CN114804316B - All-organic composite flocculant and application thereof - Google Patents
All-organic composite flocculant and application thereof Download PDFInfo
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- CN114804316B CN114804316B CN202210505794.1A CN202210505794A CN114804316B CN 114804316 B CN114804316 B CN 114804316B CN 202210505794 A CN202210505794 A CN 202210505794A CN 114804316 B CN114804316 B CN 114804316B
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- molecular weight
- flocculant
- organic
- low molecular
- weight polymer
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- 239000002131 composite material Substances 0.000 title claims abstract description 39
- 229920000642 polymer Polymers 0.000 claims abstract description 108
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 36
- 229940126062 Compound A Drugs 0.000 claims abstract description 35
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229920006158 high molecular weight polymer Polymers 0.000 claims abstract description 18
- 229920001577 copolymer Polymers 0.000 claims description 34
- -1 anion organic compounds Chemical class 0.000 claims description 32
- 239000004094 surface-active agent Substances 0.000 claims description 29
- 125000002091 cationic group Chemical group 0.000 claims description 22
- 229920002401 polyacrylamide Polymers 0.000 claims description 22
- 239000000178 monomer Substances 0.000 claims description 16
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 14
- 125000000129 anionic group Chemical group 0.000 claims description 13
- 239000008394 flocculating agent Substances 0.000 claims description 13
- 125000003342 alkenyl group Chemical group 0.000 claims description 11
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 11
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 11
- 150000003863 ammonium salts Chemical group 0.000 claims description 8
- ZQXSMRAEXCEDJD-UHFFFAOYSA-N n-ethenylformamide Chemical compound C=CNC=O ZQXSMRAEXCEDJD-UHFFFAOYSA-N 0.000 claims description 8
- 229920000620 organic polymer Polymers 0.000 claims description 8
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 8
- 229910052708 sodium Inorganic materials 0.000 claims description 7
- 239000011734 sodium Substances 0.000 claims description 7
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 6
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims description 6
- 150000001768 cations Chemical class 0.000 claims description 6
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 claims description 6
- UYMKPFRHYYNDTL-UHFFFAOYSA-N ethenamine Chemical compound NC=C UYMKPFRHYYNDTL-UHFFFAOYSA-N 0.000 claims description 6
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 6
- 125000001424 substituent group Chemical group 0.000 claims description 6
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 claims description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 4
- 229940047670 sodium acrylate Drugs 0.000 claims description 4
- RRHXZLALVWBDKH-UHFFFAOYSA-M trimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)OCC[N+](C)(C)C RRHXZLALVWBDKH-UHFFFAOYSA-M 0.000 claims description 4
- XBIPWOJKRZBTQK-UHFFFAOYSA-N 2-methylidenebut-3-enamide Chemical compound NC(=O)C(=C)C=C XBIPWOJKRZBTQK-UHFFFAOYSA-N 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims 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 claims description 3
- UEEJHVSXFDXPFK-UHFFFAOYSA-O N-dimethylethanolamine Chemical compound C[NH+](C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-O 0.000 claims description 3
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 claims description 3
- 239000004793 Polystyrene Substances 0.000 claims description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
- LHIJANUOQQMGNT-UHFFFAOYSA-N aminoethylethanolamine Chemical compound NCCNCCO LHIJANUOQQMGNT-UHFFFAOYSA-N 0.000 claims description 3
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 3
- VNKYTQGIUYNRMY-UHFFFAOYSA-N methoxypropane Chemical compound CCCOC VNKYTQGIUYNRMY-UHFFFAOYSA-N 0.000 claims description 3
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 3
- 229920001467 poly(styrenesulfonates) Polymers 0.000 claims description 3
- 229920002223 polystyrene Polymers 0.000 claims description 3
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical group [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 3
- 229940006186 sodium polystyrene sulfonate Drugs 0.000 claims description 3
- OZXPDBUJCIJMRF-UHFFFAOYSA-K trisodium styrene phosphate Chemical compound P(=O)([O-])([O-])[O-].[Na+].C=CC1=CC=CC=C1.[Na+].[Na+] OZXPDBUJCIJMRF-UHFFFAOYSA-K 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- WWAZUUULUNZNFE-UHFFFAOYSA-N [Na].NC(=O)C=C Chemical compound [Na].NC(=O)C=C WWAZUUULUNZNFE-UHFFFAOYSA-N 0.000 claims description 2
- 150000008052 alkyl sulfonates Chemical class 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 125000006702 (C1-C18) alkyl group Chemical group 0.000 claims 4
- 229940117913 acrylamide Drugs 0.000 claims 1
- 229940083542 sodium Drugs 0.000 claims 1
- 229920003169 water-soluble polymer Polymers 0.000 claims 1
- 239000010802 sludge Substances 0.000 abstract description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 34
- 239000000126 substance Substances 0.000 abstract description 26
- 239000010865 sewage Substances 0.000 abstract description 23
- 238000004064 recycling Methods 0.000 abstract description 7
- 238000001035 drying Methods 0.000 abstract description 4
- 230000000694 effects Effects 0.000 description 40
- 238000005189 flocculation Methods 0.000 description 18
- 230000016615 flocculation Effects 0.000 description 17
- 239000003921 oil Substances 0.000 description 16
- 150000001450 anions Chemical group 0.000 description 15
- 238000002474 experimental method Methods 0.000 description 14
- 239000007864 aqueous solution Substances 0.000 description 13
- 125000004122 cyclic group Chemical group 0.000 description 12
- 239000002245 particle Substances 0.000 description 11
- 239000003344 environmental pollutant Substances 0.000 description 10
- 229920001519 homopolymer Polymers 0.000 description 10
- 231100000719 pollutant Toxicity 0.000 description 10
- 238000000034 method Methods 0.000 description 9
- 150000002500 ions Chemical class 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 230000002195 synergetic effect Effects 0.000 description 8
- 125000000217 alkyl group Chemical group 0.000 description 7
- 239000003814 drug Substances 0.000 description 7
- 238000013178 mathematical model Methods 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 239000003153 chemical reaction reagent Substances 0.000 description 6
- GQOKIYDTHHZSCJ-UHFFFAOYSA-M dimethyl-bis(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C=CC[N+](C)(C)CC=C GQOKIYDTHHZSCJ-UHFFFAOYSA-M 0.000 description 6
- 238000012216 screening Methods 0.000 description 6
- 238000004062 sedimentation Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- 229920002873 Polyethylenimine Polymers 0.000 description 4
- 239000012752 auxiliary agent Substances 0.000 description 4
- 239000000356 contaminant Substances 0.000 description 4
- 230000018044 dehydration Effects 0.000 description 4
- 238000006297 dehydration reaction Methods 0.000 description 4
- 239000005416 organic matter Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- JADMAVSCPFDMLP-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate;prop-2-enamide Chemical compound NC(=O)C=C.CN(C)CCOC(=O)C(C)=C JADMAVSCPFDMLP-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000013459 approach Methods 0.000 description 3
- KHSLHYAUZSPBIU-UHFFFAOYSA-M benzododecinium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 KHSLHYAUZSPBIU-UHFFFAOYSA-M 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 229920000768 polyamine Polymers 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- MPNXSZJPSVBLHP-UHFFFAOYSA-N 2-chloro-n-phenylpyridine-3-carboxamide Chemical compound ClC1=NC=CC=C1C(=O)NC1=CC=CC=C1 MPNXSZJPSVBLHP-UHFFFAOYSA-N 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 229940048053 acrylate Drugs 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229920006317 cationic polymer Polymers 0.000 description 2
- 239000003093 cationic surfactant Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 230000001687 destabilization Effects 0.000 description 2
- WOYQCKODTASHPN-UHFFFAOYSA-M dimethyl(dipropyl)azanium;chloride Chemical compound [Cl-].CCC[N+](C)(C)CCC WOYQCKODTASHPN-UHFFFAOYSA-M 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000010408 sweeping Methods 0.000 description 2
- 229920001897 terpolymer Polymers 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229920001661 Chitosan Polymers 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920006322 acrylamide copolymer Polymers 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000012648 alternating copolymerization Methods 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229920003180 amino resin Polymers 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 238000012661 block copolymerization Methods 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 230000005591 charge neutralization Effects 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005188 flotation Methods 0.000 description 1
- 239000002920 hazardous waste Substances 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000006855 networking Effects 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N phosphonic acid group Chemical group P(O)(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 239000010773 plant oil Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920002717 polyvinylpyridine Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 230000005588 protonation Effects 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical group C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 239000008247 solid mixture Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical group S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- FZGFBJMPSHGTRQ-UHFFFAOYSA-M trimethyl(2-prop-2-enoyloxyethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CCOC(=O)C=C FZGFBJMPSHGTRQ-UHFFFAOYSA-M 0.000 description 1
- PUVAFTRIIUSGLK-UHFFFAOYSA-M trimethyl(oxiran-2-ylmethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1CO1 PUVAFTRIIUSGLK-UHFFFAOYSA-M 0.000 description 1
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical class CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 239000002888 zwitterionic surfactant Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/542—Phosphorus compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/547—Tensides
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
Abstract
The invention relates to a full-organic composite flocculant and application thereof, wherein the effective substances of the flocculant comprise composite flocculant and organic compound A, and the composite flocculant is a combination of three or more of low molecular weight polymer organic flocculant B, low molecular weight polymer organic flocculant C, medium molecular weight polymer organic flocculant D, high molecular weight polymer organic flocculant E and ultrahigh molecular weight polymer organic flocculant F. The invention solves the problems that the existing inorganic flocculant reduces the content of organic matters in sewage, but obviously increases the water-containing sludge, obviously increases the sludge dewatering, sludge drying and sludge treatment cost, improves the quality and recycling rate of organic recycled matters, reduces the sewage treatment difficulty and the operation cost and the like.
Description
Technical Field
The invention relates to the technical field of flocculating agents, in particular to a compound of a surfactant with various molecular structures, organic amine with various molecular structures and charge densities and a high molecular polymer with various molecular weights and charge density distributions, which are used for treating organic matter (such as oil) components, suspended matters, turbidity and the like in water. The method is widely applied to each process and process water treatment stage of production process flows in various industries.
Background
The national energy conservation and environmental protection work is increasingly emphasized, the pollutant recycling and emission standards are increasingly standardized, the environmental pollution punishment is increasingly strict, the enterprise is increasingly emphasized in the application of recycling pollutants, the environmental protection treatment cost borne by the enterprise is increasingly increased, and the environmental protection pressure is increasingly increased.
At present, most flocculants used in sewage treatment processes are of different types, but they can be generally classified into inorganic and organic flocculants. The inorganic flocculant is mainly aluminum chloride, ferric sulfate, aluminum ferric sulfate, polymers thereof and the like, and the polyacrylamide and the polyquaternary ammonium salt are typical representative of organic flocculant, such as single flocculant and composite flocculant of the polyacrylamide, the polyquaternary ammonium salt and the inorganic flocculant, wherein the organic flocculant composed of the polyacrylamide and the polyquaternary ammonium salt has poor treatment effect in practical application and high treatment cost.
The organic matters in the water are more in types and difficult to separate, the separation effect is not satisfactory due to the recovery technology, even if at least organic components are separated and recycled, the organic matters still contained in the water are regarded as pollutants to be treated, the treatment process flow is long, the equipment investment and the operation cost are high, the treatment efficiency is not ideal, the quality (oil in water, COD (chemical oxygen demand), suspended matters, turbidity and the like) of the discharged water often lingers around the control index, the operation management pressure is high, and the recycling of the water is seriously influenced.
In flotation and sludge sedimentation processes, large doses of inorganic flocculants are usually added to ensure the treatment effect. Although the organic matter content in the sewage is reduced, the added large-dose inorganic flocculant is used as a main component of the high-water-content sludge, so that the water-content sludge is obviously increased, and the sludge dewatering, sludge drying and sludge treatment costs are obviously increased.
In the recycled organic matters, the quality of the recycled matters is affected because the flocculant contains inorganic salt, the recycled matters are treated as hazardous waste, the treatment cost is high, and the resource is wasted. Therefore, how to effectively improve the flocculation separation efficiency of organic matters in water, improve the quality and recycling rate of the organic reclaimed matters, reduce the sewage treatment difficulty and the operating cost, and become important and difficult problems of attention in the industry.
Disclosure of Invention
The invention aims to: the invention provides an all-organic composite flocculant and application thereof, and aims to solve the problems that the existing inorganic flocculant reduces the content of organic matters in sewage, but remarkably improves the water-containing sludge, remarkably increases sludge dewatering, sludge drying and sludge treatment cost, improves the quality and recycling rate of organic reclaimed matters, reduces sewage treatment difficulty and operation cost and the like.
The technical scheme is as follows:
the effective substances of the flocculant comprise a composite flocculant and an organic compound A, wherein the composite flocculant is a combination of three or more of a low molecular weight polymer organic flocculant B, a low molecular weight polymer organic flocculant C, a medium molecular weight polymer organic flocculant D, a high molecular weight polymer organic flocculant E and an ultrahigh molecular weight polymer organic flocculant F; the weight average molecular weight of the organic compound A is below 100000, the weight average molecular weight of the low molecular weight polymer organic flocculant B is 10000-50 ten thousand, the weight average molecular weight of the low molecular weight polymer organic flocculant C is 50-500 ten thousand, the weight average molecular weight of the medium molecular weight polymer organic flocculant D is 500-1000 ten thousand, the weight average molecular weight of the high molecular weight polymer organic flocculant E is 1000-1500 ten thousand, and the weight average molecular weight of the ultrahigh molecular weight polymer organic flocculant F is 1500-4500 ten thousand.
Preferably, the flocculant comprises 0.1 to 55 parts by mass of an organic compound A and a composite flocculant, wherein the composite flocculant is a combination of three or more of 0.01 to 50 parts by mass of a low molecular weight polymer organic flocculant B, 0.01 to 45 parts by mass of a low molecular weight polymer organic flocculant C, 0.01 to 40 parts by mass of a medium molecular weight polymer organic flocculant D, 0.001 to 35 parts by mass of a high molecular weight polymer organic flocculant E and 0.001 to 30 parts by mass of an ultrahigh molecular weight polymer organic flocculant F.
Preferably, the flocculant also comprises an organic surfactant G, and the mass fraction of the organic polymer surfactant G is 0.001-10; the organic high molecular surfactant G is a water-soluble high molecular surfactant with the weight average molecular weight of 1000-40 ten thousand, and comprises homopolymers, copolymers and polycondensates of the surfactant, and the monomers are a plurality of substances which are grafted and can be copolymerized into trees with side branch molecular structures or a plurality of substances which are segmented and can be alternately copolymerized into multiple network honeycomb organic copolymers with cyclic block molecular structures.
Preferably, the ionic degree of the organic compound A is more than 30%, and the organic compound A is selected from one or more of water-soluble cationic and anionic organic compounds; when the organic compound A is a cationic organic compound, the general formula is R (NH) 2 ) 2 ，NH 2 R，NHR 1 R 2 ，NHR 1 R 2 R 3 ，NH + R R 1 R 2 R 3 ，RCONH2，RNH 3 OH，RNH 2 OH，RCONH 3 OH or- (NH) + R 1 R 2 R 3 ) n -, where the substituents R, R 1 、R 2 、R 3 Can be C 1 ～C 18 Alkyl, alkenyl, cycloalkyl or phenyl; when the organic compound A is an anionic organic compound, the general formula is RSO 2 ，R 1 R 2 SO 3 ，RCO 2 ，R 1 R 2 CO，RNO 2 ，RCN，RCOO ＝ ，RSO 3 ＝ ，,ROSO 3 ＝ ，RPO 3 ＝ Wherein the substituents R, R 1 、R 2 ，R 3 Is C 1 ～C 18 Alkyl, alkenyl, cycloalkyl or phenyl.
Preferably, when the organic compound a is a cationic organic compound, the organic compound a is selected from one or more of ethanolamine, diethanolamine, triethanolamine, morpholine, cyclohexylamine, methoxypropane, ethylenediamine, propylenediamine dimethylpropylamine, hexamethylenediamine, hydroxyethylethylenediamine, octadecylamine, N-dimethylethanolamine, N-diethylethanolamine, quaternary ammonium salt, polyquaternary ammonium salt, N-vinylformamide, methacryloxyethyltrimethylammonium chloride; when the organic compound A is an anionic organic compound, the organic compound A is selected from one or more of sodium acrylate, sodium acrylamide and alkyl sulfonate, sodium styrene phosphate or sodium alkyl phosphonate.
Preferably, the low molecular weight polymeric organic flocculant B is selected from one or more of water-soluble anionic, cationic and nonionic polymers, zwitterionic low molecular weight polymeric organic flocculants; when the low molecular weight polymer organic flocculant B is a cation, the molecular structural general formula of the flocculant B is R (NH) 2 ) 2 ，NH 2 R，NHR 1 R 2 ，NHR 1 R 2 R 3 ，NH + R 1 R 2 R 3 ，RCONH2，RNH 3 OH，RNH 2 OH，RCONH 3 OH or- (NH) + R 1 R 2 R 3 ) n -, therein R, R 1 、R 2 R3 is C 1 ～C 18 Alkyl, alkenyl, cycloalkyl or phenyl; when the low molecular weight polymer organic flocculant B is an anion, the structural general formula of the flocculant B is RCOO ＝ ，RSO 3 ＝ ,ROSO 3 ＝ ，RPO 3 ＝ Or RNO 2 Wherein R is C 1 ～C 18 Alkyl, alkenyl, cycloalkyl or phenyl.
Preferably, when the low molecular weight polymeric organic flocculant B is cationic, the low molecular weight polymeric organic flocculant B has a quaternary ammonium salt group, a quinolinium ion group, a pyridinium ion group structure, or a monomer having a vinylamine, N-vinylformamide, vinyl acrylamide structure, a copolymer composed of monomers having one or two or three groups or structures thereof; for example: homopolymers of dimethyldiallylammonium chloride, copolymers with acrylamide, copolymers of vinyltrimethoxysilane with DADMAC, terpolymers of vinyltrimethoxysilane with DADMAC and AM, polyiminopolyquaternary ammonium salts, polymethyl acryloyloxyethyl trimethyl ammonium chloride, dimethylaminoethyl methacrylate acrylamide polymers, dodecyl dimethyl benzyl ammonium bromide (chloride), (poly) dimethyl dipropylammonium chloride, poly-beta-hydroxy polyamines, polydimolecular allyl quaternary ammonium cationic polymers, high molecular copolymers of methacrylate quaternary ammonium salts with acrylamide, polyepoxy trimethyl ammonium chloride, methacrylic acid-acrylamide-dimethylaminoethyl polymers, polyethylenimine, polyethylene polyamines, chitosan;
when the low molecular weight polymer organic flocculant B is an anion, the structure of the low molecular weight polymer organic flocculant B is sodium polyacrylate, an acrylamide-sodium acrylate copolymer and sodium polystyrene sulfonate sodium polystyrene sodium phosphate;
when the low molecular weight polymeric organic flocculant B is nonionic, the structure of the low molecular weight polymeric organic flocculant B has nonionic polyacrylamide or polyethylene oxide.
Preferably, the low molecular weight high molecular weight organic flocculant C, the medium molecular weight high molecular weight organic flocculant D, the high molecular weight organic flocculant E and the ultrahigh molecular weight high molecular weight organic flocculant F are all selected from one or more of water-soluble anionic, cationic, nonionic and zwitterionic structure polymeric organic flocculants.
Preferably, the low molecular weight high molecular weight organic flocculant C is a high molecular weight organic flocculant with the weight average molecular weight of 50-500 ten thousand, the medium molecular weight high molecular weight organic flocculant D is a high molecular weight organic flocculant with the weight average molecular weight of 500-1000 ten thousand, the high molecular weight organic flocculant E is a high molecular weight organic flocculant with the weight average molecular weight of 1000-1500 ten thousand, the ultrahigh molecular weight organic flocculant F is a high molecular weight organic flocculant with the weight average molecular weight of 1500-4500 ten thousand, the high molecular weight organic flocculant comprises homopolymers, copolymers and polycondensates of the high molecular organic flocculant, and the monomers are a plurality of substances with branched energy of side branch molecular structures which can be copolymerized into a tree type or a plurality of substances with cyclic block molecular structure which can be segmented into a plurality of net-shaped honeycomb organic copolymers in an alternating manner.
The application of the all-organic composite flocculant in preparing a medicament aqueous solution with the mass concentration of 0.1-60% of active substances or in preparing a dry solid medicament with the mass concentration of 1-99.9%, wherein an auxiliary agent is added or not added into the medicament.
The beneficial effects are that:
compared with inorganic flocculant, or only one of low molecular weight flocculant or high molecular weight flocculant polymer, or compound with various molecular weight flocculants, or compound agent of organic and inorganic flocculant, the compound agent of the invention has obvious flocculation effect, and can obtain treatment effect with lower cost and higher efficiency. In addition, in the process of forming the flocculent colloid, the forming amount and forming tendency of the flocculent colloid are smaller, and the sludge with more rapid and smooth flocculation, sedimentation and drainage effects and higher dryness can be obtained. The problems of high water content, large sludge quantity, sludge dehydration, sludge drying, high sludge treatment cost and the like of the sludge generated by the inorganic flocculant are effectively solved.
Detailed Description
The invention is described in more detail below with reference to the drawings accompanying the specification.
The traditional flocculation theory is that double layer ions of opposite charge ions are used for neutralizing suspended particles to break the double layer ion structure (inorganic salts such as polymeric aluminum salt, polymeric ferric salt, polymeric silicon salt, composite salt and the like), and the adsorption bridging effect of high molecular polymer (linear chain) is utilized, and the linear long chain is connected and condensed, so that the aggregation and sedimentation effects of the suspended particles are increased, and the clarification effect is achieved. A large number of practical conditions prove that the flocculant is screened by only relying on ion neutralization, breaking double layers, linear polymer adsorption bridging, linear long chain connection, aggregation, rolling and sweeping and sedimentation theory, so that the effect is poor, the cost is high, and the impact resistance of the product performance is weak.
In order to break the limitation, two mathematical models are designed to find a path for solving the problem:
one of the mathematical models is to build a tree crown structure form with trunks, branches, tips and leaves through organic matters with different molecular weights under the condition of traditional ion neutralization and breaking double electric layers, so that the tree crown structure form has a solid and strong trunk skeleton structure, a large number of powerful branches, branch supporting structures and dense adsorption capture specific surfaces of dense branches and leaves, and the tree crown structure form is used for adsorbing, capturing and sweeping particles with various chemical structures in water just like the large-scale forest formed by the trees to adsorb air dust. Preferably, the ultrahigh molecular weight polymer with a molecular branching structure is used as a trunk, the high molecular weight polymer with a branching structure is used as a crotch, the high molecular weight polymer with a molecular weight in the branching structure is used as a branch, the low molecular weight polymer with a branching structure is used as a tree tip, the low molecular weight polymer with a branching structure is used as a tree leaf, and the polymers with a branching structure are connected into a body type structure through hydrogen bond binding force, van der Waals adsorption force and coordination bond binding force of SP tracks in a chain extension branch copolymerization.
The other mathematical model approach is still to neutralize in traditional ion, break the double electric layer, set up the network structure form with root line, approach line, crotch line, warp line, weft line, mesh through the organic matter of different molecular weights, make it have firm and strong net root skeleton structure and a large number of powerful approach line, crotch line supporting structure and dense three-dimensional multiple net type absorb and catch the specific surface, as if the aquatic networking is formed and absorbed, the roll, net catch the particle of various chemical structures in the water like the large-scale fishing. The ultra-high molecular weight polymer with a block annular molecular body type structure is preferably used as a strong root net, the high molecular weight polymer with a block body type structure is also used as a strong guide line, the high molecular weight polymer with a molecular weight in the block body type structure is used as a strong cross line, the low molecular weight polymer with a block body type structure is used as a tough longitude and latitude line, the low molecular weight polymer with a block body type structure is a compact mesh, and the polymers with the block body type structure are connected into a cellular body type structure of a multi-mesh type structure by means of hydrogen bond binding force, van der Waals adsorption force and coordination bond binding force of SP orbitals through block copolymerization and alternating copolymerization.
An all-organic composite flocculant for effectively removing organic matters, suspended matters and turbidity in water. The effective substances comprise a cationic (anion, nonionic, zwitterionic) organic compound A and a composite flocculant, wherein the composite flocculant is three or more of a cationic (anion, nonionic, zwitterionic) low molecular weight polymer organic flocculant B, a cationic (anion, nonionic, zwitterionic) low molecular weight polymer organic flocculant C, a cationic (anion, nonionic, zwitterionic) medium molecular weight polymer organic flocculant D, a cationic (anion, nonionic, zwitterionic) high molecular weight polymer organic flocculant E, a cationic (anion, nonionic, zwitterionic) ultrahigh molecular weight polymer organic flocculant F, and a cationic (anion, nonionic, zwitterionic) organic surfactant G can be added. Wherein the mass portions of the cationic organic compound A, the low molecular weight polymer organic flocculant B, the low molecular weight polymer organic flocculant C, the medium molecular weight polymer organic flocculant D, the high molecular weight polymer organic flocculant E, the ultrahigh molecular weight polymer organic flocculant F and the organic polymer surfactant G are 0.1 to 55,0.01 to 50,0.01 to 45,0.01 to 40,0.01 to 35 and 0.001 to 30 in sequence.
Preferably, the effective substances of the flocculant comprise a composite flocculant and an organic compound A, wherein the composite flocculant is a combination of four or more of a low molecular weight polymer organic flocculant B, a low molecular weight polymer organic flocculant C, a medium molecular weight polymer organic flocculant D, a high molecular weight polymer organic flocculant E and an ultrahigh molecular weight polymer organic flocculant F. The flocculant comprises a composite flocculant and an organic surfactant G, wherein the composite flocculant is a combination of four or more than four of a low molecular weight polymer organic flocculant B, a low molecular weight polymer organic flocculant C, a medium molecular weight polymer organic flocculant D, a high molecular weight polymer organic flocculant E and an ultrahigh molecular weight polymer organic flocculant F. The flocculant comprises a composite flocculant, an organic compound A and an organic surfactant G, wherein the composite flocculant is a combination of three or more of a low molecular weight polymer organic flocculant B, a low molecular weight polymer organic flocculant C, a medium molecular weight polymer organic flocculant D, a high molecular weight polymer organic flocculant E and an ultrahigh molecular weight polymer organic flocculant F.
The effective substances in the present invention refer to substances which play a main role in flocculation, and do not include other auxiliary substances such as water, auxiliary agents and the like. The cationic organic compound A in the invention has an ionic degree of more than 30% and a weight average molecular weight of 100000 or less. Mainly acts as charge neutralization and damages the double electric layer.
The weight average molecular weight of the low molecular weight polymer organic flocculant B is 10000-50 ten thousand, and the low molecular weight polymer organic flocculant B mainly plays a role of tree leaves and meshes of a net.
The weight average molecular weight of the low molecular weight high molecular weight organic flocculant C is 50-500 ten thousand, and the flocculant mainly plays roles of treetop and longitude and latitude net class of trees.
The weight average molecular weight of the medium molecular weight high molecular weight organic flocculant D is 500-1000 ten thousand, and the flocculant mainly plays roles of branches of trees and lines of nets.
The weight average molecular weight of the high molecular weight organic flocculant E is 1000 ten thousand to 1500 ten thousand, and mainly plays a role in leading the crotch and the net of the tree.
The weight average molecular weight of the ultrahigh molecular weight high molecular weight organic flocculant F is 1500-4500 ten thousand, and the ultrahigh molecular weight high molecular weight organic flocculant F mainly plays a role of tree poles and root lines of trees.
The weight average molecular weight of the organic polymer surfactant G is 1000-50 ten thousand.
The ionic degree of the organic compound A is more than 30%, the weight average molecular weight is below 100000, and the organic compound A is selected from one or more of water-soluble cation and anion organic compounds; when the organic compound A is a cationic organic compound, the general formula is R (NH) 2 ) 2 ，NH 2 R，NHR 1 R 2 ，NHR 1 R 2 R 3 ，NH + R R 1 R 2 R 3 ，RCONH2，RNH 3 OH，RNH 2 OH，RCONH 3 OH or- (NH) + R 1 R 2 R 3 ) n -, where the substituents R, R 1 、R 2 、R 3 Can be C 1 ～C 18 Alkyl, alkenyl, cycloalkyl, phenyl, as follows. When the organic compound A is an anionic organic compound, the general formula is RSO 2 ，R 1 R 2 SO 3 ，RCO 2 ，R 1 R 2 CO，RNO 2 ，RCN，RCOO ＝ ，RSO 3 ＝ ，,ROSO 3 ＝ ，RPO 3 ＝ Wherein the substituents R, R 1 、R 2 ，R 3 Is C 1 ～C 18 Alkyl, alkenyl, cycloalkyl, phenyl, as follows. Preferably, when the organic compound a is a cationic organic compound, the organic compound a is selected from one or more of ethanolamine, diethanolamine, triethanolamine, morpholine, cyclohexylamine, methoxypropane, ethylenediamine, propylenediamine dimethylpropylamine, hexamethylenediamine, hydroxyethylethylenediamine, octadecylamine, N-dimethylethanolamine, N-diethylethanolamine, quaternary ammonium salt, polyquaternary ammonium salt, N-vinylformamide, methacryloxyethyltrimethylammonium chloride; when the organic compound A is an anionic organic compound, the anionic group can be selected from carboxyl, sulfuric acid group, phosphonic acid group and nitro organic compound. The organic compound A is selected from one or more of sodium acrylate, acrylamide and sodium alkyl sulfonate, sodium styrene phosphate or sodium alkyl phosphonate.
The weight average molecular weight of the low molecular weight polymer organic flocculant B is 10000-50 ten thousand, and the low molecular weight polymer organic flocculant B is selected from water-soluble anions (such as RCOO) ＝ ，RSO 3 ＝ ，,ROSO 3 ＝ ，RPO 3 ＝ ，RNO 2 Etc.), cations (e.g. RCONH 2 ,RNH 3 OH,RNH 2 OH,RCONH 3 OH, non-ionicOne or more of a daughter, zwitterionic low molecular weight polymeric organic flocculant;
when the low molecular weight polymer organic flocculant B is a cation, the molecular structural general formula of the flocculant B is R (NH) 2 ) 2 ，NH 2 R，NHR 1 R 2 ，NHR 1 R 2 R 3 ，NH + R 1 R 2 R 3 ，RCONH2，RNH 3 OH，RNH 2 OH，RCONH 3 OH or- (NH) + R 1 R 2 R 3 ) n -, therein R, R 1 、R 2 R3 is C 1 ～C 18 Alkyl, alkenyl, cycloalkyl, phenyl, as defined below; when the low molecular weight polymer organic flocculant B is an anion, the structural general formula of the flocculant B is RCOO ＝ ，RSO 3 ＝ ,ROSO 3 ＝ ，RPO 3 ＝ Or RNO 2 。
Preferably, when the low molecular weight polymeric organic flocculant B is cationic, the low molecular weight polymeric organic flocculant B is selected from quaternary ammonium salts, quinolinium ions, pyridinium ions, in particular polyvinylamine, poly-N-vinylformamide, polyvinylacrylamide and copolymers composed of vinylamine, N-vinylformamide, vinylacrylamide monomers (two or three of these), homopolymers of dimethyldiallylammonium chloride (DADMAC) and copolymers with Acrylamide (AM), copolymers of Vinyltrimethoxysilane (VTMS) with dmac, terpolymers of VTMS with DADMAC and AM, polyimido polyquaternary ammonium salts, polyethyl trimethylammonium chloride, dimethylaminoethyl methacrylate acrylamide polymers, dodecyldimethylbenzyl ammonium bromide (chloride), ammonium (poly) dimethyldipropylammonium chloride, poly- β -hydroxy polyamines, polydimolecular allylammonium cationic polymers, high molecular copolymers of methacrylate and acrylamide, poly-epoxypropyltrimethylammonium chloride, poly-ethyleneamine (pec) chloride, poly-ethyleneamine-polyethyleneimine, poly-ethyleneamine or poly-ethyleneamine;
when the low molecular weight polymer organic flocculant B is an anion, the anion groups are carboxyl, sulfate and phosphate groups, and the low molecular weight polymer organic flocculant B is selected from sodium polyacrylate, an acrylamide-sodium acrylate copolymer and sodium polystyrene sulfonate sodium polystyrene phosphate;
when the low molecular weight polymeric organic flocculant B is nonionic, the low molecular weight polymeric organic flocculant B is selected from nonionic polyacrylamide or polyethylene oxide (PEO) and the like. Such flocculants are uncharged and generate temporary charges in aqueous solution by protonation, and aggregate by weak hydrogen bonding. The zwitterionic low molecular weight polymer organic flocculant B is an organic flocculant with both anionic and cationic groups in the molecular structure. The anionic groups are typically carboxyl, sulfate and phosphate groups, and the cationic groups are typically quaternary ammonium salt groups, quinolinium ions and pyridinium ions.
The low molecular weight high molecular weight organic flocculant C in the invention can be selected from one or more of water-soluble cationic flocculant, anionic flocculant, nonionic flocculant or zwitterionic flocculant, and the molecules of the low molecular weight high molecular weight organic flocculant C have a side branch structure or a cyclic block structure. Preferably, the water-soluble high molecular weight polyacrylamide with the weight average molecular weight of 50-500 ten thousand comprises homopolymers, copolymers, polycondensates and monomers of acrylamide, wherein the monomers are a plurality of substances which have a branched molecular structure and can be copolymerized into trees or a plurality of substances which have a cyclic block molecular structure and can be copolymerized into a multi-network honeycomb organic copolymer in an alternating manner.
The medium molecular weight high molecular weight organic flocculant D in the invention can be selected from one or more of water-soluble cationic flocculant, anionic flocculant, nonionic flocculant or zwitterionic flocculant, and the molecules of the medium molecular weight high molecular weight organic flocculant D have a side branch structure or a cyclic block structure. The water-soluble high molecular weight polyacrylamide with weight average molecular weight of 500-1000 ten thousand is preferable, and the high molecular weight polyacrylamide comprises homopolymers of acrylamide, copolymers of methacrylamide and graft copolymerization of various side branch molecular structures into tree-shaped and ring-shaped block molecular structure block copolymers, and is alternately copolymerized into multiple network honeycomb organic copolymers and the like. The polymer comprises homopolymers, copolymers, polycondensates and monomers of acrylamide, wherein the monomers are a plurality of substances which are grafted and can be copolymerized into a tree type with a side dendritic molecular structure, or a plurality of substances which are copolymerized into a multi-network honeycomb organic copolymer alternately with a cyclic block molecular structure.
The high molecular weight organic flocculant E in the invention can be selected from one or more of water-soluble cationic flocculant, anionic flocculant, nonionic flocculant or zwitterionic flocculant, and the molecules of the high molecular weight organic flocculant E have a side branch structure or a cyclic block structure. Preferably, the water-soluble high molecular weight polyacrylamide with the weight average molecular weight of 1000-1500 ten thousand comprises homopolymers, copolymers, polycondensates and monomers of acrylamide, wherein the monomers are a plurality of substances which have a branched molecular structure and can be copolymerized into trees or a plurality of substances which have a cyclic block molecular structure and can be copolymerized into a multi-network honeycomb organic copolymer in an alternating manner.
The ultrahigh molecular weight high molecular weight organic flocculant F in the invention can be selected from one or more of water-soluble cationic flocculant, anionic flocculant, nonionic flocculant or zwitterionic flocculant, and the molecules of the ultrahigh molecular weight high molecular weight organic flocculant F have a side branch structure or a cyclic block structure. Preferably, the water-soluble high molecular weight polyacrylamide with the weight average molecular weight of 1500-4500 ten thousand comprises homopolymers, copolymers, polycondensates and monomers of acrylamide, wherein the polymers are a plurality of substances which have a branched molecular structure and can be copolymerized into trees or a plurality of substances which have a cyclic block molecular structure and can be copolymerized into a multi-network honeycomb organic copolymer in an alternating manner.
The weight average molecular weight of the organic high molecular surfactant G is 1000-50 ten thousand, and the organic high molecular surfactant G is one or more selected from water-soluble cationic surfactant, anionic surfactant, nonionic surfactant and zwitterionic surfactant, and the molecules of the organic high molecular surfactant G have a side branch structure or a cyclic block structure. The polymer surfactant with water-soluble weight average molecular weight of 1000-40 ten thousand is preferable, and includes homopolymer, copolymer, polycondensate and monomer of surfactant, which are grafted and copolymerized into tree-type polymer with side dendritic molecular structure or copolymerized into multiple net honeycomb organic copolymer with cyclic block molecular structure.
The molecular structural general formula of the anionic surfactant G is RCOO - ,RSO 3 - ,RPO 3 - Cationic surfactants G include amine and quaternary ammonium salt types, preferably aminoalkyl acrylate copolymers, modified polyethyleneimine macromolecular surfactants and quaternary ammonium salt group-containing acrylamide copolymers, polyvinylbenzyl trimethylamine salts such as polyethyleneimine, polyvinylpyrrolidone, polymaleimide and derivatives thereof, quaternized polyacrylamide, polyvinylpyridine salts, polydimethyl amine epichlorohydrin.
The nonionic surfactant G is preferably polyvinyl alcohol and its partially esterified or acetalized products such as polyacrylamide, maleic anhydride copolymer, polyacrylate, polyether, polyethylene oxide-propylene oxide, water-soluble phenolic resin, amino resin, etc., modified therewith.
The amphoteric surfactant G is preferably a vinyl pyridine acrylate copolymer, an acrylic acid cationic acrylate copolymer, an amphoteric polyacrylamide, or the like.
The organic composite flocculant can be an aqueous solution with the mass concentration of an effective substance of 0.1-60%, preferably 0.2-55%, and can be a dried solid and a solid mixture with the mass concentration of the effective substance of 1-99.9%, preferably 5-99.9%. Other auxiliary substances such as auxiliary agents may be added to the aqueous solution, solid or mixture.
The invention mixes three or more of cationic organic compound A, polymer organic flocculant B, polymer organic flocculant C, polymer organic flocculant D, polymer organic flocculant E and polymer organic flocculant F according to proportion, and can also add polymer surfactant G according to proportion to prepare liquid with required concentration, which can be directly added into sewage or discharged sludge with high water content, the adding amount of effective substance is 20 ppm-600 ppm when the composite medicament is applied, and flocculation, sedimentation and dehydration can be carried out after stirring for 5 minutes (stirring strength is not more than 90 turns per minute).
In the invention, the organic compound A can form higher (anion, nonionic, zwitterionic) ion concentration in the solution because of higher ion degree (cation, anion, nonionic, zwitterionic), and the organic compound A compresses and damages the double electric layers on the surface of the particles to realize destabilization of the particles and further realize de-hydration of the particles mainly by absorbing on the surface of suspended particles and changing the surface load of the particles. The high molecular polymer B, the high molecular polymer C, the high molecular polymer D, the high molecular polymer E, the high molecular polymer F and the high molecular surfactant G are grafted and copolymerized into a tree-shaped polymer through various side branch molecular structures or are segmented and copolymerized into a multi-network honeycomb organic copolymer through various annular block molecular structures, and the high molecular weight organic copolymer is firm in structure, compact, stretched and occupies the whole liquid space, has large specific surface area, and can adsorb, connect, bridge, diffuse and net the suspended particles of destabilization in water, further concentrate and concentrate oil (organic matters) in water, flocculate and dehydrate the suspended matters, particles and sludge; and the combination of the two or more can further play a role in synergy.
The invention can obtain unexpected synergistic effect on the basis of not increasing the cost of water and sludge treatment flocculant by combining various medicaments, compacts the floccules formed in the flocculation process, avoids the phenomenon that the non-process systematic sludge amount is greatly increased due to the addition of a large amount of inorganic flocculant and polymeric flocculant due to poor treatment effect of other methods, can optimally release the water in the floccules, thereby reducing the flocculated sludge amount of sewage, reducing the water content in the sludge, and simultaneously remarkably improving the specific resistance of the sludge, thereby improving the water permeability of the sludge. The combined use of various medicaments obviously improves the flocculation efficiency of sewage, obviously reduces the sludge quantity, obviously improves the filtering characteristic of the sludge, has small dosage, can reach the effect far exceeding the prior other medicaments under the same dosage, has low specific impedance value of the sludge after treatment, high solid content of the sludge after dehydration, high combustion heat value and obviously reduces the combustion ash.
In order to examine the flocculation effect of the organic flocculant, the test adopts the sedimentation of a sewage treatment plant oil separation tank of a petrochemical company of China oil Co. The test was performed in a product quality inspection laboratory. In general, COD is measured for organic matter removal performance, oil content is measured for oil removal capacity, and suspended matter and turbidity is measured for particulate removal capacity. And a sludge specific resistance experiment is adopted to determine the dehydration performance of the sludge. It is considered that sludge having a sludge specific resistance of more than 1013m/kg is difficult to filter, and sludge having a specific resistance of less than 1011m/kg is easy to dewater. After sewage pretreatment, COD is less than or equal to 500ppm, oil content is less than or equal to 20ppm, suspended matters are less than or equal to 20ppm, and turbidity is less than or equal to 20NTU. The related main indexes of the discharged sewage are that COD is less than or equal to 50ppm, oil content is less than or equal to 2.0ppm, suspended matters are less than or equal to 2.0ppm, and turbidity is less than or equal to 2.0NTU.
1. The field control index requires: COD is less than or equal to 500PPM, suspended matters are less than or equal to 20PPM, and oil content is less than or equal to 20PPM;
2. water quality for test: the pH value is 7.50; suspension: 44mg/L; COD is 382mg/L; turbidity was 41.6 degrees;
3. experimental conditions: at room temperature.
(2) The following raw materials are numbered and prepared into uniform concentration for standby:
preparing standard aqueous solution of polyaluminum chloride with uniform concentration;
preparing a standard aqueous solution of A (methacryloyloxyethyl trimethyl ammonium chloride) with uniform concentration;
preparing a standard aqueous solution with a weight average molecular weight of about 50 ten thousand of that of a B (dimethylaminoethyl methacrylate acrylamide polymer) with uniform concentration;
preparing standard aqueous solution of C (high molecular weight polyacrylamide with weight average molecular weight of about 200 ten thousand) with uniform concentration and a side branch structure or a ring block structure;
fifthly, preparing a D (high molecular weight polyacrylamide with a side branch structure or a ring block structure) standard aqueous solution with uniform concentration, wherein the weight average molecular weight of the high molecular weight polyacrylamide is about 800 ten thousand;
preparing E (high molecular weight polyacrylamide with weight average molecular weight of about 1200 ten thousand) standard aqueous solution with uniform concentration;
preparing F (ultrahigh molecular weight polyacrylamide with weight average molecular weight of about 2500 ten thousand) standard aqueous solution with uniform concentration and side branch structure or annular block structure;
preparing a standard aqueous solution of a G (dodecyl dimethyl benzyl ammonium bromide) surfactant with uniform concentration; preparing a uniform concentration ferric chloride standard aqueous solution;
experiment one: flocculation effect screening of different dosages of single flocculant with different molecular weights
Adding flocculant with the dosage of 20, 50 and 100 parts of numbers 1-9 into 100ml three groups of parallel sewage water samples respectively, stirring for 1 minute, standing for 10 minutes, and observing the phenomenon to find:
TABLE 1 data sheet for screening flocculation effects of different single flocculants at different doses
The experimental conclusion is as follows:
1. when a single flocculant is used, the flocculation is fine, the amount is small, the transparency is almost unchanged, and the effect is not obvious.
2. When a single flocculant is used, the treatment effect of the polymeric ferric chloride is slightly better. The organic polymer has poor effect. The higher the high molecular weight average molecular weight, the lower the treatment effect.
3. The surfactant has certain treatment effect when the dosage is small. The larger the dosage, the more obvious the emulsification, and the lower the treatment effect.
4. The COD, suspended matter and turbidity were measured and the data are shown in Table 1.
5. The treatment effect of low molecular weight COD, suspended matters and turbidity is better than that of high molecular weight, but the treatment effect is reduced after reaching the peak.
6. The flocculation effect of a single flocculant cannot meet the actual requirements of the site.
7. The dosage of the single flocculant is large, and the water treatment cost is too high. The products with low cost and high effect need to be screened through experiments.
Experiment 2: flocculation synergistic effect screening by comparing different dosages of various flocculating agents with different molecular weights
Adding 0.1-55 parts by weight of organic compound A, 0.01-50 parts by weight of low molecular weight polymer organic flocculant B, 0.01-45 parts by weight of low molecular weight polymer organic flocculant C, 0.01-40 parts by weight of medium molecular weight polymer organic flocculant D, 0.01-35 parts by weight of high molecular weight polymer organic flocculant E, 0.001-30 parts by weight of ultrahigh molecular weight polymer organic flocculant F and 0.001-10 parts by weight of organic polymer surfactant G into 100ml of three groups of parallel sewage water samples respectively, stirring for 1 minute, standing for 10 minutes, taking the optimal COD and COD removal rate and phenomenon of each group, analyzing, comparing and observing the phenomenon, and finding:
TABLE 2 flocculation synergistic Effect screening of various different molecular weight flocculants at different doses
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By observing the comparative screening test, the following conclusions can be drawn:
1. the low dosage of the polymeric flocculant has synergistic effect on the removal of pollutants;
2. the surfactant G has synergism on the removal of pollutants;
3. according to the treatment effect and the analysis of the dosage proportion of the polymeric flocculant with different molecular weights, the dosage proportion is found to be in accordance with the designed treatment tree scanning and treatment net capturing mathematical model;
4. the better the treatment effect of the screened flocculant along with the increase of the dosage; but after a certain dosage, the treatment effect is increased and reduced;
5. the removal rate of the pollutants increases with the content of the pollutants;
6. the COD removal rate of the invention is not less than 66.6%, the turbidity removal rate is not less than 77.6%, and the suspended matter removal rate reaches 100%;
experiment 3 on-site verification test of composite flocculant product
The purpose of field experiment is to verify the flocculation effect of organic flocculant with fixed content and different dosages under different water quality conditions, and the experiment adopts the air floatation inlet sewage of sewage treatment plant of petrochemical company of China petroleum company.
And (3) preparation of a reagent: the preparation method comprises the steps of preparing products from 6 parts of A,19 parts of B,19 parts of C,8 parts of D,3 parts of E,3 parts of F,15 parts of G polymer surfactant and other auxiliary agents, stirring for 1 minute, and standing for 10 minutes for later use.
Experiment site: the clean water workshop is a field detection laboratory.
Experimental temperature: room temperature.
Experimental time: three days.
Experiment on the first day:
the water quality of the on-site sampling is as follows: first-stage air floatation inlet sewage: the pH value is 7.09; COD is 464mg/L; turbidity was 79.0 degrees; oil content: 18.95mg/L.
Adding 1-600 ppM prepared reagents into 100ml three groups of parallel sewage water samples respectively, stirring for 1 min, standing for 10 min, observing the phenomenon, and detecting the COD and turbidity data change of the samples, wherein the serial numbers of the reagents correspond to the serial numbers of the experiments are 31.1-1-31.1-10. The first day of experimental data is shown in Table 3-1.
Table 3-1 first day Experimental data
According to the removal rate data of COD and turbidity, the better the treatment effect of the screened flocculant along with the increase of dosage. But after a certain dose, the increase in treatment effect is reduced. At a dosage of 350ppM, the COD and turbidity removal rate is higher than 65%, the oil content removal rate is higher than 60%, and the suspended matter removal rate is up to 100%.
The following experiment:
the water quality of the on-site sampling is as follows: first-stage air floatation inlet sewage: the pH value is 7.63; COD is 1190.3mg/L; turbidity was 69.60 degrees; oil content: 50mg/L.
Adding 1-600 ppM prepared reagent into 100ml three groups of parallel sewage water samples respectively, stirring for 1 min, standing for 10 min, observing the phenomenon, and detecting the COD and turbidity data change of the samples, wherein the number of the prepared reagent corresponds to 3.2-1-3.2-10 of the experimental sequence. The next day the experimental data are shown in Table 3-2.
TABLE 3-2 Experimental data for the next day
According to the removal rate data of COD and turbidity, the better the treatment effect of the screened flocculant along with the increase of dosage. But after a certain dose, the increase in treatment effect is reduced. The removal rate of contaminants increases as its content increases. At the dosage of 350ppM, the COD removal rate is higher than 74%, the turbidity removal rate is higher than 57.6%, the oil content removal rate is higher than 85%, and the suspended matter removal rate is 100%.
Third day experiment:
the water quality of the on-site sampling is as follows: first-stage air floatation inlet sewage: the pH value is 7.63; COD is 619mg/L; turbidity was 86.5 degrees; oil content: 25.39mg/L.
Adding 1-600 ppM parts of prepared reagent into 100ml three groups of parallel sewage water samples respectively, stirring for 1 min under the condition of corresponding experiment sequence numbers of 31.3-1-31.3-10, standing for 10 min, observing the phenomenon, and detecting the change of COD and turbidity data of the samples. The third day of experimental data is shown in Table 3-3.
Tables 3-3 third day Experimental data
According to the removal rate data of COD and turbidity, the screened flocculant is still better in treatment effect along with the increase of dosage. But after a certain dose, the increase in treatment effect is reduced. The removal rate of contaminants increases as its content increases. Also at a dosage of 350ppM, the COD removal rate is higher than 50.3%, the turbidity removal rate is higher than 65.9%, the oil content removal rate is higher than 80%, and the suspended matter removal rate is 100%.
Conclusion of experiment:
by observing the comparative screening test and verifying the experimental data, the following conclusions can be drawn in summary:
1. the low-dosage polymeric flocculant has flocculation synergy on the removal of pollutants;
2. the surfactant has synergistic effect on removing pollutants;
3. according to the treatment effect and the gradient analysis of the molecular weight change of the high molecular weight polymeric flocculant, the better the flocculation synergistic effect is found as the gradient change of the molecular weight of the high molecular weight polymeric flocculant is more. The synergistic effect of the three molecular weight gradients is obviously reflected. The higher the molecular weight of the polymeric flocculant, the smaller the dosage used. The synergistic effect of three or more molecular weight gradient ratios accords with a designed processing tree scanning and processing net capturing mathematical model;
4. according to the treatment effect and the analysis of the dosage parts of the polymeric flocculant with different molecular weights, the part ratio accords with the designed treatment tree scanning and treatment net capturing mathematical model;
5. the composite flocculant which accords with the proportion of the processing tree scanning and processing net capturing mathematical model has better processing effect along with the increase of the dosage;
6. after a certain dosage is reached, the increase of the treatment effect is reduced;
7. the removal rate of contaminants increases as their contaminant content increases;
8. the compound flocculant with the preferable proportion has obvious effect at low dosage, the COD removal rate is higher than 50.3 percent, the turbidity removal rate is higher than 65.9 percent, the oil content removal rate is higher than 80 percent, and the suspended matter removal rate reaches 100 percent at the dosage of 350 ppM;
9. meets the requirements of field control index COD less than or equal to 500PPM, suspended matters less than or equal to 20PPM and oil content less than or equal to 20 PPM.
10. The composite flocculant is an all-organic component, does not contain inorganic matters, and is beneficial to the recycling of pollutants.
Claims (8)
1. An all-organic composite flocculant is characterized in that: the flocculant comprises a composite flocculant and an organic compound A, wherein the composite flocculant is a combination of three or more of a low molecular weight polymer organic flocculant B, a low molecular weight polymer organic flocculant C, a medium molecular weight polymer organic flocculant D, a high molecular weight polymer organic flocculant E and an ultrahigh molecular weight polymer organic flocculant F; the weight average molecular weight of the organic compound A is below 100000, the ionic degree is more than 30 percent, and the organic compound A is selected from one or more of water-soluble cation and anion organic compounds; the weight average molecular weight of the low molecular weight polymer organic flocculant B is 10000-50 ten thousand, the weight average molecular weight of the low molecular weight polymer organic flocculant C is 50-500 ten thousand, the weight average molecular weight of the medium molecular weight polymer organic flocculant D is 500-1000 ten thousand, the weight average molecular weight of the high molecular weight polymer organic flocculant E is 1000-1500 ten thousand, and the weight average molecular weight of the ultrahigh molecular weight polymer organic flocculant F is 1500-4500 ten thousand.
2. A fully organic composite flocculant according to claim 1, wherein: the flocculant comprises 0.1-55 parts by weight of organic compound A and a composite flocculant, wherein the composite flocculant is a combination of three or more of 0.01-50 parts by weight of low molecular weight polymer organic flocculant B, 0.01-45 parts by weight of low molecular weight polymer organic flocculant C, 0.01-40 parts by weight of medium molecular weight polymer organic flocculant D, 0.001-35 parts by weight of high molecular weight polymer organic flocculant E and 0.001-30 parts by weight of ultrahigh molecular weight polymer organic flocculant F.
3. A fully organic composite flocculant according to claim 2, wherein: the flocculant also comprises an organic polymer surfactant G, wherein the mass fraction of the organic polymer surfactant G is 0.001-10; the organic polymer surfactant G is a water-soluble polymer surfactant with a weight average molecular weight of 1000-40 ten thousand.
4. A fully organic composite flocculant according to claim 1, wherein: when the organic compound A is a cationic organic compound, the general formula is R (NH) 2 ) 2 ，NH 2 R，NHR 1 R 2 ，NHR 1 R 2 R 3 ，NH + R R 1 R 2 R 3 ，RCONH2，RNH 3 OH，RNH 2 OH，RCONH 3 OH or- (NH) + R 1 R 2 R 3 ) n -, where the substituents R, R 1 、R 2 、R 3 Is C1-C18 alkyl, alkenyl, cycloalkyl or phenyl; when the organic compound A is an anionic organic compound, the general formula is RSO 2 ，R 1 R 2 SO 3 ，RCO 2 ，R 1 R 2 CO，RNO 2 ，RCN，RCOO = ，RSO 3 = ，ROSO 3 = ，RPO 3 = Wherein the substituents R, R 1 、R 2 ，R 3 Is C1-C18 alkyl, alkenyl, cycloalkyl or phenyl.
5. A fully organic composite flocculant according to claim 4, wherein: when the organic compound A is a cationic organic compound, the organic compound A is selected from one or more of ethanolamine, diethanolamine, triethanolamine, morpholine, cyclohexylamine, methoxypropane, ethylenediamine, propylenediamine dimethylpropylamine, hexamethylenediamine, hydroxyethyl ethylenediamine, octadecylamine, N-dimethylethanolamine, N-diethylethanolamine, quaternary ammonium salt, polyquaternary ammonium salt, N-vinylformamide and methacryloxyethyl trimethyl ammonium chloride; when the organic compound A is an anionic organic compound, the organic compound A is selected from one or more of sodium acrylate, sodium acrylamide and alkyl sulfonate, sodium styrene phosphate or sodium alkyl phosphonate.
6. A fully organic composite flocculant according to claim 1, wherein: the low molecular weight polymer organic flocculant B is selected from one or more of water-soluble anionic, cationic, nonionic and zwitterionic low molecular weight polymer organic flocculants; when the low molecular weight polymer organic flocculant B is a cationic low molecular weight polymer organic flocculant, the molecular structural general formula is R (NH) 2 ) 2 ，NH 2 R，NHR 1 R 2 ，NHR 1 R 2 R 3 ，NH + R 1 R 2 R 3 ，RCONH2，RNH 3 OH，RNH 2 OH，RCONH 3 OH or- (NH) + R 1 R 2 R 3 ) n -, therein R, R 1 、R 2 R3 is C1-C18 alkyl, alkenyl, cycloalkyl or phenyl; when the low molecular weight polymer organic flocculant B is an anionic low molecular weight polymer organic flocculant, the structural general formula is RCOO = ，RSO 3 = ,ROSO 3 = ，RPO 3 = Or RNO 2 Wherein R is C1-C18 alkyl, alkenyl, cycloalkyl or phenyl.
7. The all-organic composite flocculant according to claim 6, wherein: when the low molecular weight polymer organic flocculant B is a cationic low molecular weight polymer organic flocculant, the low molecular weight polymer organic flocculant B is selected from polyvinylamine, poly-N-vinylformamide, polyvinylacrylamide, or a copolymer composed of two or three of vinylamine monomers, N-vinylformamide monomers and vinylacrylamide monomers; when the low molecular weight polymer organic flocculant B is an anionic low molecular weight polymer organic flocculant, the low molecular weight polymer organic flocculant B is selected from sodium polyacrylate, a copolymer of acrylamide and sodium acrylate, sodium polystyrene sulfonate or sodium polystyrene phosphate; when the low molecular weight polymeric organic flocculant B is a nonionic low molecular weight polymeric organic flocculant, the low molecular weight polymeric organic flocculant B is selected from nonionic polyacrylamide or polyethylene oxide.
8. A fully organic composite flocculant according to claim 1, wherein: the low molecular weight high molecular weight organic flocculant C, the medium molecular weight high molecular weight organic flocculant D, the high molecular weight organic flocculant E and the ultrahigh molecular weight high molecular weight organic flocculant F are all selected from one or more of water-soluble anionic, cationic, nonionic and zwitterionic polymeric organic flocculants.
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| JPH1099867A (en) * | 1996-09-27 | 1998-04-21 | Sony Corp | Treatment of waste water |
| JPH10249400A (en) * | 1997-03-14 | 1998-09-22 | Nippon Shokubai Co Ltd | Method for dehydrating sludge |
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