(P)の重量に基づいて、無機凝結剤は通常100%以下、凝結性能および凝集性能の観点から好ましくは5〜50%、さらに好ましくは10〜30%、有機凝結剤は通常20%以下、同様の観点から好ましくは1〜10%、さらに好ましくは2〜5%である。 When the coagulant is added to (P) in advance, the amount used is usually 100% or less based on the weight of (P), preferably from 5 to 50 from the viewpoint of coagulation performance and coagulation performance. %, More preferably 10 to 30%, and the organic coagulant is usually 20% or less, preferably 1 to 10%, more preferably 2 to 5% from the same viewpoint.
無機凝結剤および/または有機凝結剤を(P)とは別に汚泥または廃水に添加する場合[上記(iii)の方法]の無機凝結剤および/または有機凝結剤の使用量は、汚泥または廃水の種類、懸濁している粒子の大きさ、および汚泥または廃水中の固形分含量(以下TSと略記)等によって異なるが、汚泥または廃水中のTSに基づいて、無機凝結剤では、フロック強度の観点から、好ましい下限は0.5重量%、さらに好ましくは1重量%、とくに好ましくは2重量%、脱水ケーキ焼却後のスラッジ低減の観点から、好ましい上限は10重量%、さらに好ましくは8重量%、とくに好ましくは5重量%であり、有機凝結剤では、フロック強度の観点から、好ましい下限は0.01重量%、さらに好ましくは0.05重量%、とくに好ましくは0.1重量%、フロック粒径の観点から、好ましい上限は5重量%、さらに好ましくは3重量%、とくに好ましくは1重量%である。 When the inorganic coagulant and / or organic coagulant is added to sludge or waste water separately from (P), the amount of the inorganic coagulant and / or organic coagulant used in [Method (iii) above] is the sludge or waste water. Depending on the type, the size of suspended particles, and the solid content in sludge or wastewater (hereinafter abbreviated as TS), etc. Therefore, the preferred lower limit is 0.5% by weight, more preferably 1% by weight, particularly preferably 2% by weight, and from the viewpoint of sludge reduction after dewatered cake incineration, the preferred upper limit is 10% by weight, more preferably 8% by weight, Particularly preferred is 5% by weight. In the case of an organic coagulant, the preferred lower limit is 0.01% by weight, more preferably 0.05% by weight, particularly preferably from the viewpoint of floc strength. 0.1 wt%, from the viewpoint of floc particle size, the preferred upper limit is 5% by weight, more preferably 3 wt%, particularly preferably 1% by weight.
また、上記方法における高分子凝集剤(P)の汚泥または廃水への添加方法としては、特に限定はなく、(P)をそのまま汚泥または廃水に添加してもよいが、均一混合の観点から好ましいのは(P)を水溶液にした後に汚泥または廃水に添加する方法である。
(P)を水溶液として用いる場合は、その濃度(重量%)は好ましくは0.05〜3%、さらに好ましくは0.1〜1%である。溶解方法、溶解後の希釈方法は特に限定はないが、例えば予め秤りとった水をジャーテスター等の撹拌装置を用いて撹拌しながら、所定量の粉末状の(P)を加え、数時間(約1〜4時間程度)撹拌して溶解させる方法等が採用できる。
Further, the method for adding the polymer flocculant (P) to the sludge or wastewater in the above method is not particularly limited, and (P) may be added to the sludge or wastewater as it is, but is preferable from the viewpoint of uniform mixing. No. is a method of adding (P) to sludge or waste water after making it into an aqueous solution.
When (P) is used as an aqueous solution, the concentration (% by weight) is preferably 0.05 to 3%, more preferably 0.1 to 1%. The dissolution method and the dilution method after dissolution are not particularly limited. For example, a predetermined amount of powdered (P) is added while stirring a pre-weighed water using a stirring device such as a jar tester, and several hours. A method of stirring and dissolving (about 1 to 4 hours) can be employed.
上記処理方法において、汚泥または廃水に添加する際の(P)の使用量は、汚泥または廃水の種類、懸濁している粒子の含有量および該高分子凝集剤の分子量等によって異なり、とくに限定はされないが、汚泥または廃水中のTSに基づいて、フロック強度の観点から、好ましい下限は0.01重量%、さらに好ましくは0.1重量%、とくに好ましくは1重量%、最も好ましくは1.5重量%、脱水ケーキの含水率低減の観点から、好ましい上限は10重量%、さらに好ましくは8重量%、とくに好ましくは5重量%、最も好ましくは3重量%である。 In the above treatment method, the amount of (P) used when added to sludge or wastewater varies depending on the type of sludge or wastewater, the content of suspended particles, the molecular weight of the polymer flocculant, etc. However, based on the TS in the sludge or wastewater, from the viewpoint of floc strength, the preferred lower limit is 0.01% by weight, more preferably 0.1% by weight, particularly preferably 1% by weight, most preferably 1.5%. From the viewpoint of reducing the moisture content of the dehydrated cake, the upper limit is preferably 10% by weight, more preferably 8% by weight, particularly preferably 5% by weight, and most preferably 3% by weight.
また上記の処理方法により形成されたフロック状の汚泥の脱水方法(固液分離法)としては、例えば重力沈降、膜ろ過、カラムろ過、加圧浮上、濃縮装置(例えばシックナー)、脱水装置(例えば遠心脱水機、ベルトプレス脱水機、フィルタープレス脱水機、キャピラリー脱水機)を用いる方法が挙げられる。これらのうち本発明の高分子凝集剤の特異的な凝集性能である高フロック強度の観点から好ましいのは、脱水装置、とくに遠心脱水機、ベルトプレス脱水機、フィルタープレス脱水機を用いる方法である。 In addition, as a dehydration method (solid-liquid separation method) of floc sludge formed by the above processing method, for example, gravity sedimentation, membrane filtration, column filtration, pressurized flotation, a concentration device (for example, thickener), a dewatering device (for example, Examples include a method using a centrifugal dehydrator, a belt press dehydrator, a filter press dehydrator, and a capillary dehydrator. Among these, preferred from the viewpoint of high floc strength, which is the specific aggregation performance of the polymer flocculant of the present invention, is a method using a dehydrator, particularly a centrifugal dehydrator, a belt press dehydrator, or a filter press dehydrator. .
本発明の高分子凝集剤の、汚泥または廃水処理用途以外のその他の用途としては、例えば掘削・泥水処理用凝集剤、製紙用薬剤(製紙工業用地合形成助剤、濾水歩留向上剤、濾水性向上剤、紙力増強剤等)、原油増産用添加剤(原油の二、三次回収用添加剤)、分散剤、スケール防止剤、凝結剤、脱色剤、増粘剤、帯電防止剤および繊維用処理剤が挙げられる。 Other uses of the polymer flocculant of the present invention other than sludge or wastewater treatment include, for example, a flocculant for excavation and muddy water treatment, a papermaking agent (formation aid for paper industry, drainage yield improver, Drainage improver, paper strength enhancer, etc.), crude oil production additive (crude oil secondary and tertiary recovery additive), dispersant, scale inhibitor, coagulant, decolorizer, thickener, antistatic agent and Examples thereof include a treating agent for fibers.
以下実施例をもって本発明を具体的に説明するが、本発明はこれらの実施例に限定されるものではない。なお、実施例中の部は重量部、%は重量%を表す。 EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. In addition, the part in an Example represents a weight part and% represents weight%.
水溶性(共)重合体(A)のVw、Vs、高分子凝集剤(P)の固形分含量は、前記の方法によって測定した。
なお、下水汚泥等中のTS、浮遊物質(SS)、有機分(強熱減量)は、「下水試験方法」(日本下水道協会、1984年度版)記載の分析方法に準じて行った。
また、本実施例中のフロック粒径、ろ液量、ろ布剥離性、ケーキ含水率は以下の方法に従って評価した。
The Vw and Vs of the water-soluble (co) polymer (A) and the solid content of the polymer flocculant (P) were measured by the method described above.
TS in sewage sludge and the like, suspended solids (SS), and organic content (loss on ignition) were performed according to the analysis method described in “Sewage test method” (Japan Sewerage Association, 1984 version).
Moreover, the floc particle diameter, filtrate amount, filter cloth peelability, and cake moisture content in this example were evaluated according to the following methods.
(1)フロック粒径(単位:mm)
ジャーテスター[宮本理研工業(株)製、形式JMD−6HS−A]に板状の塩ビ製撹拌羽根(直径5cm、高さ2cm、厚さ0.2cm)2枚を十字になるように上下に連続して撹拌棒に取り付け、下水汚泥等200gを500mlのビーカーに取り、ジャーテスターにセットした。ジャーテスターの回転数を120rpmにし、ゆっくり下水汚泥等を撹拌しながら、所定量の0.2%の高分子凝集剤水溶液を一気に添加し、30秒間撹拌した後、撹拌を止め凝集物の大きさを目視にて計測した。
続いて回転数を300rpmにセットし、さらに30秒間撹拌した後、撹拌を止め凝集物の大きさを再度目視にて計測した。
(1) Flock particle size (unit: mm)
Jar tester [Miyamoto Riken Kogyo Co., Ltd., Model JMD-6HS-A] with two plate-shaped PVC stirring blades (diameter 5 cm, height 2 cm, thickness 0.2 cm) up and down to form a cross It was continuously attached to a stirring rod, 200 g of sewage sludge and the like were taken in a 500 ml beaker and set in a jar tester. While rotating the jar tester at 120 rpm and slowly stirring sewage sludge, etc., a predetermined amount of 0.2% polymer flocculant aqueous solution was added at once, stirred for 30 seconds, and then the stirring was stopped and the size of the aggregates Was measured visually.
Subsequently, the number of revolutions was set to 300 rpm, and after stirring for 30 seconds, stirring was stopped and the size of the aggregate was visually measured again.
(2)ろ液量(単位:mL)
T−1189のナイロン製ろ布[敷島カンバス(株)製、円形状、直径9cm]、ヌッチェ漏斗、300mlが測れるメスシリンダーをセットし、上記フロック粒径試験後の汚泥を一度に投入して濾過し、ストップウォッチを用いて投入直後から60秒後のろ液量を測定し処理速度を評価した。
(2) Filtrate (unit: mL)
T-1189 nylon filter cloth [Shikishima Kanbusu Co., Ltd., circular shape, diameter 9 cm], Nutsche funnel, graduated cylinder that can measure 300 ml, set sludge after the above floc particle size test and filter at once Then, using a stopwatch, the amount of filtrate after 60 seconds from immediately after the addition was measured to evaluate the treatment speed.
(3)ろ布剥離性
(2)のろ布上の濾過物の一部をスパチュラで取り出し、プレスフィルター試験機を用いて脱水試験(荷重2kg/cm2、60秒)を行い、試験後のろ布に付着した脱水ケーキをスパチュラで剥離させた場合の脱水ケーキのろ布からの剥離性を下記の基準に従って評価した。
◎:非常に剥がれやすい(ろ布付着物ほとんどなし)
○:剥がれやすい (わずかにろ布付着物あり)
△:多少剥がれにくい (ろ布付着物あり、わずかにろ布内部まで付着)
×:剥がれにくい (ろ布内部まで付着)
(3) Filter cloth peelability A part of the filtered material on the filter cloth of (2) is taken out with a spatula and subjected to a dehydration test (load 2 kg / cm 2 , 60 seconds) using a press filter tester. The peelability of the dehydrated cake from the filter cloth when the dewatered cake attached to the filter cloth was peeled off with a spatula was evaluated according to the following criteria.
A: Very easy to peel off (almost no filter cloth deposits)
○: Easy to peel off (Slightly attached filter cloth)
Δ: Slightly difficult to peel off (there is a filter cloth deposit, slightly sticking to the inside of the filter cloth)
×: Hard to peel off (attaches to the inside of the filter cloth)
(4)ケーキ含水率(単位:%)
上記ろ布剥離性試験後の脱水ケーキ約3.0gをシャーレ(内径105cm、深さ20cm)に秤量(W3)して、循風乾燥機中で完全に水分が蒸発するまで(105±5℃で8時間)乾燥させた後、シャーレ内に残った乾燥ケーキの重量を(W4)として、次式からケーキ含水率を算出した。
ケーキ含水率(%)=[(W3)−(W4)]×100/(W3)
(4) Moisture content of cake (unit:%)
About 3.0 g of the dehydrated cake after the filter cloth peelability test was weighed (W3) in a petri dish (inner diameter: 105 cm, depth: 20 cm) until the water completely evaporated in the circulating dryer (105 ± 5 ° C. 8 hours), the moisture content of the cake was calculated from the following equation, assuming that the weight of the dry cake remaining in the petri dish was (W4).
Cake moisture content (%) = [(W3) − (W4)] × 100 / (W3)
(5)フロック強度
上記(1)における回転数120rpmおよび300rpmでのフロック粒径を比較し、フロック粒径の変化からフロック強度を下記の基準に従って評価した。
<評価基準>
◎ 非常に強固 (粒径に変化なし)
○ 強固 (ごく一部細分化)
△ やや弱い (部分的に細分化)
× 弱い (全体的に細分化)
(5) Flock strength The floc particle diameters at 120 rpm and 300 rpm in the above (1) were compared, and the floc strength was evaluated from the change in the floc particle size according to the following criteria.
<Evaluation criteria>
◎ Very strong (no change in particle size)
○ Strong (partially subdivided)
△ Slightly weak (partially subdivided)
× Weak (Overall segmentation)
以下において、<高分子凝集剤の製造>の実施例もしくは比較例と、<凝集性能評価>の実施例もしくは比較例は、便宜上同じ番号で表記することとする。 In the following, the examples of <Manufacturing polymer coagulant> or comparative examples and the examples or comparative examples of <aggregation performance evaluation> will be denoted by the same numbers for convenience.
<塩(B)の製造>
製造例1
撹拌翼付ガラス製反応槽にメタンスルホン酸70%水溶液1,000部を仕込んだ後、撹拌しながら、モノエタノールアミン445部を60分間かけて滴下した。滴下後、槽内を減圧にし、水を留去した。反応槽からモノエタノールアミンメタンスルホン酸塩(B−1)(白色固体、水分0.1%)1,145部を得た。
<Production of salt (B)>
Production Example 1
After charging 1,000 parts of a 70% aqueous solution of methanesulfonic acid in a glass reaction vessel with a stirring blade, 445 parts of monoethanolamine was added dropwise over 60 minutes while stirring. After dripping, the inside of a tank was pressure-reduced and water was distilled off. 1,145 parts of monoethanolamine methanesulfonate (B-1) (white solid, moisture 0.1%) were obtained from the reaction vessel.
製造例2
製造例1においてメタンスルホン酸70%水溶液1,000部、モノエタノールアミン445部に代えて、硫酸1,000部、モノプロパノールアミン750部とした以外は、製造例1と同様にしてモノプロパノールアミン硫酸塩(B−2)1,710部を得た。
Production Example 2
Monopropanolamine in the same manner as in Production Example 1 except that 1,000 parts of sulfuric acid and 750 parts of monopropanolamine were used instead of 1,000 parts of 70% aqueous methanesulfonic acid and 445 parts of monoethanolamine in Production Example 1. 1,710 parts of sulfate (B-2) was obtained.
製造例3
製造例1においてモノエタノールアミン445部に代えて、エチルアミン70%水溶液470部とした以外は、製造例1と同様にしてエチルアミンメタンスルホン酸塩(B−3)1,010部を得た。
Production Example 3
In Production Example 1, 1,010 parts of ethylamine methanesulfonate (B-3) was obtained in the same manner as in Production Example 1 except that 445 parts of ethylamine was used instead of 445 parts of monoethanolamine.
比較製造例1
製造例1においてモノエタノールアミン445部を水酸化ナトリウム48%水溶液608部に代えた以外は、製造例1と同様にしてメタンスルホン酸ナトリウム塩(B’−1)860部を得た。
Comparative production example 1
860 parts of sodium methanesulfonate (B′-1) was obtained in the same manner as in Production Example 1, except that 445 parts of monoethanolamine was replaced with 608 parts of a 48% aqueous solution of sodium hydroxide in Production Example 1.
<高分子凝集剤の製造>
実施例1
アミノエチルメタアクリレートの硫酸塩(a1−1)の80%水溶液750部、製造例1で製造した塩(B−1)12部、イオン交換水237部、連鎖移動剤として1−チオグリセロール(c−1)の10%水溶液0.36部の混合液を室温(20〜25℃)で調製した。さらにスルファミン酸を用いてモノマー水溶液のpH(20℃)をpHメーターで監視しながら3.0に調整した。得られた混合液を十分に窒素(純度99.999%以上。以下同じ。)で置換(溶存酸素濃度100ppb以下)した後、アゾビスアミジノプロパン塩酸塩の10%水溶液0.60部を加えて均一溶液とし、モノマー水溶液を調製した。
別に還流脱水配管、滴下漏斗、窒素導入管および撹拌翼(マックスブレンド翼)を備えた反応槽にn−デカン1,000部を仕込んだ後、これに分散剤として、無水マレイン酸変性されたエチレン・酢酸ビニル共重合体[商品名「Orevac930S」、アルケマ(株)製]7.0部を加えて、撹拌翼を500rpmの回転数にて撹拌しながら、反応槽内を窒素置換(気相酸素濃度10ppm以下)した後、50℃まで昇温した。50℃に到達後、常圧条件下(103kPa)で、予め滴下漏斗内に仕込んだ前述のモノマー水溶液を反応槽中に60分間かけて全量投入し、投入完了後180分間50℃で撹拌を継続し逆相懸濁重合させた。
重合後、マグネチックスターラーで撹拌しながら、イソプロピルアルコール1,000部に重合後スラリーを加え、10分撹拌した。撹拌後、デカンテーションで上澄み液を取り除き、沈殿物を減圧濾過した。濾過固形物をステンレス製の容器に広げ、50℃の循風乾燥機で10時間乾燥し、水溶性(共)重合体(A−1)を含有してなる高分子凝集剤(P−1)648部を得た(固形分含量92.6%)。
<Manufacture of polymer flocculant>
Example 1
750 parts of an 80% aqueous solution of aminoethyl methacrylate sulfate (a1-1), 12 parts of salt (B-1) produced in Production Example 1, 237 parts of ion-exchanged water, 1-thioglycerol (c A mixture of 0.36 parts of a 10% aqueous solution of -1) was prepared at room temperature (20-25 ° C). Further, the pH (20 ° C.) of the aqueous monomer solution was adjusted to 3.0 using sulfamic acid while monitoring with a pH meter. The obtained mixed solution was sufficiently substituted with nitrogen (purity 99.999% or more; the same applies hereinafter) (dissolved oxygen concentration of 100 ppb or less), and then 0.60 part of a 10% aqueous solution of azobisamidinopropane hydrochloride was added. A homogeneous solution was prepared to prepare an aqueous monomer solution.
Separately, 1,000 parts of n-decane was charged into a reaction vessel equipped with a reflux dehydration pipe, a dropping funnel, a nitrogen introduction pipe, and a stirring blade (Max Blend blade), and then maleic anhydride-modified ethylene as a dispersant. Add 7.0 parts of vinyl acetate copolymer [trade name “Orevac 930S”, manufactured by Arkema Co., Ltd.] and stir the stirring blade at a rotation speed of 500 rpm. Then, the temperature was raised to 50 ° C. After reaching 50 ° C., the above-mentioned monomer aqueous solution previously charged in the dropping funnel was charged into the reaction vessel over 60 minutes under normal pressure (103 kPa), and stirring was continued at 50 ° C. for 180 minutes after completion of the charging. Reverse phase suspension polymerization was then carried out.
After polymerization, the slurry after polymerization was added to 1,000 parts of isopropyl alcohol while stirring with a magnetic stirrer, and the mixture was stirred for 10 minutes. After stirring, the supernatant was removed by decantation, and the precipitate was filtered under reduced pressure. A polymer flocculant (P-1) containing a water-soluble (co) polymer (A-1), which is spread in a stainless steel container and dried for 10 hours in a circulating dryer at 50 ° C. 648 parts were obtained (solid content 92.6%).
実施例2
実施例1において、(B−1)12部に代えて、(B−1)42部の混合液とした以外は実施例1と同様にして、水溶性(共)重合体(A−2)を含有してなる高分子凝集剤(P−2)647部を得た(固形分含量92.8%)。
Example 2
In Example 1, instead of 12 parts of (B-1), a water-soluble (co) polymer (A-2) was obtained in the same manner as in Example 1 except that a mixed solution of 42 parts of (B-1) was used. 647 parts of a polymer flocculant (P-2) containing (solid content 92.8%) were obtained.
実施例3
実施例1において、(B−1)12部に代えて、(B−1)114部の混合液とした以外は実施例1と同様にして、水溶性(共)重合体(A−3)を含有してなる高分子凝集剤(P−3)695部を得た(固形分含量93.8%)。
Example 3
In Example 1, instead of 12 parts of (B-1), a water-soluble (co) polymer (A-3) was obtained in the same manner as in Example 1 except that 114 parts of (B-1) was used. 695 parts of a polymer flocculant (P-3) containing (solid content 93.8%) was obtained.
実施例4
実施例1において、(a1−1)の80%水溶液750部、(B−1)12部、イオン交換水249部、(c−1)の10%水溶液0.36部、アゾビスアミジノプロパン塩酸塩の10%水溶液0.60部に代えて、アミノエチルメタアクリレートのメタンスルホン酸塩(a1−2)の80%水溶液895部、(B−1)50部、イオン交換水300部、(c−1)の10%水溶液0.54部、アゾビスアミジノプロパン塩酸塩の10%水溶液0.72部の混合液とした以外は実施例1と同様にして、水溶性(共)重合体(A−4)を含有してなる高分子凝集剤(P−4)680部を得た(固形分含量93.5%)。
Example 4
In Example 1, 750 parts of an 80% aqueous solution of (a1-1), 12 parts of (B-1), 249 parts of ion-exchanged water, 0.36 part of a 10% aqueous solution of (c-1), azobisamidinopropane hydrochloride Instead of 0.60 part of 10% aqueous solution of salt, 895 parts of 80% aqueous solution of methanesulfonate (a1-2) of aminoethyl methacrylate, 50 parts of (B-1), 300 parts of ion-exchanged water, (c Water-soluble (co) polymer (A) in the same manner as in Example 1, except that 0.54 part of 10% aqueous solution of -1) and 0.72 part of 10% aqueous solution of azobisamidinopropane hydrochloride were used. -4) was obtained, and 680 parts of polymer flocculants (P-4) were obtained (solid content 93.5%).
実施例5
ガラス製断熱反応容器に(a1−2)の80%水溶液783部、(B−1)12.5部、(c−1)の10%水溶液0.47部、系内のモノマーの合計濃度が60%となるようにイオン交換水246部を加え、系内が均一の水溶液になるまで撹拌した。さらに撹拌を続けながら、硫酸を用いてモノマー水溶液のpH(20℃)をpHメーターで監視しながら2.0に調整した。次に、水溶液の温度を25℃に調整し、系内を窒素(純度99.999%以上)で充分に置換した(気相酸素濃度10ppm以下)。次いで開始剤としてアゾビスアミジノプロパン塩酸塩の10%水溶液19部、硫酸鉄(II)の1%水溶液0.3部、過酸化水素の1%水溶液0.3部を、撹拌しながら一気に加えた。内容物温度が50℃に到達後、外部から加熱し内容物温度を80℃に調整した。その後同温度を2時間維持して重合反応を完結させた。なお重合中、内容物が高粘度となり撹拌が困難となったため、撹拌は途中で停止した。その後、得られた含水ゲルを取り出し、ミートチョッパー機[型番「12VR−400K」、ROYAL(株)製、目皿の目開き6mm]により混合、混練、さらにミンチ状に細断し、80℃の熱風で2時間乾燥後ジューサーミキサーで粉砕して、粉末状の水溶性(共)重合体(A−5)を含有してなる高分子凝集剤(P−5)650部(固形分含量92.9%)を得た。
Example 5
In a glass adiabatic reaction vessel, 783 parts of 80% aqueous solution of (a1-2), 12.5 parts of (B-1), 0.47 part of 10% aqueous solution of (c-1), the total concentration of monomers in the system is 246 parts of ion-exchanged water was added so that it might become 60%, and it stirred until the inside of a system became uniform aqueous solution. While further stirring, the pH (20 ° C.) of the monomer aqueous solution was adjusted to 2.0 using sulfuric acid while monitoring with a pH meter. Next, the temperature of the aqueous solution was adjusted to 25 ° C., and the inside of the system was sufficiently replaced with nitrogen (purity 99.999% or more) (gas phase oxygen concentration 10 ppm or less). Next, 19 parts of a 10% aqueous solution of azobisamidinopropane hydrochloride, 0.3 part of a 1% aqueous solution of iron (II) sulfate, and 0.3 part of a 1% aqueous solution of hydrogen peroxide as initiators were added all at once with stirring. . After the content temperature reached 50 ° C., the content temperature was adjusted to 80 ° C. by heating from the outside. Thereafter, the same temperature was maintained for 2 hours to complete the polymerization reaction. During the polymerization, the content became highly viscous and stirring became difficult, so stirring was stopped halfway. Thereafter, the obtained hydrogel was taken out, mixed and kneaded by a meat chopper machine [model number “12VR-400K”, manufactured by ROYAL Co., Ltd., mesh opening 6 mm], and further minced into 80 ° C. 650 parts of a polymer flocculant (P-5) containing a water-soluble (co) polymer (A-5) in powder form after being dried with hot air for 2 hours and then pulverized with a juicer mixer (solid content 92. 9%).
実施例6
実施例5において、(a1−2)の80%水溶液783部、(B−1)12.5部、(c−1)の10%水溶液0.47部、イオン交換水246部、アゾビスアミジノプロパン塩酸塩の10%水溶液19部に代えて、(a1−2)の80%水溶液928部、(B−1)52部、(c−1)の10%水溶液0.56部、イオン交換水290部、アゾビスアミジノプロパン塩酸塩の10%水溶液23部とした以外は実施例5と同様にして、水溶性(共)重合体(A−6)を含有してなる高分子凝集剤(P−6)720部を得た(固形分含量92.7%)。
Example 6
In Example 5, 783 parts of an 80% aqueous solution of (a1-2), 12.5 parts of (B-1), 0.47 part of a 10% aqueous solution of (c-1), 246 parts of ion-exchanged water, azobisamidino Instead of 19 parts of 10% aqueous solution of propane hydrochloride, 928 parts of 80% aqueous solution of (a1-2), 52 parts of (B-1), 0.56 parts of 10% aqueous solution of (c-1), ion-exchanged water A polymer flocculant (P) containing a water-soluble (co) polymer (A-6) in the same manner as in Example 5 except that 290 parts and 23 parts of a 10% aqueous solution of azobisamidinopropane hydrochloride were used. -6) 720 parts were obtained (solid content 92.7%).
実施例7
実施例5において、(a1−2)の80%水溶液783部、(B−1)12.5部、(c−1)の10%水溶液0.47部、イオン交換水246部、アゾビスアミジノプロパン塩酸塩の10%水溶液19部に代えて、(a1−2)の80%水溶液839部、アクリルアミド(a2−1)の50%水溶液31.8部、(B−1)131部、(c−1)の10%水溶液0.52部、イオン交換水270部、アゾビスアミジノプロパン塩酸塩の10%水溶液21部とした以外は実施例5と同様にして、水溶性(共)重合体(A−7)を含有してなる高分子凝集剤(P−7)795部を得た(固形分含量92.7%)。
Example 7
In Example 5, 783 parts of an 80% aqueous solution of (a1-2), 12.5 parts of (B-1), 0.47 part of a 10% aqueous solution of (c-1), 246 parts of ion-exchanged water, azobisamidino Instead of 19 parts of 10% aqueous solution of propane hydrochloride, 839 parts of 80% aqueous solution of (a1-2), 31.8 parts of 50% aqueous solution of acrylamide (a2-1), 131 parts of (B-1), (c -1) water-soluble (co) polymer in the same manner as in Example 5 except that 0.52 parts of 10% aqueous solution, 270 parts of ion-exchanged water, and 21 parts of 10% aqueous solution of azobisamidinopropane hydrochloride were used. 795 parts of a polymer flocculant (P-7) containing A-7) was obtained (solid content 92.7%).
実施例8
実施例6において、(a1−2)928部、(B−1)52部、イオン交換水290部に代えて、(a1−2)689部、(a2−1)の50%水溶液61部、(B−1)41部、イオン交換水210部とした以外は実施例6と同様にして、水溶性(共)重合体(A−8)を含有してなる高分子凝集剤(P−8)687部を得た(固形分含量93.5%)。
Example 8
In Example 6, instead of (a1-2) 928 parts, (B-1) 52 parts, and ion-exchanged water 290 parts, (a1-2) 689 parts, (a2-1) 50% aqueous solution 61 parts, (B-1) Polymer flocculant (P-8) containing a water-soluble (co) polymer (A-8) in the same manner as in Example 6 except that 41 parts and 210 parts of ion-exchanged water were used. 687 parts were obtained (solid content 93.5%).
実施例9
実施例6において、(c−1)の10%水溶液0.56部に代えて、(c−1)の10%水溶液0.074部とした以外は実施例6と同様にして、水溶性(共)重合体(A−9)を含有してなる高分子凝集剤(P−9)666部を得た(固形分含量93.5%)。
Example 9
In Example 6, in place of 0.56 parts of the 10% aqueous solution of (c-1), 0.074 parts of the 10% aqueous solution of (c-1) was used, and the water-soluble ( 666 parts of a polymer flocculant (P-9) containing the (co) polymer (A-9) was obtained (solid content 93.5%).
実施例10
実施例2において、(B−1)に代えて、(B−2)とした以外は実施例2と同様にして、水溶性(共)重合体(A−10)を含有してなる高分子凝集剤(P−10)634部を得た(固形分含量91.0%)。
Example 10
In Example 2, a polymer containing the water-soluble (co) polymer (A-10) in the same manner as in Example 2 except that (B-2) was used instead of (B-1). 634 parts of flocculant (P-10) were obtained (solid content 91.0%).
実施例11
実施例4において、(B−1)に代えて、(B−3)とした以外は実施例4と同様にして、水溶性(共)重合体(A−11)を含有してなる高分子凝集剤(P−11)684部を得た(固形分含量94.0%)。
Example 11
In Example 4, a polymer comprising the water-soluble (co) polymer (A-11) in the same manner as in Example 4 except that (B-3) was used instead of (B-1). 684 parts of flocculant (P-11) were obtained (solid content 94.0%).
実施例12
実施例5において、(a1−2)の80%水溶液783部、(B−1)12.5部、(c−1)の10%水溶液0.47部、イオン交換水246部、アゾビスアミジノプロパン塩酸塩の10%水溶液19部に代えて、(a1−2)の80%水溶液928部、(B−2)0部、(c−1)の10%水溶液0.56部、イオン交換水290部、アゾビスアミジノプロパン塩酸塩の10%水溶液23部とし、さらに得られた含水ゲルに(B−2)52部を加えて、ミートチョッパー機により混合、混練した以外は、実施例5と同様にして、水溶性(共)重合体(A−12)を含有してなる高分子凝集剤(P−12)659部を得た(固形分含量93.3%)。
Example 12
In Example 5, 783 parts of an 80% aqueous solution of (a1-2), 12.5 parts of (B-1), 0.47 part of a 10% aqueous solution of (c-1), 246 parts of ion-exchanged water, azobisamidino Instead of 19 parts of 10% aqueous solution of propane hydrochloride, 928 parts of 80% aqueous solution of (a1-2), 0 part of (B-2), 0.56 part of 10% aqueous solution of (c-1), ion-exchanged water Example 5 except that 290 parts, 23 parts of 10% aqueous solution of azobisamidinopropane hydrochloride, and 52 parts of (B-2) were further added to the obtained hydrous gel and mixed and kneaded by a meat chopper machine. Similarly, 659 parts of a polymer flocculant (P-12) containing the water-soluble (co) polymer (A-12) was obtained (solid content: 93.3%).
実施例13
実施例5において、(B−1)12.5部、(c−1)の10%水溶液0.47部に代えて、(c−1)0.062部、とした以外は実施例5と同様にして、粉末状の水溶性(共)重合体(A−13)を得て、その後(B−2)12.5部を加えてミキサーで混合させて、水溶性(共)重合体(A−13)を含有してなる高分子凝集剤(P−13)657部を得た(固形分含量94.0%)。
Example 13
Example 5 is the same as Example 5 except that (B-1) 12.5 parts and (c-1) 0.062 parts instead of 0.47 parts of (c-1) 10% aqueous solution were used. Similarly, a powdery water-soluble (co) polymer (A-13) is obtained, and then 12.5 parts of (B-2) is added and mixed with a mixer to obtain a water-soluble (co) polymer ( 657 parts of a polymer flocculant (P-13) containing A-13) was obtained (solid content 94.0%).
比較例1
実施例1において、(B−1)12部に代えて、(B−1)150部とした以外は実施例1と同様にして、水溶性(共)重合体(比A−1)を含有してなる高分子凝集剤(比P−1)652部を得た。(固形分含量93.6%)。
Comparative Example 1
In Example 1, a water-soluble (co) polymer (ratio A-1) was contained in the same manner as in Example 1 except that instead of 12 parts of (B-1), it was 150 parts of (B-1). Thus, 652 parts of a polymer flocculant (ratio P-1) was obtained. (Solid content 93.6%).
比較例2
実施例1において、(B−1)12部に代えて、(B−1)2.4部とした以外は実施例1と同様にして、水溶性(共)重合体(比A−2)を含有してなる高分子凝集剤(比P−2)662部を得た。(固形分含量93.0%)。
Comparative Example 2
In Example 1, a water-soluble (co) polymer (ratio A-2) was used in the same manner as in Example 1 except that instead of 12 parts of (B-1), 2.4 parts of (B-1) were used. There were obtained 662 parts of a polymer flocculant (ratio P-2). (Solid content 93.0%).
比較例3
実施例6において、(B−1)52部に代えて、メタンスルホン酸ナトリウム塩(B’−1)52部とした以外は実施例6と同様にして、水溶性(共)重合体(比A−3)を含有してなる高分子凝集剤(比P−3)650部を得た(固形分含量93.4%)。
Comparative Example 3
In Example 6, a water-soluble (co) polymer (ratio) was obtained in the same manner as in Example 6 except that 52 parts of (B-1) was replaced with 52 parts of sodium methanesulfonate (B′-1). 650 parts of a polymer flocculant (ratio P-3) containing A-3) was obtained (solid content 93.4%).
比較例4
実施例2において、(a1−1)の80%水溶液750部、(c−1)の10%水溶液0.36部に代えて、N,N−ジメチルアミノエチルメタアクリレートのメチルクライド4級アンモニウム塩(a2−2)の80%水溶液750部、(c−1)の10%水溶液0.042部とした以外は実施例2と同様にして、水溶性(共)重合体(比A−4)を含有してなる高分子凝集剤(比P−4)625部を得た(固形分含量93.6%)。
Comparative Example 4
In Example 2, instead of 750 parts of an 80% aqueous solution of (a1-1) and 0.36 part of a 10% aqueous solution of (c-1), a methylclad quaternary ammonium salt of N, N-dimethylaminoethyl methacrylate A water-soluble (co) polymer (ratio A-4) in the same manner as in Example 2 except that 750 parts of an 80% aqueous solution of (a2-2) and 0.042 part of a 10% aqueous solution of (c-1) were used. 625 parts of a polymer flocculant (ratio P-4) was obtained (solid content 93.6%).
上記で得られた高分子凝集剤について表1に示す。表1中の記号の内容は下記のとおりである。
AEMS(a1−1) :アミノエチルメタアクリレートの硫酸塩
AEMCS(a1−2):アミノエチルメタアクリレートのメタンスルホン酸塩
AAm (a2−1) :アクリルアミド
DAMQ(a2−2) :N,N−ジメチルアミノエチルメタアクリレートの
メチルクライド4級アンモニウム塩
塩(B−1) :モノエタノールアミン・メタンスルホン酸塩
塩(B−2) :モノプロパノールアミン・硫酸塩
塩(B−3) :エチルアミン・メタンスルホン酸塩
塩(B’−1) :メタンスルホン酸ナトリウム塩
The polymer flocculants obtained above are shown in Table 1. The contents of the symbols in Table 1 are as follows.
AEMS (a1-1): Sulfate of aminoethyl methacrylate AEMCS (a1-2): Methanesulfonate of aminoethyl methacrylate AAm (a2-1): Acrylamide DAMQ (a2-2): N, N-dimethyl Of aminoethyl methacrylate
Methyl Clyde Quaternary Ammonium Salt Salt (B-1): Monoethanolamine / Methanesulfonate Salt (B-2): Monopropanolamine / Sulfate Salt (B-3): Ethylamine / Methanesulfonate Salt (B '-1): Methanesulfonic acid sodium salt
<凝集性能評価>
実施例1〜13、比較例1〜4
高分子凝集剤(P−1)〜(P−13)、(比P−1)〜(比P−4)をそれぞれイオン交換水に溶解して固形分含量が0.2%の水溶液とした。
J下水処理場から採取した余剰汚泥[pH6.2、TS0.8%、有機分83%]を200部ずつ17個の別々の500mLビーカーに採り、撹拌下で、(P−1)〜(P−13)、(比P−1)〜(比P−4)それぞれの上記水溶液8部を各ビーカーに加え、それぞれのビーカーについて前記評価方法(1)に従って混合処理した〔この時の(P−1)〜(P−13)、(比P−1)〜(比P−4)の固形分添加量は0.4%/TS〕。これらの処理物について前記評価方法(1)〜(5)に従ってフロック粒径、ろ液量、ろ布剥離性、ケーキ含水率およびフロック強度を評価した。結果を表2に示す。
<Aggregation performance evaluation>
Examples 1-13, Comparative Examples 1-4
The polymer flocculants (P-1) to (P-13) and (ratio P-1) to (ratio P-4) were each dissolved in ion-exchanged water to obtain an aqueous solution having a solid content of 0.2%. .
J Excess sludge collected from the sewage treatment plant [pH 6.2, TS 0.8%, organic content 83%] was put in 17 separate 500 mL beakers of 200 parts each, and (P-1) to (P -13), 8 parts of each of the above aqueous solutions (ratio P-1) to (ratio P-4) were added to each beaker, and each beaker was mixed according to the evaluation method (1) [(P- The solid content of 1) to (P-13) and (ratio P-1) to (ratio P-4) is 0.4% / TS]. These treated products were evaluated for floc particle size, filtrate amount, filter cloth peelability, cake moisture content and floc strength according to the evaluation methods (1) to (5). The results are shown in Table 2.
表2の結果から、本発明の高分子凝集剤(P)は、比較のものに比べて、大粒径の粗大フロックを形成し、高撹拌下(300rpm)でも一旦形成されたフロックが壊れにくく(フロックが強固)、ろ布剥離性、脱水性(ケーキ含水率)のいずれにおいても優れた効果を有することがわかる。 From the results in Table 2, the polymer flocculant (P) of the present invention forms a coarse floc having a large particle size compared to the comparative one, and the floc once formed is not easily broken even under high agitation (300 rpm). It can be seen that the film has excellent effects in any of (floc is strong), filter cloth peelability, and dewaterability (cake moisture content).
本発明の高分子凝集剤は、従来のものと比較して高い脱水率(すなわち低いケーキ含水率)を示すことから、下水等または工場廃水等の有機性もしくは無機性汚泥または廃水の脱水処理用高分子凝集剤として用いることができ、とくに有機性汚泥の脱水処理用として好適に用いられる。また、その他の用途としては、例えば掘削・泥水処理用凝集剤、製紙用薬剤(例えば製紙工業用地合形成助剤、濾水歩留向上剤、濾水性向上剤および紙力増強剤)、原油増産用添加剤(原油の二、三次回収用添加剤)、分散剤、スケール防止剤、凝結剤、脱色剤、増粘剤、帯電防止剤および繊維用処理剤が挙げられ、これらのうちとくに掘削・泥水処理用凝集剤、製紙用薬剤および原油増産用添加剤として好適に用いられる。 Since the polymer flocculant of the present invention exhibits a higher dewatering rate (that is, lower cake water content) than conventional ones, it is used for dehydration treatment of organic or inorganic sludge such as sewage or factory wastewater or wastewater. It can be used as a polymer flocculant and is particularly preferably used for dehydration treatment of organic sludge. Other uses include, for example, agglomerating agents for drilling and muddy water treatment, papermaking chemicals (for example, paper industry formation aids, drainage yield improvers, drainage improvers, and paper strength enhancers), and increased crude oil production. Additives (crude oil secondary and tertiary recovery additives), dispersants, scale inhibitors, coagulants, decolorizers, thickeners, antistatic agents, and textile treatment agents. It is suitably used as a flocculant for muddy water treatment, a papermaking chemical and an additive for increasing crude oil production.
Claims (4)
CH2=C(CH3)−CO−X1−Q−N+R1R2R3・Z- (1)
[式中、R1〜R3はH、X1はOまたはNH、Qは炭素数1〜4のアルキレン基、Z-はプロトン酸のH+を除く残基を表す。]
X2−N+R4R5R6・Y- (2)
[式中、X2はヘテロ原子を有していてもよい炭素数1〜5の1価の炭化水素基、R4〜R6はH、Y-はプロトン酸のH+を除く残基を表す。] A water-soluble (co) polymer (A) having a water-soluble unsaturated monomer (a) containing a water-soluble cationic monomer (a1) represented by the following general formula (1) as a structural unit, and the following general formula (2) And (B) based on the weight of (A), and the content of (B) based on the weight of (A) is 1 to 20%.
CH 2 = C (CH 3) -CO-X 1 -Q-N + R 1 R 2 R 3 · Z - (1)
[Wherein R 1 to R 3 are H, X 1 is O or NH, Q is an alkylene group having 1 to 4 carbon atoms, and Z − represents a residue other than H + of a protonic acid. ]
X 2 −N + R 4 R 5 R 6 · Y − (2)
[Wherein X 2 is a monovalent hydrocarbon group having 1 to 5 carbon atoms which may have a hetero atom, R 4 to R 6 are H, and Y − is a residue other than H + of a protonic acid. Represent. ]
6≦Vw/Vs≦35
[式中、Vwは0.2重量%水溶液の粘度(mPa・s、25℃)、Vsは0.5重量%塩水溶液の粘度(mPa・s、25℃)を表す。] The polymer flocculant according to claim 1 or 2, wherein the water-soluble (co) polymer (A) satisfies the following relational expression.
6 ≦ Vw / Vs ≦ 35
[In formula, Vw represents the viscosity (mPa * s, 25 degreeC) of 0.2 weight% aqueous solution, and Vs represents the viscosity (mPa * s, 25 degreeC) of 0.5 weight% salt aqueous solution. ]
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JP2017119272A (en) * | 2015-12-25 | 2017-07-06 | 三洋化成工業株式会社 | Flocculant |
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JP2012170853A (en) * | 2011-02-18 | 2012-09-10 | Sanyo Chem Ind Ltd | Polymer flocculant |
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JPH1053617A (en) * | 1996-04-22 | 1998-02-24 | Sanyo Chem Ind Ltd | Polymer coagulant |
EP1069140A1 (en) * | 1997-10-22 | 2001-01-17 | Sanyo Chemical Industries, Ltd. | Water-soluble polymer, process for the production of the same, and use thereof as polymeric coagulant |
JP2001011124A (en) * | 1999-06-25 | 2001-01-16 | Sanyo Chem Ind Ltd | Polymer coagulant |
JP2001009208A (en) * | 1999-06-28 | 2001-01-16 | Sanyo Chem Ind Ltd | Polymer flocculant |
JP2005205403A (en) * | 2003-12-26 | 2005-08-04 | Sanyo Chem Ind Ltd | Polymeric flocculant |
JP2006167584A (en) * | 2004-12-15 | 2006-06-29 | Tomooka Kaken Kk | Treatment method for sludge or wastewater |
JP2007029766A (en) * | 2005-07-22 | 2007-02-08 | Sanyo Chem Ind Ltd | Organic coagulant and method for treating waste water or sludge |
JP2012170853A (en) * | 2011-02-18 | 2012-09-10 | Sanyo Chem Ind Ltd | Polymer flocculant |
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JP2017119272A (en) * | 2015-12-25 | 2017-07-06 | 三洋化成工業株式会社 | Flocculant |
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