JP4868127B2 - Organic sludge dewatering method - Google Patents
Organic sludge dewatering method Download PDFInfo
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- JP4868127B2 JP4868127B2 JP2006097272A JP2006097272A JP4868127B2 JP 4868127 B2 JP4868127 B2 JP 4868127B2 JP 2006097272 A JP2006097272 A JP 2006097272A JP 2006097272 A JP2006097272 A JP 2006097272A JP 4868127 B2 JP4868127 B2 JP 4868127B2
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- sludge
- polymer flocculant
- mol
- cationic
- flocculant
- Prior art date
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- 239000010802 sludge Substances 0.000 title claims description 135
- 238000000034 method Methods 0.000 title claims description 37
- 229920000642 polymer Polymers 0.000 claims description 71
- 229920006317 cationic polymer Polymers 0.000 claims description 53
- 239000007864 aqueous solution Substances 0.000 claims description 28
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 20
- 229920002554 vinyl polymer Polymers 0.000 claims description 20
- 125000002091 cationic group Chemical group 0.000 claims description 17
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 claims description 16
- 239000010865 sewage Substances 0.000 claims description 14
- 230000003647 oxidation Effects 0.000 claims description 9
- 238000007254 oxidation reaction Methods 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- 229940050176 methyl chloride Drugs 0.000 claims description 8
- 239000008394 flocculating agent Substances 0.000 claims description 7
- 239000010800 human waste Substances 0.000 claims description 6
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 claims description 5
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- WQHCGPGATAYRLN-UHFFFAOYSA-N chloromethane;2-(dimethylamino)ethyl prop-2-enoate Chemical compound ClC.CN(C)CCOC(=O)C=C WQHCGPGATAYRLN-UHFFFAOYSA-N 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- 229920006322 acrylamide copolymer Polymers 0.000 claims 1
- 239000000701 coagulant Substances 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 30
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 28
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 28
- -1 halide ions Chemical class 0.000 description 28
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 28
- 239000000178 monomer Substances 0.000 description 23
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 14
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 14
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 14
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 14
- 239000000243 solution Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 11
- 229920001577 copolymer Polymers 0.000 description 11
- 239000004744 fabric Substances 0.000 description 10
- 239000002245 particle Substances 0.000 description 10
- 239000000470 constituent Substances 0.000 description 9
- 239000000706 filtrate Substances 0.000 description 9
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 9
- 208000005156 Dehydration Diseases 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 125000000129 anionic group Chemical group 0.000 description 8
- 230000018044 dehydration Effects 0.000 description 8
- 238000006297 dehydration reaction Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 7
- 230000005484 gravity Effects 0.000 description 7
- 239000004317 sodium nitrate Substances 0.000 description 7
- 235000010344 sodium nitrate Nutrition 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 125000000217 alkyl group Chemical group 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- 239000004677 Nylon Substances 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- 150000001408 amides Chemical class 0.000 description 4
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 4
- 229940073608 benzyl chloride Drugs 0.000 description 4
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 description 4
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 description 4
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 4
- 238000011038 discontinuous diafiltration by volume reduction Methods 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910000039 hydrogen halide Inorganic materials 0.000 description 4
- 239000012433 hydrogen halide Substances 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229920001778 nylon Polymers 0.000 description 4
- 239000005416 organic matter Substances 0.000 description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 4
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 3
- 230000015271 coagulation Effects 0.000 description 3
- 238000005345 coagulation Methods 0.000 description 3
- 239000011362 coarse particle Substances 0.000 description 3
- 239000003431 cross linking reagent Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229920000620 organic polymer Polymers 0.000 description 3
- 239000003505 polymerization initiator Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-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
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- 150000008360 acrylonitriles Chemical class 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000004931 aggregating effect Effects 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-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
- 150000001450 anions Chemical class 0.000 description 2
- AGEZXYOZHKGVCM-UHFFFAOYSA-N benzyl bromide Chemical compound BrCC1=CC=CC=C1 AGEZXYOZHKGVCM-UHFFFAOYSA-N 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 description 2
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 2
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- DENRZWYUOJLTMF-UHFFFAOYSA-N diethyl sulfate Chemical compound CCOS(=O)(=O)OCC DENRZWYUOJLTMF-UHFFFAOYSA-N 0.000 description 2
- 229940008406 diethyl sulfate Drugs 0.000 description 2
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 2
- 229960003750 ethyl chloride Drugs 0.000 description 2
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 125000001188 haloalkyl group Chemical group 0.000 description 2
- BICAGYDGRXJYGD-UHFFFAOYSA-N hydrobromide;hydrochloride Chemical compound Cl.Br BICAGYDGRXJYGD-UHFFFAOYSA-N 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 2
- HVTICUPFWKNHNG-UHFFFAOYSA-N iodoethane Chemical compound CCI HVTICUPFWKNHNG-UHFFFAOYSA-N 0.000 description 2
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 125000005641 methacryl group Chemical group 0.000 description 2
- 229940102396 methyl bromide Drugs 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- QRWZCJXEAOZAAW-UHFFFAOYSA-N n,n,2-trimethylprop-2-enamide Chemical compound CN(C)C(=O)C(C)=C QRWZCJXEAOZAAW-UHFFFAOYSA-N 0.000 description 2
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 description 2
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- 159000000001 potassium salts Chemical class 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 229920001567 vinyl ester resin Polymers 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 1
- WROUWQQRXUBECT-UHFFFAOYSA-N 2-ethylacrylic acid Chemical compound CCC(=C)C(O)=O WROUWQQRXUBECT-UHFFFAOYSA-N 0.000 description 1
- NDAJNMAAXXIADY-UHFFFAOYSA-N 2-methylpropanimidamide Chemical compound CC(C)C(N)=N NDAJNMAAXXIADY-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000005591 charge neutralization Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000012024 dehydrating agents Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 244000144992 flock Species 0.000 description 1
- 238000005188 flotation Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 1
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 1
- QYZFTMMPKCOTAN-UHFFFAOYSA-N n-[2-(2-hydroxyethylamino)ethyl]-2-[[1-[2-(2-hydroxyethylamino)ethylamino]-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound OCCNCCNC(=O)C(C)(C)N=NC(C)(C)C(=O)NCCNCCO QYZFTMMPKCOTAN-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
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- 230000004044 response Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 description 1
- 229910000342 sodium bisulfate Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Description
本発明は、有機性汚泥の脱水方法に関する。さらに詳しくは、本発明は、難脱水性の有機性汚泥を処理して、ろ過性が良好であり、含水率が低い脱水ケーキを得ることができる有機性汚泥の脱水方法に関する。 The present invention relates to a method for dewatering organic sludge. More specifically, the present invention relates to a method for dehydrating organic sludge that can treat a hardly dehydrated organic sludge to obtain a dehydrated cake with good filterability and low moisture content.
食品工場、化学工場、下水処理場などで発生する汚泥の脱水処理には、ほとんどの場合、高分子凝集剤が使用されている。高分子凝集剤としては、カチオン性構成単位を単独で重合、又は、カチオン性構成単位とノニオン性構成単位とを共重合したカチオン性高分子凝集剤が広く使われてきた。 In most cases, polymer flocculants are used for dewatering sludge generated in food factories, chemical factories, sewage treatment plants, and the like. As the polymer flocculant, a cationic polymer flocculant obtained by polymerizing a cationic structural unit alone or copolymerizing a cationic structural unit and a nonionic structural unit has been widely used.
最近では、カチオン性構成単位に、アニオン性構成単位とノニオン性構成単位を共重合した両性高分子凝集剤がよく使用されるが、両性高分子凝集剤は、凝集時に分子間架橋をすることにより、はじめて高い凝集性能を発揮する。これらの高分子凝集剤は、汚泥の性質、汚泥の減容目標値に合わせて、使いこなされているが、汚泥の難脱水化に伴い、さらなる脱水性能向上、汚泥減容化が要望され、開発が進められている。 Recently, amphoteric polymer flocculants obtained by copolymerizing anionic structural units and nonionic structural units are often used as cationic structural units. For the first time, it exhibits high agglomeration performance. These polymer flocculants have been used according to the properties of sludge and the target volume of sludge reduction, but as sludge becomes difficult to dewater, further dewatering performance and sludge volume reduction have been requested and developed. Is underway.
例えば、低い添加率で難脱水性汚泥を効果的に脱水することができ、強固な凝集フロックを形成して汚泥処理能力を高めることができる汚泥脱水剤として、カチオン性高分子凝集剤と両性高分子凝集剤とを含む汚泥脱水剤であって、カチオン性高分子凝集剤のカチオン性構成単位（Ｃ）とノニオン性構成単位（Ｎ）のモル組成比Ｃ／Ｎが０.２以上であり、両性高分子凝集剤のアニオン性構成単位（Ａ）とカチオン性構成単位（Ｃ）のモル組成比Ａ／Ｃが０.８〜１.５であり、カチオン性高分子凝集剤と両性高分子凝集剤の重量比が３５：６５〜９５：５である汚泥脱水剤が提案されている（特許文献１）。しかし、この汚泥脱水剤を用いても、下水処理場の混合汚泥、し尿処理場の三次汚泥を含んだ余剰汚泥、凝集汚泥を含んだ混合汚泥、消化汚泥、オキシデーションディッチ法による余剰汚泥、無機凝集剤が添加された余剰汚泥などの難脱水性汚泥を処理して、含水率の低い脱水ケーキを得ることは困難であった。 For example, as a sludge dewatering agent capable of effectively dewatering hardly dewatering sludge at a low addition rate and forming a strong coagulation floc to increase the sludge treatment capacity, cationic polymer flocculants and amphoteric high sludges can be used. A sludge dewatering agent comprising a molecular flocculant, wherein the molar composition ratio C / N of the cationic structural unit (C) and the nonionic structural unit (N) of the cationic polymer flocculant is 0.2 or more; The molar composition ratio A / C of the anionic structural unit (A) and the cationic structural unit (C) of the amphoteric polymer flocculant is 0.8 to 1.5, and the cationic polymer flocculant and the amphoteric polymer flocculant A sludge dewatering agent having a weight ratio of 35:65 to 95: 5 has been proposed (Patent Document 1). However, even with this sludge dewatering agent, mixed sludge from sewage treatment plants, excess sludge containing tertiary sludge from human waste treatment plants, mixed sludge containing coagulated sludge, digested sludge, excess sludge by oxidation ditch method, inorganic It has been difficult to obtain a dehydrated cake having a low water content by treating a hardly dewatering sludge such as excess sludge to which a flocculant has been added.
食品工場、化学工場、下水処理場などで発生する汚泥の脱水処理では、前述の如く、汚泥の質、汚泥の減容目標に合わせて種々の脱水剤が使用されているが、近年の汚泥の難脱水化と汚泥減容の高度化の要求に対して、比較的高い凝集性能と脱水性が得られるカチオン性高分子凝集剤と両性高分子凝集剤が使用されるようになってきた。しかし、両者の高分子凝集剤をもってしても、十分な脱水効果を得ることは難しくなっているのが現状と言える。例えば、汚泥を長時間曝気するオキシデーションディッチ法では、汚泥は生物分解され、有機物含有量が低くはなるが、性状的には繊維分が少なくなり、汚泥粒子は粒子径分布が広い上に、高分子凝集剤と反応するための吸着点が少なくなり、高分子どうしを橋かけする溶解性のアニオン物質が少なくなるために、逆に脱水性が悪化する。また、汚泥を嫌気性にして消化分解する方法は、汚泥の減容化の目的には適っているが、この場合汚泥粒子が小さくなり、分散状態となるために、脱水時の高分子凝集剤の添加量が多くなるとか、脱水したときの含水率が高くなるという問題点が発生する。また、汚泥を減容化するための脱水機が、高い脱水効果を得るような構造になっている場合、フロックに強いせん断力がかかる。このために、適用する高分子凝集剤は、強いフロックを形成する性能を有することが必要となる。
本発明は、難脱水性の有機性汚泥を処理して、ろ過性が良好であり、含水率が低い脱水ケーキを得ることができる有機性汚泥の脱水方法を提供することを目的としてなされたものである。 The present invention was made for the purpose of providing a method for dewatering organic sludge that can treat a hardly dehydrated organic sludge to obtain a dehydrated cake with good filterability and low moisture content. It is.
本発明者は、上記の課題を解決すべく鋭意研究を重ねた結果、有機性汚泥の脱水処理に際してカチオン性高分子凝集剤と両性高分子凝集剤とを併用し、かつ溶液粘度／固有粘度の比の大きいカチオン性高分子凝集剤を用いることにより、ろ過性が良好であって、含水率が低い脱水ケーキを得ることができ、さらに特定の構成単位を有する両性高分子凝集剤を用いることにより、脱水性がいっそう向上することを見いだし、この知見に基づいて本発明を完成するに至った。 As a result of intensive studies to solve the above-mentioned problems, the present inventor has used a cationic polymer flocculant and an amphoteric polymer flocculant in dehydration treatment of organic sludge, and has a solution viscosity / intrinsic viscosity. By using a cationic polymer flocculant with a large ratio, a dehydrated cake with good filterability and low water content can be obtained, and by using an amphoteric polymer flocculant having a specific structural unit The inventors have found that the dehydrating property is further improved and have completed the present invention based on this finding.
すなわち、本発明は、
（１）有機性汚泥に、凝集剤として、カチオン性高分子凝集剤３０〜７０重量％及び両性高分子凝集剤７０〜３０重量％の割合で添加して脱水する有機性汚泥の脱水方法において、前記カチオン性高分子凝集剤が、ブルックフィールドＢ形回転粘度計を用いて、回転速度３０ｒｐｍ、ＳＢ２号スピンドル、３０℃で測定した０.２重量％水溶液の粘度（ｍＰａ・ｓ）を、１モル／Ｌ硝酸ナトリウム水溶液を溶媒として、３０℃で測定した固有粘度（ｄＬ／ｇ）で除した商が７０以上のジメチルアミノエチルアクリレートのメチルクロリド四級化物２０〜８０モル％とアクリルアミドの共重合体８０〜２０モル％からなるカチオン性ビニル系高分子凝集剤であって、前記両性高分子凝集剤が、ジメチルアミノエチルアクリレートのメチルクロリド四級化物及び該ジメチルアミノエチルアクリレートのメチルクロリド四級化物より少ないモル量のジメチルアミノエチルメタクリレートのメチルクロリド四級化物からなるカチオン性構成単位２０〜５０モル％、アクリル酸からなるアニオン性構成単位１０〜４０モル％並びにアクリルアミドからなるノニオン性構成単位１０〜７０モル％からなる凝集剤を用いることを特徴とする有機性汚泥の脱水方法、及び、
（２）有機性汚泥が、下水処理場の混合汚泥、し尿処理場の三次汚泥を含んだ余剰汚泥、凝集汚泥を含んだ混合汚泥、消化汚泥又はオキシデーションディッチ法による余剰汚泥である(１)記載の有機性汚泥の脱水方法、
を提供するものである。
That is, the present invention
(1) In the dewatering method of organic sludge, which is added to organic sludge as a flocculant at a ratio of 30 to 70% by weight of cationic polymer flocculant and 70 to 30% by weight of amphoteric polymer flocculant, and dehydrated. The cationic polymer flocculant has a viscosity (mPa · s) of 1% by weight of a 0.2 wt% aqueous solution measured at 30 ° C. using a Brookfield B-type rotational viscometer at a rotation speed of 30 rpm and an SB2 spindle. Copolymer of acrylamide and 20 to 80 mol% of dimethylaminoethyl acrylate methyl chloride having a quotient divided by intrinsic viscosity (dL / g) measured at 30 ° C. using an aqueous solution of / L sodium nitrate as a solvent A cationic vinyl polymer flocculant comprising 80 to 20 mol% , wherein the amphoteric polymer flocculant is methyl chloride of dimethylaminoethyl acrylate. A cationic constituent unit comprising 20 to 50 mol% of a quaternized product and a methyl chloride quaternized product of dimethylaminoethyl methacrylate in a molar amount less than that of the methyl chloride quaternized product of the dimethylaminoethyl acrylate, an anionic constituent unit comprising acrylic acid A method for dewatering organic sludge characterized by using a flocculant comprising 10 to 40 mol% and 10 to 70 mol% of a nonionic structural unit comprising acrylamide ; and
( 2 ) Organic sludge is mixed sludge from sewage treatment plants, excess sludge containing tertiary sludge from human waste treatment plants, mixed sludge containing coagulated sludge, digested sludge, or excess sludge by oxidation ditch method (1) Dehydration method of organic sludge as described,
Is to provide.
本発明の有機性汚泥の処理方法によれば、難脱水性の汚泥を処理して、ろ過性が良好であり、含水率の低い脱水ケーキを得ることができる。本発明方法によれば、従来の方法と比べて、脱水ケーキの含水率が約２重量％低下し、ケーキ収量が３０〜５０重量％向上する。この結果から、汚泥は約１０体積％減容化され、脱水時の処理量は３０〜５０重量％向上することが推定される。そして、最終的には汚泥の処理処分費の低減に寄与することができる。 According to the organic sludge treatment method of the present invention, it is possible to obtain a dehydrated cake having a good filterability and a low water content by treating a hardly dewaterable sludge. According to the method of the present invention, the moisture content of the dehydrated cake is reduced by about 2% by weight and the cake yield is improved by 30 to 50% by weight, compared with the conventional method. From this result, it is estimated that the sludge is reduced in volume by about 10% by volume, and the treatment amount during dehydration is improved by 30 to 50% by weight. And finally, it can contribute to reduction of the treatment disposal cost of sludge.
本発明の有機性汚泥の脱水方法においては、有機性汚泥にカチオン性高分子凝集剤と両性高分子凝集剤とを添加して脱水する有機性汚泥の脱水方法において、カチオン性高分子凝集剤が、ブルックフィールドＢ形回転粘度計を用いて、回転速度３０ｒｐｍ、ＳＢ２号スピンドル、３０℃で測定した０.２重量％水溶液の粘度（ｍＰａ・ｓ）を、１モル／Ｌ硝酸ナトリウム水溶液を溶媒として、３０℃で測定した固有粘度（ｄＬ／ｇ）で除した商が７０以上であるカチオン性ビニル系高分子凝集剤である。 In the organic sludge dewatering method of the present invention, the cationic polymer flocculant is added to the organic sludge by adding a cationic polymer flocculant and an amphoteric polymer flocculant to dehydrate. Using a Brookfield B-type rotational viscometer, the viscosity (mPa · s) of a 0.2 wt% aqueous solution measured at 30 ° C. with a rotational speed of 30 rpm, SB 2 spindle, 1 mol / L sodium nitrate aqueous solution as a solvent The cationic vinyl polymer flocculant having a quotient of 70 or more divided by the intrinsic viscosity (dL / g) measured at 30 ° C.
カチオン性高分子凝集剤の０.２重量％水溶液の粘度（ｍＰａ・ｓ）は、基本的にはＪＩＳ Ｋ ７１１７−１にしたがって測定することができるが、本発明においては、測定温度は３０℃で測定される。ブルックフィールドＢ形回転粘度計としては、(株)東京計器製のＢ型粘度計を用いることができる。また、カチオン性高分子凝集剤の０.２重量％水溶液は、精製した高分子約１ｇを精秤し、５００ｍＬガラス製ビーカーに移した後に、カチオン性高分子凝集剤濃度が０.２重量％となるようスターラーで撹拌しながら脱イオン水をビーカーに添加していき、その後５００ｒｐｍで２時間撹拌したのち、室温で１日放置して溶解させたものを用いる。なお、高分子凝集剤の製品形態がエマルション、ディスパージョン又は水溶液などの液状品である場合には、アセトンなどの溶媒を用いて予め精製してから０.２重量％水溶液を調製する。ブルックフィールドＢ形回転粘度計を用いて、回転速度３０ｒｐｍ、ＳＢ２号スピンドル、３０℃で測定したカチオン性高分子凝集剤の０.２重量％水溶液の粘度は、４００〜１,０００ｍＰａ・ｓであることが好ましく、５００〜９００ｍＰａ・ｓであることがより好ましい。０.２重量％水溶液の粘度が４００ｍＰａ・ｓ未満であると、凝集力が弱く、汚泥の処理性能が低下するおそれがある。０.２重量％水溶液の粘度が１,０００ｍＰａ・ｓを超えると、水溶液が高粘度になって、作業性が低下するおそれがある。 The viscosity (mPa · s) of a 0.2% by weight aqueous solution of the cationic polymer flocculant can basically be measured according to JIS K 7117-1, but in the present invention, the measurement temperature is 30 ° C. Measured in As the Brookfield B-type rotational viscometer, a B-type viscometer manufactured by Tokyo Keiki Co., Ltd. can be used. In addition, a 0.2% by weight aqueous solution of the cationic polymer flocculant was precisely weighed about 1 g of the purified polymer, transferred to a 500 mL glass beaker, and then the cationic polymer flocculant concentration was 0.2% by weight. Then, deionized water is added to the beaker while stirring with a stirrer, and the mixture is stirred for 2 hours at 500 rpm and then allowed to stand at room temperature for 1 day for dissolution. In addition, when the product form of the polymer flocculant is a liquid product such as an emulsion, a dispersion, or an aqueous solution, a 0.2 wt% aqueous solution is prepared after purification in advance using a solvent such as acetone. Using a Brookfield B-type rotational viscometer, the viscosity of a 0.2% by weight aqueous solution of the cationic polymer flocculant measured at 30 ° C. with a rotational speed of 30 rpm, SB 2 spindle is 400 to 1,000 mPa · s. It is preferably 500 to 900 mPa · s. When the viscosity of the 0.2% by weight aqueous solution is less than 400 mPa · s, the cohesive force is weak and the sludge treatment performance may be reduced. When the viscosity of the 0.2 wt% aqueous solution exceeds 1,000 mPa · s, the aqueous solution becomes highly viscous, and workability may be reduced.
カチオン性高分子凝集剤の固有粘度は、キャノンフェンスケ粘度計、オストワルド粘度計、ウベローデ型粘度計などを用いて測定することができ、キャノンフェンスケ粘度計を好適に用いることができる。１モル／Ｌ硝酸ナトリウム水溶液を溶媒として、３０℃で測定したカチオン性高分子凝集剤の固有粘度は、１〜１５ｄＬ／ｇであることが好ましく、３〜１２ｄＬ／ｇであることがより好ましい。固有粘度が１ｄＬ／ｇ未満であると、凝集力が弱く、汚泥の処理性能が低下するおそれがある。固有粘度が１５ｄＬ／ｇを超えると、水溶液が高粘度になって、作業性が低下するおそれがある。 The intrinsic viscosity of the cationic polymer flocculant can be measured using a Cannon-Fenceke viscometer, an Ostwald viscometer, an Ubbelohde viscometer, etc., and the Cannon-Fenceke viscometer can be preferably used. The intrinsic viscosity of the cationic polymer flocculant measured at 30 ° C. using a 1 mol / L sodium nitrate aqueous solution as a solvent is preferably 1 to 15 dL / g, and more preferably 3 to 12 dL / g. If the intrinsic viscosity is less than 1 dL / g, the cohesive force is weak and the sludge treatment performance may be reduced. If the intrinsic viscosity exceeds 15 dL / g, the aqueous solution becomes highly viscous, and workability may be reduced.
本発明方法においては、カチオン性高分子凝集剤が、ブルックフィールドＢ形回転粘度計を用いて、回転速度３０ｒｐｍ、ＳＢ２号スピンドル、３０℃で測定した０.２重量％水溶液の粘度（ｍＰａ・ｓ）を、１モル／Ｌ硝酸ナトリウム水溶液を溶媒として、３０℃で測定した固有粘度（ｄＬ／ｇ）で除した商が７０以上であり、より好ましくは７０〜２００であり、さらに好ましくは１２０〜１６０である。該溶液粘度を該固有粘度で除した商が７０未満であると、有機性汚泥に対する凝集作用が弱く、脱水ケーキの含水率が十分に低下しないおそれがある。該溶液粘度を該固有粘度で除した商が２００を超えると、高分子凝集剤の水に対する溶解性が低下するおそれがある。 In the method of the present invention, the cationic polymer flocculant is a viscosity (mPa · s) of a 0.2 wt% aqueous solution measured at 30 ° C. using a Brookfield B type rotational viscometer at a rotational speed of 30 rpm, SB2 spindle. ) Is a quotient of 70 or more, more preferably 70 to 200, still more preferably 120 to 200, divided by the intrinsic viscosity (dL / g) measured at 30 ° C. using a 1 mol / L sodium nitrate aqueous solution as a solvent. 160. If the quotient obtained by dividing the solution viscosity by the intrinsic viscosity is less than 70, the coagulation action on the organic sludge is weak, and the moisture content of the dehydrated cake may not be sufficiently reduced. If the quotient obtained by dividing the solution viscosity by the intrinsic viscosity exceeds 200, the solubility of the polymer flocculant in water may be reduced.
本発明方法に用いるカチオン性高分子凝集剤は、カチオン性ビニル単量体とノニオン性ビニル単量体の共重合によって得られる共重合物であり、カチオン性構成単位（Ｃ）とノニオン性構成単位（Ｎ）のモル比Ｃ／Ｎが０.２以上の共重合物であることが好ましい。カチオン性ビニル単量体としては、例えば、一般式［１］で表される単量体を挙げることができる。
一般式［１］において、Ｒ1は水素又はメチル基であり、Ｒ2はメチレン基、エチレン基、プロピレン基、ブチレン基などの炭素数１〜４のアルキレン基であり、プロピレン基及びブチレン基は直鎖状であってもよく、側鎖を有するものであってもよい。Ｒ3はメチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、sec−ブチル基、tert−ブチル基などの炭素数１〜４のアルキル基であり、Ｒ4は水素、炭素数１〜４のアルキル基又はベンジル基である。また、−Ａ−は−Ｏ−又は−ＮＨ−であり、Ｘ-は塩素イオン、臭素イオン、ヨウ素イオンなどのハロゲンイオン、１／２ＳＯ4 2-、ＮＯ3 -、ＣＨ3ＣＯＯ-、ＣＨ3ＳＯ4 -、Ｃ2Ｈ5ＳＯ4 -などのアニオンである。 In the general formula [1], R 1 is hydrogen or a methyl group, R 2 is an alkylene group having 1 to 4 carbon atoms such as a methylene group, an ethylene group, a propylene group, or a butylene group, and the propylene group and the butylene group are It may be a straight chain or may have a side chain. R 3 is an alkyl group having 1 to 4 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, R 4 is Hydrogen, an alkyl group having 1 to 4 carbon atoms, or a benzyl group. Further, -A- is -O- or -NH-, X - is chloride, bromide, halide ions such as iodide ion, 1 / 2SO 4 2-, NO 3 -, CH 3 COO -, CH 3 Anions such as SO 4 − and C 2 H 5 SO 4 — .
一般式［１］で表される単量体としては、例えば、ジメチルアミノ(メチル、エチル、プロピル又はブチル)アクリレート又はメタクリレート、ジエチルアミノ(メチル、エチル、プロピル又はブチル)アクリレート又はメタクリレート、ジ−ｎ−プロピルアミノ(メチル、エチル、プロピル又はブチル)アクリレート又はメタクリレート、ジイソプロピルアミノ(メチル、エチル、プロピル又はブチル)アクリレート又はメタクリレート、ジ−ｎ−ブチルアミノ(メチル、エチル、プロピル又はブチル)アクリレート又はメタクリレート、ジ−sec−ブチルアミノ(メチル、エチル、プロピル又はブチル)アクリレート又はメタクリレート、ジイソブチルアミノ(メチル、エチル、プロピル又はブチル)アクリレート又はメタクリレート、ジメチルアミノ(メチル、エチル、プロピル又はブチル)アクリルアミド又はメタクリルアミド、ジエチルアミノ(メチル、エチル、プロピル又はブチル)アクリルアミド又はメタクリルアミド、ジ−ｎ−プロピルアミノ(メチル、エチル、プロピル又はブチル)アクリルアミド又はメタクリルアミド、ジイソプロピルアミノ(メチル、エチル、プロピル又はブチル)アクリルアミド又はメタクリルアミド、ジ−ｎ−ブチルアミノ(メチル、エチル、プロピル又はブチル)アクリルアミド又はメタクリルアミド、ジ−sec−ブチルアミノ(メチル、エチル、プロピル又はブチル)アクリルアミド又はメタクリルアミド、ジイソブチルアミノ(メチル、エチル、プロピル又はブチル)アクリルアミド又はメタクリルアミドなどのハロゲン化水素、硫酸、硝酸、酢酸などによる中和塩、ハロゲン化アルキル、ハロゲン化ベンジル、ジメチル硫酸、ジエチル硫酸などによる四級化物などを挙げることができる。ハロゲン化水素としては、例えば、塩化水素、臭化水素などを、ハロゲン化アルキルとしては、例えば、塩化メチル、臭化メチル、ヨウ化メチル、塩化エチル、臭化エチル、ヨウ化エチルなどを、ハロゲン化ベンジルとしては、塩化ベンジル、臭化ベンジルなどを挙げることができる。これらのカチオン性ビニル系単量体は、１種を単独で用いることができ、あるいは、２種以上を組み合わせて用いることもできる。 Examples of the monomer represented by the general formula [1] include dimethylamino (methyl, ethyl, propyl or butyl) acrylate or methacrylate, diethylamino (methyl, ethyl, propyl or butyl) acrylate or methacrylate, di-n- Propylamino (methyl, ethyl, propyl or butyl) acrylate or methacrylate, diisopropylamino (methyl, ethyl, propyl or butyl) acrylate or methacrylate, di-n-butylamino (methyl, ethyl, propyl or butyl) acrylate or methacrylate, di- -Sec-butylamino (methyl, ethyl, propyl or butyl) acrylate or methacrylate, diisobutylamino (methyl, ethyl, propyl or butyl) acrylate or methacrylate, dimethylamino (methyl Ethyl, propyl or butyl) acrylamide or methacrylamide, diethylamino (methyl, ethyl, propyl or butyl) acrylamide or methacrylamide, di-n-propylamino (methyl, ethyl, propyl or butyl) acrylamide or methacrylamide, diisopropylamino (methyl , Ethyl, propyl or butyl) acrylamide or methacrylamide, di-n-butylamino (methyl, ethyl, propyl or butyl) acrylamide or methacrylamide, di-sec-butylamino (methyl, ethyl, propyl or butyl) acrylamide or methacryl Neutralized salts such as amide, diisobutylamino (methyl, ethyl, propyl or butyl) acrylamide or methacrylamide, hydrogen halide, sulfuric acid, nitric acid, acetic acid, halogen Alkyl, benzyl halide, dimethyl sulfate, quaternary products due diethyl sulfate and the like. Examples of the hydrogen halide include hydrogen chloride and hydrogen bromide, and examples of the halogenated alkyl include methyl chloride, methyl bromide, methyl iodide, ethyl chloride, ethyl bromide, and ethyl iodide. Examples of benzyl chloride include benzyl chloride and benzyl bromide. These cationic vinyl monomers can be used alone or in combination of two or more.
カチオン性有機高分子凝集剤の合成に用いるノニオン性ビニル単量体としては、例えば、アクリルアミド、メタクリルアミド、Ｎ,Ｎ−ジメチルアクリルアミド、Ｎ,Ｎ−ジメチルメタクリルアミドなどのアミド類、アクリロニトリル、メタクリロニトリルなどのシアン化ビニル系化合物、アクリル酸メチル、アクリル酸エチル、メタクリル酸メチル、メタクリル酸エチルなどの(メタ)アクリル酸のアルキルエステル、酢酸ビニルなどのビニルエステル、スチレン、α−メチルスチレン、ｐ−メチルスチレンなどの芳香族ビニル系化合物などを挙げることができる。これらのノニオン性ビニル単量体は、１種を単独で用いることができ、あるいは、２種以上を組み合わせて用いることもできる。 Nonionic vinyl monomers used for the synthesis of cationic organic polymer flocculants include, for example, amides such as acrylamide, methacrylamide, N, N-dimethylacrylamide, N, N-dimethylmethacrylamide, acrylonitrile, methacrylo Vinyl cyanide compounds such as nitriles, alkyl esters of (meth) acrylic acid such as methyl acrylate, ethyl acrylate, methyl methacrylate and ethyl methacrylate, vinyl esters such as vinyl acetate, styrene, α-methylstyrene, p -Aromatic vinyl compounds such as methylstyrene can be mentioned. These nonionic vinyl monomers can be used individually by 1 type, or can also be used in combination of 2 or more type.
本発明において、カチオン性高分子凝集剤のカチオン性構成単位（Ｃ）とノニオン性構成単位（Ｎ）のモル比はＣ／Ｎは、０.２以上であることが好ましく、０.４〜５であることがより好ましい。Ｃ／Ｎが０.２未満であると、汚泥脱水剤の最適添加率が高くなり、重力ろ過性が劣り、ケーキの含水率とろ液の濁度が高くなるなど、全般的に凝集脱水性能が低下するおそれがある。 In the present invention, the molar ratio of the cationic structural unit (C) to the nonionic structural unit (N) of the cationic polymer flocculant is preferably C / N of 0.2 or more, and 0.4 to 5 It is more preferable that When the C / N is less than 0.2, the optimum addition rate of the sludge dehydrating agent is increased, the gravity filterability is inferior, the moisture content of the cake and the turbidity of the filtrate are increased, and so on. May decrease.
本発明方法に用いるカチオン性高分子凝集剤の製造方法は特に限定されるものではないが、通常は、カチオン性ビニル単量体とノニオン性ビニル単量体と架橋剤（メチレンビスアクリルアミド等の架橋性単量体を含む）とを重合開始剤の存在下にＷ／Ｏ型乳化重合することによって好適に製造することができる。なお、ブルックフィールドＢ形回転粘度計を用いて、回転速度３０ｒｐｍ、ＳＢ２号スピンドル、３０℃で測定した０.２重量％水溶液の粘度（ｍＰａ・ｓ）を、１モル／Ｌ硝酸ナトリウム水溶液を溶媒として、３０℃で測定した固有粘度（ｄＬ／ｇ）で除した商は、製造方法、具体的には単量体濃度、架橋剤濃度、重合開始剤濃度や重合温度などを種々調整することにより調整され、一般には架橋剤濃度が高いほど、当該値は大きくなる傾向にある。 The method for producing the cationic polymer flocculant used in the method of the present invention is not particularly limited. Usually, a cationic vinyl monomer, a nonionic vinyl monomer, and a crosslinking agent (such as a cross-linking agent such as methylene bisacrylamide) are used. Can be suitably produced by W / O emulsion polymerization in the presence of a polymerization initiator. The viscosity (mPa · s) of a 0.2 wt% aqueous solution measured at 30 ° C. using a Brookfield B-type rotational viscometer with a rotation speed of 30 rpm, SB2 spindle, 1 mol / L sodium nitrate aqueous solution as solvent The quotient divided by the intrinsic viscosity (dL / g) measured at 30 ° C. is obtained by variously adjusting the production method, specifically the monomer concentration, the crosslinking agent concentration, the polymerization initiator concentration, the polymerization temperature, etc. In general, the higher the crosslinker concentration, the greater the value.
本発明方法に用いる両性高分子凝集剤は、カチオン性構成単位が２０〜５０モル％であることが好ましく、２５〜４０モル％であることがより好ましく、アニオン性構成単位が１０〜４０モル％であることが好ましく、１５〜３５モル％であることがより好ましく、ノニオン性構成単位が１０〜７０モル％であることが好ましく、２５〜６５モル％であることがより好ましい。両性高分子凝集剤のカチオン性構成単位が２０〜５０モル％、アニオン性構成単位が１０〜４０モル％、ノニオン性構成単位が１０〜７０モル％であると、有機性汚泥の処理において、重力ろ過性が良好であり、脱水ケーキの含水率が低く、ケーキ収量が多く、濁度の低いろ液を得ることができる。本発明方法に用いる両性高分子凝集剤の１モル／Ｌ硝酸ナトリウム水溶液を溶媒として３０℃で測定した固有粘度は、２〜１５ｄＬ／ｇであることが好ましく、４〜１０ｄＬ／ｇであることがより好ましい。 In the amphoteric polymer flocculant used in the method of the present invention, the cationic constituent unit is preferably 20 to 50 mol%, more preferably 25 to 40 mol%, and the anionic constituent unit is 10 to 40 mol%. It is preferable that it is 15-35 mol%, it is preferable that it is 10-70 mol%, and it is more preferable that it is 25-65 mol%. In the treatment of organic sludge, the amphoteric polymer flocculant has a cationic constituent unit of 20 to 50 mol%, an anionic constituent unit of 10 to 40 mol%, and a nonionic constituent unit of 10 to 70 mol%. A filter with good filterability, low moisture content of the dehydrated cake, high cake yield, and low turbidity can be obtained. The intrinsic viscosity measured at 30 ° C. using a 1 mol / L aqueous sodium nitrate solution of the amphoteric polymer flocculant used in the method of the present invention as a solvent is preferably 2 to 15 dL / g, and preferably 4 to 10 dL / g. More preferred.
本発明方法に用いる両性高分子凝集剤は、カチオン性ビニル単量体とアニオン性ビニル単量体とノニオン性ビニル単量体を共重合することにより得ることができる。カチオン性ビニル単量体としては、例えば、一般式［１］で表される化合物を挙げることができる。
一般式［１］において、Ｒ1は水素又はメチル基であり、Ｒ2はメチレン基、エチレン基、プロピレン基、ブチレン基などの炭素数１〜４のアルキレン基であり、プロピレン基及びブチレン基は直鎖状であってもよく、側鎖を有するものであってもよい。Ｒ3はメチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、sec−ブチル基、tert−ブチル基などの炭素数１〜４のアルキル基であり、Ｒ4は水素、炭素数１〜４のアルキル基又はベンジル基である。また、−Ａ−は−Ｏ−又は−ＮＨ−であり、Ｘ-は塩素イオン、臭素イオン、ヨウ素イオンなどのハロゲンイオン、１／２ＳＯ4 2-、ＮＯ3 -、ＣＨ3ＣＯＯ-、ＣＨ3ＳＯ4 -、Ｃ2Ｈ5ＳＯ4 -などのアニオンである。 In the general formula [1], R 1 is hydrogen or a methyl group, R 2 is an alkylene group having 1 to 4 carbon atoms such as a methylene group, an ethylene group, a propylene group, or a butylene group, and the propylene group and the butylene group are It may be a straight chain or may have a side chain. R 3 is an alkyl group having 1 to 4 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, R 4 is Hydrogen, an alkyl group having 1 to 4 carbon atoms, or a benzyl group. Further, -A- is -O- or -NH-, X - is chloride, bromide, halide ions such as iodide ion, 1 / 2SO 4 2-, NO 3 -, CH 3 COO -, CH 3 Anions such as SO 4 − and C 2 H 5 SO 4 — .
一般式［１］で表される単量体としては、例えば、ジメチルアミノ(メチル、エチル、プロピル又はブチル)アクリレート又はメタクリレート、ジエチルアミノ(メチル、エチル、プロピル又はブチル)アクリレート又はメタクリレート、ジ−ｎ−プロピルアミノ(メチル、エチル、プロピル又はブチル)アクリレート又はメタクリレート、ジイソプロピルアミノ(メチル、エチル、プロピル又はブチル)アクリレート又はメタクリレート、ジ−ｎ−ブチルアミノ(メチル、エチル、プロピル又はブチル)アクリレート又はメタクリレート、ジ−sec−ブチルアミノ(メチル、エチル、プロピル又はブチル)アクリレート又はメタクリレート、ジイソブチルアミノ(メチル、エチル、プロピル又はブチル)アクリレート又はメタクリレート、ジメチルアミノ(メチル、エチル、プロピル又はブチル)アクリルアミド又はメタクリルアミド、ジエチルアミノ(メチル、エチル、プロピル又はブチル)アクリルアミド又はメタクリルアミド、ジ−ｎ−プロピルアミノ(メチル、エチル、プロピル又はブチル)アクリルアミド又はメタクリルアミド、ジイソプロピルアミノ(メチル、エチル、プロピル又はブチル)アクリルアミド又はメタクリルアミド、ジ−ｎ−ブチルアミノ(メチル、エチル、プロピル又はブチル)アクリルアミド又はメタクリルアミド、ジ−sec−ブチルアミノ(メチル、エチル、プロピル又はブチル)アクリルアミド又はメタクリルアミド、ジイソブチルアミノ(メチル、エチル、プロピル又はブチル)アクリルアミド又はメタクリルアミドなどのハロゲン化水素、硫酸、硝酸、酢酸などによる中和塩、ハロゲン化アルキル、ハロゲン化ベンジル、ジメチル硫酸、ジエチル硫酸などによる四級化物などを挙げることができる。ハロゲン化水素としては、例えば、塩化水素、臭化水素などを、ハロゲン化アルキルとしては、例えば、塩化メチル、臭化メチル、ヨウ化メチル、塩化エチル、臭化エチル、ヨウ化エチルなどを、ハロゲン化ベンジルとしては、塩化ベンジル、臭化ベンジルなどを挙げることができる。これらのカチオン性ビニル系単量体は、１種を単独で用いることができ、あるいは、２種以上を組み合わせて用いることもできる。 Examples of the monomer represented by the general formula [1] include dimethylamino (methyl, ethyl, propyl or butyl) acrylate or methacrylate, diethylamino (methyl, ethyl, propyl or butyl) acrylate or methacrylate, di-n- Propylamino (methyl, ethyl, propyl or butyl) acrylate or methacrylate, diisopropylamino (methyl, ethyl, propyl or butyl) acrylate or methacrylate, di-n-butylamino (methyl, ethyl, propyl or butyl) acrylate or methacrylate, di- -Sec-butylamino (methyl, ethyl, propyl or butyl) acrylate or methacrylate, diisobutylamino (methyl, ethyl, propyl or butyl) acrylate or methacrylate, dimethylamino (methyl Ethyl, propyl or butyl) acrylamide or methacrylamide, diethylamino (methyl, ethyl, propyl or butyl) acrylamide or methacrylamide, di-n-propylamino (methyl, ethyl, propyl or butyl) acrylamide or methacrylamide, diisopropylamino (methyl , Ethyl, propyl or butyl) acrylamide or methacrylamide, di-n-butylamino (methyl, ethyl, propyl or butyl) acrylamide or methacrylamide, di-sec-butylamino (methyl, ethyl, propyl or butyl) acrylamide or methacryl Neutralized salts such as amide, diisobutylamino (methyl, ethyl, propyl or butyl) acrylamide or methacrylamide, hydrogen halide, sulfuric acid, nitric acid, acetic acid, halogen Alkyl, benzyl halide, dimethyl sulfate, quaternary products due diethyl sulfate and the like. Examples of the hydrogen halide include hydrogen chloride and hydrogen bromide, and examples of the halogenated alkyl include methyl chloride, methyl bromide, methyl iodide, ethyl chloride, ethyl bromide, and ethyl iodide. Examples of benzyl chloride include benzyl chloride and benzyl bromide. These cationic vinyl monomers can be used alone or in combination of two or more.
本発明方法に用いる両性有機高分子凝集剤のアニオン性構成単位となるアニオン性ビニル単量体としては、例えば、アクリル酸、メタクリル酸、α−エチルアクリル酸及びこれらのナトリウム塩、カリウム塩、アンモニウム塩、マレイン酸、フマル酸、イタコン酸などの二塩基酸及びこれらのナトリウム塩、カリウム塩、アンモニウム塩などを挙げることができる。これらのアニオン性ビニル単量体は、１種を単独で用いることができ、あるいは、２種以上を組み合わせて用いることもできる。 Examples of the anionic vinyl monomer that is an anionic constituent unit of the amphoteric organic polymer flocculant used in the method of the present invention include acrylic acid, methacrylic acid, α-ethylacrylic acid, and sodium salts, potassium salts, and ammonium thereof. Examples thereof include salts, dibasic acids such as maleic acid, fumaric acid and itaconic acid, and sodium salts, potassium salts and ammonium salts thereof. These anionic vinyl monomers can be used individually by 1 type, or can also be used in combination of 2 or more type.
本発明方法に用いる両性有機高分子凝集剤のノニオン性構成単位となるノニオン性ビニル単量体としては、例えば、アクリルアミド、メタクリルアミド、Ｎ,Ｎ−ジメチルアクリルアミド、Ｎ,Ｎ−ジメチルメタクリルアミドなどのアミド類、アクリロニトリル、メタクリロニトリルなどのシアン化ビニル系化合物、アクリル酸メチル、アクリル酸エチル、メタクリル酸メチル、メタクリル酸エチルなどの(メタ)アクリル酸のアルキルエステル、酢酸ビニルなどのビニルエステル、スチレン、α−メチルスチレン、ｐ−メチルスチレンなどの芳香族ビニル系化合物などを挙げることができる。これらのノニオン性ビニル単量体は、１種を単独で用いることができ、あるいは、２種以上を組み合わせて用いることもできる。 Nonionic vinyl monomers that are nonionic constituent units of the amphoteric organic polymer flocculant used in the method of the present invention include, for example, acrylamide, methacrylamide, N, N-dimethylacrylamide, N, N-dimethylmethacrylamide and the like. Amides, vinyl cyanide compounds such as acrylonitrile and methacrylonitrile, alkyl acrylates such as methyl acrylate, ethyl acrylate, methyl methacrylate and ethyl methacrylate, vinyl esters such as vinyl acetate, styrene And aromatic vinyl compounds such as α-methylstyrene and p-methylstyrene. These nonionic vinyl monomers can be used individually by 1 type, or can also be used in combination of 2 or more type.
本発明方法に用いる両性高分子凝集剤の製造方法に特に制限はなく、溶液重合、懸濁重合、エマルション重合などを挙げることができる。水溶液重合においては、単量体を水に溶解し、雰囲気を不活性ガスで置換し、重合温度まで昇温したのち、重合開始剤として、過硫酸アンモニウム、過硫酸カリウム、２,２'−アゾビス(２−アミジノプロパン)二塩酸塩などの水溶性重合開始剤を加えて重合することができる。 There is no restriction | limiting in particular in the manufacturing method of the amphoteric polymer flocculent used for this invention method, Solution polymerization, suspension polymerization, emulsion polymerization, etc. can be mentioned. In aqueous solution polymerization, the monomer is dissolved in water, the atmosphere is replaced with an inert gas, the temperature is raised to the polymerization temperature, and ammonium persulfate, potassium persulfate, 2,2′-azobis ( The polymerization can be carried out by adding a water-soluble polymerization initiator such as 2-amidinopropane) dihydrochloride.
本発明方法において、カチオン性高分子凝集剤と両性高分子凝集剤の重量比は、２０：８０〜８０：２０であることが好ましく、３０：７０〜７０：３０であることがより好ましい。カチオン性高分子凝集剤と両性高分子凝集剤の重量比が２０：８０未満でカチオン性高分子凝集剤が少ないと、最適添加率が上昇して多量の高分子凝集剤が必要となり、重力ろ過性が不良でろ過速度が遅く、ケーキの含水率とろ液の濁度が高くなるおそれがある。カチオン性高分子凝集剤と両性高分子凝集剤の重量比が８０：２０を超えてカチオン性高分子凝集剤が多いと、最適添加率が上昇して多量の高分子凝集剤が必要となり、重力ろ過性が不良でろ過速度が遅く、ケーキの含水率とろ液の濁度が高くなるおそれがある。 In the method of the present invention, the weight ratio of the cationic polymer flocculant to the amphoteric polymer flocculant is preferably 20:80 to 80:20, and more preferably 30:70 to 70:30. If the weight ratio of the cationic polymer flocculant to the amphoteric polymer flocculant is less than 20:80 and the amount of the cationic polymer flocculant is small, the optimum addition rate increases and a large amount of the polymer flocculant is required. And the filtration rate is slow, and the moisture content of the cake and the turbidity of the filtrate may increase. If the weight ratio of the cationic polymer flocculant to the amphoteric polymer flocculant exceeds 80:20 and the amount of the cationic polymer flocculant is large, the optimum addition rate is increased, and a large amount of the polymer flocculant is required. The filterability is poor and the filtration rate is slow, which may increase the moisture content of the cake and the turbidity of the filtrate.
本発明方法においては、カチオン性高分子凝集剤と両性高分子凝集剤に加えて、酸性物質を添加することができる。酸性物質は、両性高分子凝集剤のカルボキシル基の解離を抑え、カチオン性高分子凝集剤と両性高分子凝集剤の反応物の生成を防止する効果を有する。本発明方法において使用する酸性物質に特に制限はなく、例えば、スルファミン酸、硫酸水素ナトリウム、塩化水素、硫酸などを挙げることができる。 In the method of the present invention, an acidic substance can be added in addition to the cationic polymer flocculant and the amphoteric polymer flocculant. The acidic substance has an effect of suppressing the dissociation of the carboxyl group of the amphoteric polymer flocculant and preventing the formation of a reaction product of the cationic polymer flocculant and the amphoteric polymer flocculant. There is no restriction | limiting in particular in the acidic substance used in this invention method, For example, sulfamic acid, sodium hydrogensulfate, hydrogen chloride, a sulfuric acid etc. can be mentioned.
本発明方法において、有機性汚泥にカチオン性高分子凝集剤と両性高分子凝集剤を添加する順序に特に制限はないが、カチオン性高分子凝集剤を先に添加するか、あるいは、カチオン性高分子凝集剤と両性高分子凝集剤とを同時に添加することが好ましい。添加する前の状態としては、カチオン性高分子凝集剤と両性高分子凝集剤を溶解槽で別々に溶解することができ、あるいは、カチオン性高分子凝集剤と両性高分子凝集剤を同じ溶解槽で溶解することもできる。カチオン性高分子凝集剤と両性高分子凝集剤を同じ溶解槽で溶解する場合、高分子凝集剤の合計濃度は、０.１〜１重量％であることが好ましい。 In the method of the present invention, the order in which the cationic polymer flocculant and the amphoteric polymer flocculant are added to the organic sludge is not particularly limited, but the cationic polymer flocculant is added first, or the cationic polymer flocculant is added. It is preferable to add the molecular flocculant and the amphoteric polymer flocculant simultaneously. As a state before addition, the cationic polymer flocculant and the amphoteric polymer flocculant can be dissolved separately in the dissolution tank, or the cationic polymer flocculant and the amphoteric polymer flocculant can be dissolved in the same dissolution tank. Can also be dissolved. When the cationic polymer flocculant and the amphoteric polymer flocculant are dissolved in the same dissolution tank, the total concentration of the polymer flocculant is preferably 0.1 to 1% by weight.
本発明方法によれば、カチオン性高分子凝集剤は、凝集時に汚泥中の微細粒子を架橋性カチオン性高分子凝集剤の網目構造の中に取り込み、微細粒子から粗粒子まで幅広く吸着することによりフロック化する。一方、両性高分子凝集剤は、粗粒子から、架橋性カチオン性高分子凝集剤で生成されたフロックどうしまでをさらに吸着して、粗大フロックを形成する。このようにしてできたフロックは剛直であるが、せん断力が加わったときには、未使用の官能基、すなわち、架橋性カチオン性高分子凝集剤のカチオン基と両性高分子凝集剤のアニオン基が、徐々に未中和の汚泥と反応するために、壊れかかったフロックが再凝集するとともに、フロックの緻密化が行われる。このようにして高い脱水性が得られるものと考えられる。 According to the method of the present invention, the cationic polymer flocculant absorbs fine particles in the sludge into the network structure of the crosslinkable cationic polymer flocculant during aggregation and adsorbs a wide range of particles from fine particles to coarse particles. Flock. On the other hand, the amphoteric polymer flocculant further adsorbs from the coarse particles to the flocs generated by the crosslinkable cationic polymer flocculant to form coarse flocs. The flocs thus produced are rigid, but when a shear force is applied, the unused functional groups, that is, the cationic groups of the crosslinkable cationic polymer flocculant and the anionic groups of the amphoteric polymer flocculant, Since it gradually reacts with unneutralized sludge, the broken flocs reagglomerate and the flocs are densified. Thus, it is considered that high dehydrating properties can be obtained.
また、汚泥によっては、有機物量が非常に多く、高分子凝集剤だけでは十分な脱水効果が得られない場合がある。このような場合には、ポリ塩化アルミニウム、ポリ硫酸第二鉄などの無機凝集剤を併用すると、より高い脱水効果を得ることができる。この際に、無機凝集剤が汚泥と反応した状態として、汚泥粒子のマイナス荷電が高く、荷電中和が十分に行われないために、あるいは、汚泥のアルカリ度が高く荷電中和が行われる前に、アルミニウム又は鉄が金属水酸化物となってしまうために、生成した粒子の粒度分布が広くなっていると考えられる。このような場合においても、架橋性カチオン性高分子凝集剤が、微細粒子から粗粒子までを幅広く吸着してフロック化し、両性高分子凝集剤によりさらにフロックが粗大化されると考えられる。 In addition, depending on the sludge, the amount of organic matter is very large, and a sufficient dehydrating effect may not be obtained with only the polymer flocculant. In such a case, when an inorganic flocculant such as polyaluminum chloride or polyferric sulfate is used in combination, a higher dehydrating effect can be obtained. At this time, since the inorganic flocculant has reacted with the sludge, the sludge particles have a high negative charge and the charge neutralization is not sufficiently performed, or before the neutralization of the sludge with a high alkalinity is performed. Moreover, since aluminum or iron becomes a metal hydroxide, it is considered that the particle size distribution of the generated particles is wide. Even in such a case, it is considered that the crosslinkable cationic polymer flocculant adsorbs a wide range of fine particles to coarse particles to form a floc, and the amphoteric polymer flocculant further coarsens the floc.
本発明方法を好適に適用することができる有機性汚泥としては、下水処理場の混合汚泥、し尿処理場の三次汚泥を含んだ余剰汚泥、凝集汚泥を含んだ混合汚泥、消化汚泥、オキシデーションディッチ法による余剰汚泥、無機凝集剤が添加された余剰汚泥などを挙げることができる。下水処理場の混合汚泥は、下水処理場において発生する初沈汚泥と余剰汚泥が混合された汚泥である。し尿処理場の三次汚泥を含んだ余剰汚泥は、し尿処理場における活性汚泥処理によって発生した余剰汚泥に、硫酸バンドやＰＡＣ等の無機凝集剤を当該活性汚泥処理水に添加して、凝集沈殿処理又は凝集加圧浮上処理して分離された汚泥（三次汚泥）が添加された汚泥である。凝集汚泥を含んだ混合汚泥は、凝集槽内に滞留した凝集汚泥と余剰汚泥が混合された汚泥である。消化汚泥は、濃縮汚泥を密閉し、メタン菌の作用によりメタンガスや二酸化炭素を発生させて分解した汚泥である。オキシデーションディッチ法による余剰汚泥は、家庭汚水を主とする下水を機械曝気装置を設置した無終端水路を反応槽として低負荷で行う活性汚泥処理により発生する汚泥である。無機凝集剤が添加された余剰汚泥は、ポリ塩化アルミニウム、ポリ硫酸第二鉄などの無機凝集剤が添加されて生成した粒子の粒度分布が広くなった汚泥であり、この場合の余剰汚泥としては、下水処理場やし尿処理場で発生する余剰汚泥のみならず、食品、化学工場などで排出される有機性廃水を生物処理した際に発生する余剰汚泥も含まれる。 Examples of the organic sludge to which the method of the present invention can be suitably applied include mixed sludge from sewage treatment plants, excess sludge containing tertiary sludge from human waste treatment plants, mixed sludge containing coagulated sludge, digested sludge, and oxidation ditch. Excess sludge by law, surplus sludge to which an inorganic flocculant is added, and the like. The mixed sludge in the sewage treatment plant is a sludge in which primary sludge generated in the sewage treatment plant and excess sludge are mixed. Surplus sludge containing tertiary sludge from the human waste treatment plant is added to the activated sludge treatment water in the sludge treatment plant by adding an inorganic flocculant such as sulfuric acid band or PAC to the activated sludge treatment water. Or it is the sludge to which the sludge (tertiary sludge) isolate | separated by the coagulation pressurization flotation process was added. The mixed sludge containing agglomerated sludge is a sludge in which agglomerated sludge staying in the agglomeration tank and excess sludge are mixed. Digested sludge is sludge that has been decomposed by sealing the concentrated sludge and generating methane gas and carbon dioxide by the action of methane bacteria. Excess sludge by the oxidation ditch method is sludge generated by activated sludge treatment with a low load using an endless water channel equipped with a mechanical aeration device as sewage mainly for domestic sewage. The excess sludge to which the inorganic flocculant is added is sludge in which the particle size distribution of the particles produced by adding inorganic flocculant such as polyaluminum chloride and polyferric sulfate is widened. This includes not only excess sludge generated at sewage treatment plants and human waste treatment plants, but also excess sludge generated when biologically treating organic wastewater discharged from food, chemical factories, and the like.
以下に、実施例を挙げて本発明をさらに詳細に説明するが、本発明はこれらの実施例によりなんら限定されるものではない。
なお、用いた高分子凝集剤のモノマー単位の略号を下記に示す。
ＤＡＡ：ジメチルアミノエチルアクリレートのメチルクロリド四級化物
ＤＡＭ：ジメチルアミノエチルメタクリレートのメチルクロリド四級化物
ＡＡｍ：アクリルアミド
ＡＡ：アクリル酸
また、カチオン性高分子凝集剤の溶液粘度は、０.２重量％水溶液について、ブルックフィールドＢ形回転粘度計を用い、回転速度３０ｒｐｍ、ＳＢ２号スピンドル、３０℃で測定した。固有粘度は、キャノンフェンスケ粘度計を用い、１モル／Ｌ硝酸ナトリウム水溶液を溶媒として、３０℃で測定した。
Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
In addition, the symbol of the monomer unit of the used polymer flocculant is shown below.
DAA: Methyl chloride quaternized product of dimethylaminoethyl acrylate DAM: Methyl chloride quaternized product of dimethylaminoethyl methacrylate AAm: Acrylamide AA: Acrylic acid The solution viscosity of the cationic polymer flocculant is 0.2% by weight aqueous solution. Was measured using a Brookfield B-type rotational viscometer at a rotation speed of 30 rpm, a SB2 spindle, and 30 ° C. Intrinsic viscosity was measured at 30 ° C. using a Cannon-Fenske viscometer using a 1 mol / L sodium nitrate aqueous solution as a solvent.
実施例１
造粒濃縮とベルトプレス脱水を想定して、下水混合生汚泥について机上試験を行った。
汚泥の性状は、懸濁物質（ＴＳ）１.８重量％、有機物量（ＶＴＳ／ＴＳ）７８重量％、繊維分２７重量％であり、粒度分布は、１０μｍ以下が１０体積％、１０〜１００μｍが２０体積％、１００〜１５０μｍが４０体積％、１５０μｍ以上が３０体積％であった。
カチオン性高分子凝集剤として、ＤＡＡ(８０モル％)／ＡＡｍ(２０モル％)共重合体を用いた。この共重合体の０.２重量％水溶液の粘度は６００ｍＰａ・ｓ、固有粘度は５ｄＬ／ｇであり、溶液粘度／固有粘度の比は１２０であった。両性高分子凝集剤として、ＤＡＡ(２８モル％)／ＤＡＭ(２モル％)／ＡＡｍ(３５モル％)／ＡＡ(３５モル％)共重合体を用いた。高分子凝集剤水溶液として、カチオン性高分子凝集剤０.１重量％と両性高分子凝集剤０.１重量％とを含有する水溶液を調製した。
汚泥２００ｍＬを容量３００ｍＬのビーカーにとり、ポリ塩化アルミニウム０.３６ｇを添加して、撹拌速度７５０ｒｐｍで２０秒間撹拌し、次いで、高分子凝集剤水溶液２５.２ｇを添加して、撹拌速度１８０ｒｐｍで６０秒間撹拌した。６０メッシュのナイロンろ布を敷いたブフナーロートに内径５ｃｍの塩化ビニル樹脂製円筒を置き、その中に凝集した汚泥を一気に注ぎ込んだ。１０秒後の重力ろ液量は、１４４ｍＬであった。さらに、ナイロンろ布上の汚泥を９８ｋＰａの圧力で６０秒間圧搾して脱水した。得られた脱水ケーキの含水率は７１.６重量％であり、ろ布上のケーキ収量は乾燥重量で１２４ｍｇ／ｃｍ2であった。
Example 1
On the assumption of granulation concentration and belt press dewatering, a desktop test was conducted on sewage mixed raw sludge.
The properties of the sludge are 1.8% by weight of suspended solids (TS), 78% by weight of organic matter (VTS / TS), 27% by weight of fiber, and the particle size distribution is 10% by volume or less, and 10 to 100 μm. Was 20% by volume, 100 to 150 μm was 40% by volume, and 150 μm or more was 30% by volume.
As a cationic polymer flocculant, a DAA (80 mol%) / AAm (20 mol%) copolymer was used. The viscosity of a 0.2% by weight aqueous solution of this copolymer was 600 mPa · s, the intrinsic viscosity was 5 dL / g, and the solution viscosity / intrinsic viscosity ratio was 120. A DAA (28 mol%) / DAM (2 mol%) / AAm (35 mol%) / AA (35 mol%) copolymer was used as the amphoteric polymer flocculant. An aqueous solution containing 0.1% by weight of a cationic polymer flocculant and 0.1% by weight of an amphoteric polymer flocculant was prepared as an aqueous polymer flocculant solution.
Take 200 mL of sludge in a beaker with a capacity of 300 mL, add 0.36 g of polyaluminum chloride, stir for 20 seconds at a stirring speed of 750 rpm, then add 25.2 g of aqueous polymer flocculant solution, and then for 60 seconds at a stirring speed of 180 rpm. Stir. A cylinder made of vinyl chloride resin having an inner diameter of 5 cm was placed on a Buchner funnel laid with a 60 mesh nylon filter cloth, and sludge aggregated was poured into the cylinder at once. The amount of gravity filtrate after 10 seconds was 144 mL. Furthermore, the sludge on the nylon filter cloth was squeezed for 60 seconds at a pressure of 98 kPa for dehydration. The moisture content of the obtained dehydrated cake was 71.6% by weight, and the cake yield on the filter cloth was 124 mg / cm 2 by dry weight.
実施例２〜１０
第１表に示す高分子凝集剤を調製し、実施例１と同様にして、下水混合生汚泥について机上試験を行った。
比較例１〜９
第２表に示す高分子凝集剤を調製し、実施例１と同様にして、下水混合生汚泥について机上試験を行った。
実施例１〜１０で用いた高分子凝集剤の構成を第１表に、比較例１〜９で用いた高分子凝集剤の構成を第２表に、実施例１〜１０及び比較例１〜９の評価結果を第３表に示す。
Examples 2-10
A polymer flocculant shown in Table 1 was prepared, and a desktop test was conducted on the sewage mixed raw sludge in the same manner as in Example 1.
Comparative Examples 1-9
A polymer flocculant shown in Table 2 was prepared, and a desktop test was conducted on sewage mixed raw sludge in the same manner as in Example 1.
The constitution of the polymer flocculant used in Examples 1 to 10 is shown in Table 1, the constitution of the polymer flocculant used in Comparative Examples 1 to 9 is shown in Table 2, Examples 1 to 10 and Comparative Examples 1 to 1 The evaluation results of 9 are shown in Table 3.
第１〜３表に見られるように、溶液粘度／固有粘度の比が７５〜１６０であるカチオン性高分子凝集剤と、ＤＡＡ(２８モル％)／ＤＡＭ(２モル％)／ＡＡｍ(３５モル％)／ＡＡ(３５モル％)共重合体からなる両性高分子凝集剤を、重量比１：１、１：２又は２：１で混合した高分子凝集剤を用いた実施例１〜１０では、１０秒間の重力ろ液量が１３８〜１６４ｍＬであってろ過性が良好であり、脱水ケーキの含水率が７１.２〜７４.０重量％と低く、ろ布１ｃｍ2当たり１１３〜１３３ｍｇのケーキが得られている。
これに対して、カチオン性高分子凝集剤のみを用いた比較例１〜４、両性高分子凝集剤のみを用いた比較例５、カチオン性高分子凝集剤と両性高分子凝集剤を、重量比１：１で混合した高分子凝集剤を用いているが、カチオン性高分子凝集剤の溶液粘度／固有粘度の比が３６〜５０である比較例６〜９では、１０秒間の重力ろ液量が９８〜１３６ｍＬであってろ過性が不良であり、脱水ケーキの含水率が７３.５〜７６.９重量％と高く、ろ布１ｃｍ2当たり６８〜９７ｍｇのケーキしか得られていない。
As can be seen from Tables 1 to 3, the cationic polymer flocculant having a solution viscosity / intrinsic viscosity ratio of 75 to 160, DAA (28 mol%) / DAM (2 mol%) / AAm (35 mol) %) / AA (35 mol%) copolymer in Examples 1 to 10 using a polymer flocculant mixed with an amphoteric polymer flocculant in a weight ratio of 1: 1, 1: 2 or 2: 1. Gravity filtrate amount for 10 seconds is 138 to 164 mL, filterability is good, moisture content of dehydrated cake is as low as 71.2 to 74.0% by weight, 113 to 133 mg cake per cm 2 of filter cloth Is obtained.
In contrast, Comparative Examples 1 to 4 using only the cationic polymer flocculant, Comparative Example 5 using only the amphoteric polymer flocculant, the cationic polymer flocculant and the amphoteric polymer flocculant, Although the polymer flocculant mixed by 1: 1 is used, in Comparative Examples 6-9 in which the ratio of the solution viscosity / intrinsic viscosity of the cationic polymer flocculant is 36-50, the gravity filtrate amount for 10 seconds Is 98 to 136 mL, the filterability is poor, the water content of the dehydrated cake is as high as 73.5 to 76.9% by weight, and only 68 to 97 mg of cake is obtained per cm 2 of filter cloth.
実施例１１
遠心脱水を想定して、オキシデーションディッチ方式余剰汚泥について机上試験を行った。
汚泥の性状は、懸濁物質（ＴＳ）１.２重量％、有機物量（ＶＴＳ／ＴＳ）７２重量％、繊維分３.４重量％であり、粒度分布は、１０μｍ以下が３０体積％、１０〜１００μｍが３５体積％、１００〜１５０μｍが３０体積％、１５０μｍ以上が５体積％であった。
カチオン性高分子凝集剤として、ＤＡＡ(８０モル％)／ＡＡｍ(２０モル％)共重合体を用いた。この共重合体の０.２重量％水溶液の粘度は６００ｍＰａ・ｓ、固有粘度は５ｄＬ／ｇであり、溶液粘度／固有粘度の比は１２０であった。両性高分子凝集剤として、ＤＡＡ(１５モル％)／ＤＡＭ(１０モル％)／ＡＡｍ(６０モル％)／ＡＡ(１５モル％)共重合体を用いた。高分子凝集剤水溶液として、カチオン性高分子凝集剤０.１重量％と両性高分子凝集剤０.１重量％とを含有する水溶液を調製した。
汚泥２００ｍＬを容量３００ｍＬのビーカーにとり、高分子凝集剤水溶液１６.８ｇを添加して、撹拌速度１,０００ｒｐｍで３０秒間撹拌した。次いで、６０メッシュのナイロンろ布を敷いたブフナーロートに内径５ｃｍの塩化ビニル樹脂製円筒を置き、その中に凝集した汚泥を一気に注ぎ込んだ。１０秒後の重力ろ液量は、１２６ｍＬであった。さらに、ナイロンろ布上の汚泥を４９ｋＰａの圧力で６０秒間圧搾して脱水した。得られた脱水ケーキの含水率は８１.５重量％であり、ろ布上のケーキ収量は乾燥重量で４５ｍｇ／ｃｍ2であった。
Example 11
On the assumption of centrifugal dehydration, a desktop test was conducted on the oxidation ditch system excess sludge.
The sludge has a suspended solid (TS) content of 1.2% by weight, an organic matter content (VTS / TS) of 72% by weight, and a fiber content of 3.4% by weight. -100 μm was 35% by volume, 100-150 μm was 30% by volume, and 150 μm or more was 5% by volume.
As a cationic polymer flocculant, a DAA (80 mol%) / AAm (20 mol%) copolymer was used. The viscosity of a 0.2% by weight aqueous solution of this copolymer was 600 mPa · s, the intrinsic viscosity was 5 dL / g, and the solution viscosity / intrinsic viscosity ratio was 120. As the amphoteric polymer flocculant, a DAA (15 mol%) / DAM (10 mol%) / AAm (60 mol%) / AA (15 mol%) copolymer was used. An aqueous solution containing 0.1% by weight of a cationic polymer flocculant and 0.1% by weight of an amphoteric polymer flocculant was prepared as an aqueous polymer flocculant solution.
200 mL of sludge was placed in a 300 mL capacity beaker, 16.8 g of a polymer flocculant aqueous solution was added, and the mixture was stirred for 30 seconds at a stirring speed of 1,000 rpm. Next, a vinyl chloride resin cylinder having an inner diameter of 5 cm was placed on a Buchner funnel laid with a 60 mesh nylon filter cloth, and the agglomerated sludge was poured into it at once. The amount of gravity filtrate after 10 seconds was 126 mL. Further, the sludge on the nylon filter cloth was dehydrated by pressing it at a pressure of 49 kPa for 60 seconds. The moisture content of the obtained dehydrated cake was 81.5% by weight, and the cake yield on the filter cloth was 45 mg / cm 2 by dry weight.
実施例１２〜１４
第４表に示す高分子凝集剤を調製し、実施例１１と同様にして、オキシデーションディッチ方式余剰汚泥について机上試験を行った。
比較例１０〜１３
第４表に示す高分子凝集剤を調製し、実施例１１と同様にして、オキシデーションディッチ方式余剰汚泥について机上試験を行った。
実施例１１〜１４及び比較例１０〜１３で用いた高分子凝集剤の構成を第４表に、実施例１１〜１４及び比較例１０〜１３の評価結果を第５表に示す。
Examples 12-14
A polymer flocculant shown in Table 4 was prepared, and a desktop test was conducted on the oxidation ditch system excess sludge in the same manner as in Example 11.
Comparative Examples 10-13
A polymer flocculant shown in Table 4 was prepared, and a desktop test was conducted on the oxidation ditch system excess sludge in the same manner as in Example 11.
The constitution of the polymer flocculant used in Examples 11-14 and Comparative Examples 10-13 is shown in Table 4, and the evaluation results of Examples 11-14 and Comparative Examples 10-13 are shown in Table 5.
第４〜５表に見られるように、溶液粘度／固有粘度の比が１２０〜１６０であるカチオン性高分子凝集剤と、ＤＡＡ(１５〜２５モル％)／ＤＡＭ(０〜１０モル％)／ＡＡｍ(６０モル％)／ＡＡ(１５モル％)共重合体からなる両性高分子凝集剤を、重量比１：１で混合した高分子凝集剤を用いた実施例１１〜１４では、１０秒間の重力ろ液量が１２４〜１５６ｍＬであってろ過性が良好であり、脱水ケーキの含水率が８１.５〜８３.１重量％と低く、ろ布１ｃｍ2当たり４０〜４５ｍｇのケーキが得られている。
これに対して、カチオン性高分子凝集剤のみを用いた比較例１０、両性高分子凝集剤のみを用いた比較例１１、カチオン性高分子凝集剤と両性高分子凝集剤を、重量比１：１で混合した高分子凝集剤を用いているが、カチオン性高分子凝集剤の溶液粘度／固有粘度の比が３６〜４３である比較例１２〜１３では、１０秒間の重力ろ液量が６７〜１３２ｍＬであってろ過性が不良であり、脱水ケーキの含水率が８２.８〜８４.１重量％と高く、ろ布１ｃｍ2当たり３３〜３８ｍｇのケーキしか得られていない。
As seen in Tables 4-5, a cationic polymer flocculant having a ratio of solution viscosity / intrinsic viscosity of 120-160, DAA (15-25 mol%) / DAM (0-10 mol%) / In Examples 11 to 14 using a polymer flocculant mixed with an amphoteric polymer flocculant composed of an AAm (60 mol%) / AA (15 mol%) copolymer at a weight ratio of 1: 1, Gravity filtrate amount is 124-156mL, filterability is good, moisture content of dehydrated cake is as low as 81.5-83.1% by weight, and cake of 40-45 mg per 1 cm 2 of filter cloth is obtained. Yes.
In contrast, Comparative Example 10 using only the cationic polymer flocculant, Comparative Example 11 using only the amphoteric polymer flocculant, the cationic polymer flocculant and the amphoteric polymer flocculant in a weight ratio of 1: In Comparative Examples 12 to 13 in which the ratio of the solution viscosity / intrinsic viscosity of the cationic polymer flocculant is 36 to 43, the gravity filtrate amount for 10 seconds is 67. It is ˜132 mL, the filterability is poor, the moisture content of the dehydrated cake is as high as 82.8 to 84.1% by weight, and only 33 to 38 mg of cake is obtained per 1 cm 2 of filter cloth.
本発明の有機性汚泥の処理方法によれば、難脱水性の汚泥を処理して、ろ過性が良好であり、含水率の低い脱水ケーキを得ることができる。本発明方法によれば、従来の方法と比べて、脱水ケーキの含水率が約２重量％低下し、ケーキ収量が３０〜５０重量％向上する。この結果から、汚泥は約１０体積％減容化され、脱水時の処理量は３０〜５０重量％向上することが推定される。そして、最終的には汚泥の処理処分費の低減に寄与することができる。 According to the organic sludge treatment method of the present invention, it is possible to obtain a dehydrated cake having a good filterability and a low water content by treating a hardly dewaterable sludge. According to the method of the present invention, the moisture content of the dehydrated cake is reduced by about 2% by weight and the cake yield is improved by 30 to 50% by weight, compared with the conventional method. From this result, it is estimated that the sludge is reduced in volume by about 10% by volume, and the treatment amount during dehydration is improved by 30 to 50% by weight. And finally, it can contribute to reduction of the treatment disposal cost of sludge.
Claims (2)
The organic sludge according to claim 1, wherein the organic sludge is mixed sludge from a sewage treatment plant, surplus sludge containing tertiary sludge from a human waste treatment plant, mixed sludge containing coagulated sludge, digested sludge, or surplus sludge by oxidation ditch method. Method for dewatering activated sludge.
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