CN105504163A - Cationic flocculant and preparation method thereof - Google Patents
Cationic flocculant and preparation method thereof Download PDFInfo
- Publication number
- CN105504163A CN105504163A CN201610037541.0A CN201610037541A CN105504163A CN 105504163 A CN105504163 A CN 105504163A CN 201610037541 A CN201610037541 A CN 201610037541A CN 105504163 A CN105504163 A CN 105504163A
- Authority
- CN
- China
- Prior art keywords
- reaction
- cationic
- cationic flocculant
- radical initiator
- flocculant
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 125000002091 cationic group Chemical group 0.000 title claims abstract description 102
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 239000000178 monomer Substances 0.000 claims abstract description 68
- 238000006243 chemical reaction Methods 0.000 claims abstract description 53
- -1 acryloyloxyethyl alkyl quaternary ammonium salts Chemical class 0.000 claims abstract description 32
- 239000003999 initiator Substances 0.000 claims abstract description 28
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 21
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 14
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims abstract description 10
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 10
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims abstract description 7
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims abstract description 6
- 235000019400 benzoyl peroxide Nutrition 0.000 claims abstract description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 5
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims abstract description 5
- UICXTANXZJJIBC-UHFFFAOYSA-N 1-(1-hydroperoxycyclohexyl)peroxycyclohexan-1-ol Chemical compound C1CCCCC1(O)OOC1(OO)CCCCC1 UICXTANXZJJIBC-UHFFFAOYSA-N 0.000 claims abstract description 4
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims abstract description 4
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 3
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims abstract description 3
- 150000003254 radicals Chemical class 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 5
- 238000010528 free radical solution polymerization reaction Methods 0.000 claims description 5
- 238000012688 inverse emulsion polymerization Methods 0.000 claims description 5
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 4
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 239000003995 emulsifying agent Substances 0.000 claims description 4
- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000002736 nonionic surfactant Substances 0.000 claims description 4
- NZIDBRBFGPQCRY-UHFFFAOYSA-N octyl 2-methylprop-2-enoate Chemical compound CCCCCCCCOC(=O)C(C)=C NZIDBRBFGPQCRY-UHFFFAOYSA-N 0.000 claims description 4
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 claims description 4
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 4
- 238000010008 shearing Methods 0.000 claims description 4
- 230000001502 supplementing effect Effects 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
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 3
- YIOJGTBNHQAVBO-UHFFFAOYSA-N dimethyl-bis(prop-2-enyl)azanium Chemical compound C=CC[N+](C)(C)CC=C YIOJGTBNHQAVBO-UHFFFAOYSA-N 0.000 claims description 3
- 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 claims description 3
- 239000000839 emulsion Substances 0.000 claims description 3
- ACWKAVFAONSRKJ-UHFFFAOYSA-M hexadecyl-dimethyl-prop-2-enylazanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)CC=C ACWKAVFAONSRKJ-UHFFFAOYSA-M 0.000 claims description 3
- 239000003350 kerosene Substances 0.000 claims description 3
- 229940057995 liquid paraffin Drugs 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 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 claims description 3
- TZYULTYGSBAILI-UHFFFAOYSA-M trimethyl(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC=C TZYULTYGSBAILI-UHFFFAOYSA-M 0.000 claims description 3
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- RWXMAAYKJDQVTF-UHFFFAOYSA-N 2-(2-hydroxyethoxy)ethyl prop-2-enoate Chemical compound OCCOCCOC(=O)C=C RWXMAAYKJDQVTF-UHFFFAOYSA-N 0.000 claims description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 2
- 239000011837 N,N-methylenebisacrylamide Substances 0.000 claims description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 2
- AVWKSSYTZYDQFG-UHFFFAOYSA-M dimethyl-octadecyl-prop-2-enylazanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CC=C AVWKSSYTZYDQFG-UHFFFAOYSA-M 0.000 claims description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 2
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 2
- 229940065472 octyl acrylate Drugs 0.000 claims description 2
- 239000003208 petroleum Substances 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- 229920000136 polysorbate Polymers 0.000 claims description 2
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 claims description 2
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- XDFFVDDBWQREAJ-UHFFFAOYSA-M trimethyl(2-prop-2-enoyloxyethyl)azanium;bromide Chemical compound [Br-].C[N+](C)(C)CCOC(=O)C=C XDFFVDDBWQREAJ-UHFFFAOYSA-M 0.000 claims description 2
- FMMTUUIZTMQIFC-UHFFFAOYSA-M trimethyl(prop-2-enyl)azanium;bromide Chemical compound [Br-].C[N+](C)(C)CC=C FMMTUUIZTMQIFC-UHFFFAOYSA-M 0.000 claims description 2
- FGKCGMMQJOWMFW-UHFFFAOYSA-M trimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azanium;bromide Chemical compound [Br-].CC(=C)C(=O)OCC[N+](C)(C)C FGKCGMMQJOWMFW-UHFFFAOYSA-M 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 26
- 239000000975 dye Substances 0.000 abstract description 20
- 125000000129 anionic group Chemical group 0.000 abstract description 8
- 150000001450 anions Chemical class 0.000 abstract description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract description 3
- 230000003311 flocculating effect Effects 0.000 abstract description 3
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 abstract 1
- 229960003328 benzoyl peroxide Drugs 0.000 abstract 1
- 230000002349 favourable effect Effects 0.000 abstract 1
- 230000007935 neutral effect Effects 0.000 abstract 1
- 239000002351 wastewater Substances 0.000 description 38
- 238000005189 flocculation Methods 0.000 description 34
- 230000016615 flocculation Effects 0.000 description 34
- 238000004043 dyeing Methods 0.000 description 30
- 239000008394 flocculating agent Substances 0.000 description 20
- 239000006081 fluorescent whitening agent Substances 0.000 description 17
- 239000000243 solution Substances 0.000 description 15
- 238000001556 precipitation Methods 0.000 description 14
- 239000000203 mixture Substances 0.000 description 12
- 239000000985 reactive dye Substances 0.000 description 11
- 238000004064 recycling Methods 0.000 description 11
- SJEYSFABYSGQBG-UHFFFAOYSA-M Patent blue Chemical compound [Na+].C1=CC(N(CC)CC)=CC=C1C(C=1C(=CC(=CC=1)S([O-])(=O)=O)S([O-])(=O)=O)=C1C=CC(=[N+](CC)CC)C=C1 SJEYSFABYSGQBG-UHFFFAOYSA-M 0.000 description 9
- 239000000980 acid dye Substances 0.000 description 9
- 150000001768 cations Chemical class 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- CNGYZEMWVAWWOB-VAWYXSNFSA-N 5-[[4-anilino-6-[bis(2-hydroxyethyl)amino]-1,3,5-triazin-2-yl]amino]-2-[(e)-2-[4-[[4-anilino-6-[bis(2-hydroxyethyl)amino]-1,3,5-triazin-2-yl]amino]-2-sulfophenyl]ethenyl]benzenesulfonic acid Chemical compound N=1C(NC=2C=C(C(\C=C\C=3C(=CC(NC=4N=C(N=C(NC=5C=CC=CC=5)N=4)N(CCO)CCO)=CC=3)S(O)(=O)=O)=CC=2)S(O)(=O)=O)=NC(N(CCO)CCO)=NC=1NC1=CC=CC=C1 CNGYZEMWVAWWOB-VAWYXSNFSA-N 0.000 description 6
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 6
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 6
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- LEJBBGNFPAFPKQ-UHFFFAOYSA-N 2-(2-prop-2-enoyloxyethoxy)ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOC(=O)C=C LEJBBGNFPAFPKQ-UHFFFAOYSA-N 0.000 description 4
- 238000004042 decolorization Methods 0.000 description 4
- 230000001804 emulsifying effect Effects 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 3
- 238000002835 absorbance Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 238000005273 aeration Methods 0.000 description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 125000001165 hydrophobic group Chemical group 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 description 1
- IYFATESGLOUGBX-YVNJGZBMSA-N Sorbitan monopalmitate Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O IYFATESGLOUGBX-YVNJGZBMSA-N 0.000 description 1
- PRXRUNOAOLTIEF-ADSICKODSA-N Sorbitan trioleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](OC(=O)CCCCCCC\C=C/CCCCCCCC)[C@H]1OC[C@H](O)[C@H]1OC(=O)CCCCCCC\C=C/CCCCCCCC PRXRUNOAOLTIEF-ADSICKODSA-N 0.000 description 1
- 238000004847 absorption spectroscopy Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001045 blue dye Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- VFRQEVIIBMUKCQ-UHFFFAOYSA-M ethyl-dimethyl-(2-prop-2-enoyloxyethyl)azanium;chloride Chemical compound [Cl-].CC[N+](C)(C)CCOC(=O)C=C VFRQEVIIBMUKCQ-UHFFFAOYSA-M 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000001471 micro-filtration Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000001728 nano-filtration Methods 0.000 description 1
- 239000012875 nonionic emulsifier Substances 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 description 1
- 229920000053 polysorbate 80 Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- MLGWTHRHHANFCC-UHFFFAOYSA-N prop-2-en-1-amine;hydrochloride Chemical compound Cl.NCC=C MLGWTHRHHANFCC-UHFFFAOYSA-N 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000001044 red dye Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000002207 thermal evaporation Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
- C08F226/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a single or double bond to nitrogen
-
- 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
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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
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Abstract
The invention discloses a cationic flocculant and a preparation method thereof. The cationic flocculant is prepared by carrying out polymerization reaction on reaction monomers comprising a cationic monomer and a hydrophobic monomer under the action of a free-radical initiator, wherein the cationic monomer comprises one or combination of more of acryloyloxyethyl alkyl quaternary ammonium salts and/or allyl alkyl quaternary ammonium salts; the hydrophobic monomer comprises one or combination of more of styrene, acrylonitrile, vinyl acetate, vinyltrimethoxysilane, vinyltriethoxysilane and acrylate; and the free-radical initiator comprises one or combination of more of azodiisobutyronitrile, azodiisohexyl cyanide, azodiisobutylamidine hydrochloride, cyclohexanone peroxide, benzoperoxide and persulfate. The flocculant can adsorb anionic dyes, has favorable affinity with electrically neutral organic matters or organic matters with a small amount of anions, and has excellent flocculating settling effect.
Description
Technical Field
The invention relates to a cationic flocculant and a preparation method thereof, belonging to the field of wastewater treatment.
Background
Printing and dyeing wastewater is one of the important bottlenecks limiting the development of the printing and dyeing industry. The printing and dyeing mill can generate 3-5 tons of wastewater when processing 100 meters of fabrics, so the pollution problem of the printing and dyeing industry must be solved to realize the sustainable development of the printing and dyeing industry.
The printing and dyeing wastewater discharged by different procedures contains different contents of organic matters (including various printing and dyeing auxiliaries, dyes, fluorescent brighteners and the like) and inorganic salts, and the requirements of different process stages on water quality are different.
The scheme for recycling the printing and dyeing wastewater in practical application at home and abroad at present mainly comprises the following steps: the method comprises the following steps of firstly, wastewater-secondary biochemical treatment-sand filter-recycling, dyeing wastewater-secondary biochemical treatment-electrochemical treatment-chemical flocculation-ion exchange resin-recycling, dyeing wastewater-secondary biological treatment-second-sample chlorine oxidation (or ozone oxidation/catalytic oxidation) -filtration-recycling, secondly, dyeing wastewater-grid-water storage tank-ozone oxidation-activated carbon adsorption tower-pH adjusting tank-recycling, fifthly, dyeing wastewater-coagulating sedimentation-anaerobic acidification (24h) -HCR or biological activated carbon-secondary sedimentation tank-fiber ball filtration-recycling, and thirdly, wastewater-secondary biological treatment-Microfiltration (MF) -Nanofiltration (NF) -recycling; seventhly, printing and dyeing wastewater is clarified, sand filtered, anaerobically oxidized, Ultrafiltered (UF) and recycled, and the process comprises the steps of hydrolysis, coagulation and compound biological tank; ninthly hydrolysis, contact oxidation and active carbon (the detailed content refers to the literature that the recycling of the Pujiuqing dyeing wastewater and the influence factors thereof are researched [ D ]. Tianjin: Tianjin industry university, 2006], [ Liuweijing: deep degradation process and engineering application research of the printing and dyeing wastewater [ D ]. Nanjing: Nanjing Physician university, 2013 ]).
In the scheme, multi-stage treatment is generally needed, the treatment effect on the printing and dyeing wastewater with high concentration, high chromaticity and complex components is good, the treatment effect can meet the water quality requirement of partial working procedures, and the application of the printing and dyeing wastewater is limited only because the regeneration cost is overhigh and higher than that of fresh water.
In the printing and dyeing processes of reactive dyes or acid dyes, some processes or steps discharge wastewater with low chroma, such as liquid ammonia mercerizing washing wastewater and partial washing wastewater of a dyeing process, if the wastewater can be directly recycled to partial washing processes through simple flocculation treatment (the requirements on chroma and fluorescent brightener content are higher, but the requirements on COD content and inorganic salt content are low), the wastewater discharge amount can be reduced, the water consumption can be reduced, and the treatment cost of the collected wastewater can be reduced (the collected wastewater generally needs multistage advanced treatment due to complex sources).
Among the flocculants for treating printing and dyeing wastewater of a plurality of reactive dyes, the macromolecular cationic flocculant is widely used by virtue of the advantages of small using amount, high relative molecular weight, high flocculation speed, small influence of factors such as salt, temperature and the like. The commercial cationic flocculants sold in the market at present are copolymers of quaternary ammonium salt monomers (such as dimethyl diallyl ammonium chloride, (methyl) acryloyloxyethyl trimethyl ammonium chloride and allyl ammonium chloride) and acrylamide, and have the advantages of high molecular weight, high cation content (high cation degree) of high polymer per unit mass, good water solubility and good flocculation effect. The commercial cationic flocculant is mainly used for adsorbing anionic dyes through electrostatic attraction, although most of active dyes, acid dyes and fluorescent whitening agents can be flocculated, incomplete flocculation is easy to generate during flocculation treatment, particularly for low-concentration active dyes, acid dyes and fluorescent whitening agent wastewater, after flocculation precipitation is finished, a water body obtained by filtration is still a light-colored solution, the direct reuse standard cannot be achieved, and ozone aeration or other modes for decolorization treatment are further adopted.
Therefore, it is an urgent problem to be solved in the art to provide a cationic flocculant suitable for use in dyeing wastewater containing anionic dyes.
Disclosure of Invention
In order to solve the above technical problems, an object of the present invention is to provide a cationic flocculant which has not only a good electrostatic attraction effect on various anionic substances but also a good affinity for various organic substances having no or a small amount of anions, and has an excellent flocculation precipitation effect.
In order to achieve the above object, the present invention provides a cationic flocculant obtained by polymerizing reaction monomers under the action of a radical initiator; the reaction monomer comprises 30-80 parts of cationic monomer and 20-50 parts of hydrophobic monomer, and 0.1-2 parts of free radical initiator; wherein,
the cationic monomer comprises one or more of acryloxyethyl alkyl quaternary ammonium salt and/or allyl alkyl quaternary ammonium salt;
the hydrophobic monomer comprises one or a combination of more of styrene, acrylonitrile, vinyl acetate, vinyl trimethoxy silane, vinyl triethoxy silane and acrylate;
the free radical initiator comprises one or a combination of a plurality of azodiisobutyronitrile, azodiisoheptonitrile, azodiisobutyl amidine hydrochloride, cyclohexanone peroxide, benzoyl peroxide and persulfate.
The commercial cationic flocculant sold in the market at present only utilizes the electrostatic attraction of cations, when some active or acid dyes containing less anions exist in the solution, the electrostatic attraction of the cations to the cationic flocculant is insufficient, particularly, a large amount of fluorescent whitening agent exists in the solution, and because the auxiliary agent contains less anionic groups (such as sulfonic groups and carboxyl groups) and the flocculant has good water solubility, the flocculant is difficult to completely flocculate and precipitate by the electrostatic attraction alone, and the flocculant cannot completely precipitate even if the dosage of the flocculant is increased, so that the recycling requirement is met; the cationic flocculant provided by the invention not only contains a large number of cationic groups, but also contains a large number of hydrophobic groups, wherein the cationic groups can adsorb substances with a large number of anions (such as reactive dyes and acid dyes) through electrostatic attraction, and the hydrophobic groups can rapidly aggregate organic substances without electricity or with a small number of anions (such as fluorescent whitening agents) into insoluble flocs through hydrophobic association; therefore, compared with the traditional cationic flocculant, the cationic flocculant provided by the invention has the advantages of high flocculation speed and more thorough flocculation effect.
In the above cationic flocculant, preferably, the acryloyloxyethyl alkyl quaternary ammonium salt includes one or a combination of several of acryloyloxyethyl trimethyl ammonium chloride, acryloyloxyethyl trimethyl ammonium bromide, methacryloyloxyethyl trimethyl ammonium chloride and methacryloyloxyethyl trimethyl ammonium bromide.
In the above cationic flocculant, preferably, the allyl alkyl quaternary ammonium salt includes one or a combination of several of allyl trimethyl ammonium chloride, allyl trimethyl ammonium bromide, dimethyl diallyl ammonium chloride, dimethyl diallyl ammonium bromide, dodecyl dimethyl allyl ammonium chloride, dodecyl dimethyl allyl ammonium bromide, tetradecyl dimethyl allyl ammonium chloride, tetradecyl dimethyl allyl ammonium bromide, hexadecyl dimethyl allyl ammonium chloride, hexadecyl dimethyl allyl ammonium bromide, octadecyl dimethyl allyl ammonium chloride, and octadecyl dimethyl allyl ammonium bromide.
The cationic monomer provided by the invention can form good electrostatic attraction with substances with a large number of anions (such as reactive dyes and acid dyes).
In the above cationic flocculant, preferably, the acrylate includes one or a combination of methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, octyl acrylate, octyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, pentaerythritol triacrylate, diethylene glycol acrylate.
The special hydrophobic structure of the hydrophobic monomer provided by the invention has good affinity to organic matters (such as fluorescent whitening agents) without electric charges or with a small amount of anions, and the hydrophobic monomer can be easily aggregated into insoluble flocs through hydrophobic association, so that the speed of flocculation and precipitation is accelerated, and the flocculation effect is more thorough.
In the above cationic flocculant, preferably, the reactive monomer further includes a water-soluble monomer; more preferably, the water-soluble monomer comprises one or a combination of more of acrylamide, acrylic acid, methacrylic acid, maleic anhydride and N, N-methylene-bisacrylamide; further preferably, the amount of the water-soluble monomer added is not more than 20 parts by mass. The water-soluble monomer is added to regulate the solubility of the cationic flocculant in water.
The invention also provides a preparation method of the cationic flocculant, which comprises the process of carrying out polymerization reaction on reaction monomers under the action of a free radical initiator; wherein, the reaction temperature is 40-90 ℃ and the reaction time is 4-12h when the polymerization reaction is carried out.
In the above production method, preferably, when the polymerization reaction is carried out, the polymerization manner includes solution polymerization, emulsion polymerization or inverse emulsion polymerization.
In the above production method, preferably, the solution polymerization comprises the steps of:
step one, adding an organic solvent and a reaction monomer into a reaction container, stirring and heating to 60-85 ℃; wherein, the reaction monomer comprises a cationic monomer and a hydrophobic monomer, and can also comprise a water-soluble monomer;
step two, adding a part of free radical initiator (the adding amount of the part of free radical initiator is preferably 50 percent of the total mass of the free radical initiator) into a reaction vessel for heat preservation reaction, wherein the reaction time is preferably 5-8h, and adding the rest free radical initiator into the reaction vessel in batches in the reaction process; after the reaction is finished, cooling the reaction container to room temperature to obtain a cationic flocculant, wherein the solid content of the flocculant is 20-70%; wherein, the free radical initiator comprises one or a combination of a plurality of azodiisobutyronitrile, azodiisoheptonitrile, azodiisobutyl amidine hydrochloride, cyclohexanone peroxide and benzoyl peroxide.
In the above solution polymerization method, preferably, the total addition amount of the organic solvent is 50 to 200 parts by mass; more preferably, the organic solvent comprises one or more of methanol, ethanol, propanol, isopropanol, N-butanol, tetrahydrofuran, ethyl acetate, butyl acetate, acetone, 1, 4-dioxane, N-dimethylformamide, N-dimethylacetamide and dimethyl sulfoxide.
In the above production method, preferably, the emulsion polymerization comprises the steps of:
step one, adding water and partial reaction monomers into a reaction container, stirring and heating to 60-85 ℃; wherein, the reactive monomer comprises a cationic monomer and a hydrophobic monomer (the adding amount of the part of the hydrophobic monomer is 25-40% of the total mass of the hydrophobic monomer), and can also comprise a water-soluble monomer (the adding amount of the part of the water-soluble monomer is 25-40% of the total mass of the water-soluble monomer);
step two, adding a part of free radical initiator (the adding amount of the part of free radical initiator is preferably 50 percent of the total mass of the free radical initiator) into a reaction container, simultaneously dropwise adding the rest reaction monomers into the reaction container, completing dropwise adding within 1-3h, supplementing the rest free radical initiator after completing dropwise adding, and then reacting for 4-7h at 70-90 ℃; after the reaction is finished, cooling the reaction container to room temperature to obtain a cationic flocculant, wherein the solid content of the flocculant is 20-60%; wherein, the free radical initiator is one or the combination of a plurality of azodiisobutyl amidine hydrochloride and persulfate.
In the above emulsion polymerization method, preferably, the total amount of the water added is 100-200 parts by mass.
In the above production method, preferably, the inverse emulsion polymerization comprises the steps of:
step one, adding water, a disperse phase medium and an emulsifier into a reaction vessel, and carrying out high-speed shearing to form an emulsion, wherein the high-speed shearing refers to the shearing rate of 12000 r/min; in actual operation, the shear rate needs to be adjusted according to the stability of the emulsion, so the shear rate is not particularly limited in the invention;
adding a reaction monomer into a reaction container, introducing nitrogen into the reaction container, heating the reaction container to 45-80 ℃, adding a free radical initiator into the reaction container, reacting for 3-8h, demulsifying, and removing a dispersed phase medium to obtain a cationic flocculant; wherein the disperse phase medium comprises one or a combination of several of C6-C18 alkane, petroleum ether, kerosene, liquid paraffin, toluene and xylene; the emulsifier is a nonionic surfactant, and the nonionic surfactant comprises one or a combination of more of Span series, Tween series and/or OP series; the free radical initiator comprises one or a combination of more of persulfate-sulfite, azobisisobutyronitrile and azobisisobutylamidine hydrochloride; the reactive monomer comprises a cationic monomer and a hydrophobic monomer, and can also comprise a water-soluble monomer; the demulsification means includes, but is not limited to, thermal evaporation, sonication, centrifugation, demulsification agent addition, or freezing.
In the above-mentioned inverse emulsion polymerization method, preferably, the total addition amount of the water is 20 to 80 parts, the total addition amount of the dispersed phase medium is 80 to 160 parts, and the total addition amount of the nonionic emulsifier is 4 to 10 parts by mass.
The cationic flocculant provided by the invention can be applied to printing and dyeing wastewater containing anionic dyes and/or fluorescent whitening agents, and particularly has excellent flocculation and precipitation effects on the printing and dyeing wastewater with the content of the anionic dyes and/or the fluorescent whitening agents being lower than 50 mg/L.
The invention has the beneficial effects that:
1) the flocculant provided by the invention contains a large amount of cations in the structure, and has good electrostatic attraction effect on various anionic substances (such as reactive dyes and acid dyes); meanwhile, the structure of the flocculant also contains a large number of special hydrophobic structures, the flocculant has good affinity to various organic matters without electricity or with a small number of anions (such as fluorescent whitening agents), and the organic matters can be rapidly aggregated into insoluble flocs through hydrophobic association, so that the speed of flocculation and precipitation is increased, and the flocculation effect is more thorough;
2) the traditional cationic flocculant has incomplete flocculation effect, and particularly for wastewater containing low-concentration reactive dyes, acid dyes and fluorescent whitening agents, the flocculated water body still has colors and cannot reach the recycling standard; the cationic flocculant provided by the invention has a very good flocculation effect on wastewater containing active dyes, acid dyes and fluorescent whitening agents, particularly low-chroma dyeing wastewater and wastewater containing the fluorescent whitening agents, and researches show that when the total content of the fluorescent whitening agents and the active dyes in the wastewater is lower than 50mg/L, the cationic flocculant provided by the invention has a very good removal rate on the fluorescent whitening agents and the active dyes, the wastewater can meet the recycling requirement after flocculation precipitation, and the effect is very obvious without advanced treatment such as ozone aeration and the like.
Detailed Description
The technical solutions of the present invention will be described in detail below in order to clearly understand the technical features, objects, and advantages of the present invention, but the present invention is not limited to the practical scope of the present invention.
Example 1
This example provides a cationic flocculant. The composition of the cation flocculated feed is shown in table 1.
TABLE 1 feed composition of cationic flocculants
The preparation method of the cationic flocculant comprises the following steps:
adding 80g of ethanol and all monomers (hydrophobic monomers, water-soluble monomers and cationic monomers) into a three-neck flask, stirring and mixing uniformly, heating to 70 ℃, adding 0.4g of azobisisobutyronitrile, preserving heat for 2 hours, supplementing 0.2g of azobisisobutyronitrile, heating to 80 ℃, continuing to react for 7 hours, finishing the polymerization reaction, and cooling to obtain the cationic flocculant.
Example 2
This example provides a cationic flocculant. The composition of the cation flocculated feed is shown in table 2.
The preparation method of the cationic flocculant comprises the following steps:
adding 40g of ethanol, 30g of n-propanol, 20g of dimethyl diallyl ammonium bromide, 20g of allyl trimethyl ammonium chloride, 4g of ethyl acrylate and 4g of n-octyl methacrylate into a three-neck flask, uniformly stirring and mixing, heating to 85 ℃, adding 0.3g of benzoyl peroxide, keeping the temperature for 30min, beginning to dropwise add a mixed solution of 8g of ethyl acrylate, 8g of n-octyl methacrylate and 10g of n-propanol (the dropwise addition is completed within 2 h), supplementing 0.2g of benzoyl peroxide after the dropwise addition is completed, heating to 90 ℃, continuing to react for 5h, finishing the polymerization reaction, and cooling to obtain the cationic flocculant.
TABLE 2 feed composition of cationic flocculants
Example 3
This example provides a cationic flocculant having a feed composition as shown in table 3.
TABLE 3 feed composition of cationic flocculants
The preparation method of the cationic flocculant comprises the following steps:
(1) adding 80g of water, 10g of hexadecyl dimethyl allyl ammonium chloride, 40g of acryloyloxyethyl trimethyl ammonium chloride, 2.5g of methyl methacrylate, 0.5g of vinyl triethoxysilane, 4g of styrene and 1g of diethylene glycol diacrylate into a reaction vessel, and stirring and heating to 75 ℃;
(2) after the temperature is raised to 75 ℃, 0.2g of potassium persulfate and 0.2g of sodium bisulfite are added into a reaction vessel, polymerization is carried out for 30-45min at the temperature, and then the rest 17.5g of methyl methacrylate, 1.5g of vinyltriethoxysilane, 12g of styrene and 3g of diethylene glycol diacrylate are dropwise added into the reaction vessel, and the dropwise addition is finished within 2 h; after the dripping is finished, adding a free radical initiator (0.2g of potassium persulfate and 0.1g of sodium bisulfite), and finally carrying out heat preservation reaction at 80-85 ℃ for 7 h;
(3) and cooling to room temperature to obtain the cationic flocculant.
Example 4
This example provides a cationic flocculant having a feed composition as shown in table 4.
TABLE 4 feed composition of cationic flocculants
The preparation method of the cationic flocculant comprises the following steps:
(1) adding 80g of water, 10g of tetradecyl dimethyl allyl ammonium chloride, 10g of methacryloyloxyethyl trimethyl ammonium chloride, 3.75g of methyl acrylate, 0.5g of vinyl triethoxysilane, 3g of vinyl acetate and 2g of n-octyl acrylate into a reaction container, and stirring and heating to 75 ℃;
(2) after the temperature had risen to 75 ℃, 0.15g of potassium persulfate, 0.1g of sodium bisulfite, and 0.05g of azobisisobutylamidine hydrochloride were added to the reaction vessel, and polymerized at that temperature for 30 to 45min, and then the remaining 11.25g of methyl acrylate, 1.5g of vinyltriethoxysilane, 9g of vinyl acetate, 6g of n-octyl acrylate, and 30g of methacryloyloxyethyltrimethylammonium chloride were added dropwise to the reaction vessel over 2 hours; after the dropwise addition, the rest of free radical initiator (0.15g of potassium persulfate, 0.1g of sodium bisulfite and 0.15g of azodiisobutyl amidine hydrochloride) is added, and finally the reaction is carried out for 7 hours at the temperature of 80-85 ℃;
(3) and cooling to room temperature to obtain the cationic flocculant.
Example 5
This example provides a cationic flocculant having a feed composition as shown in table 5.
The preparation method of the cationic flocculant comprises the following steps:
adding 200mL of liquid paraffin, 4.8g of span80, 1.6g of Tween80, 120mL of deionized water and all the polymerized monomers (hydrophobic monomers, water-soluble monomers and cationic monomers) into a three-neck flask, then emulsifying for 45min at high speed on an emulsifying machine, and introducing nitrogen for protection; and then heating the three-neck flask to 60 ℃, preserving heat for 15min, adding 0.2g of azodiisobutyl amidine hydrochloride, 0.1g of potassium persulfate and 0.06g of sodium bisulfite into the three-neck flask, reacting at the constant temperature of 60 ℃ for 6h, finishing the polymerization reaction, finally heating the three-neck flask to 110 ℃ to stratify the oil and water, and removing the oil phase to obtain the cationic flocculant.
TABLE 5 feed composition of cationic flocculants
Example 6
This example provides a cationic flocculant having a feed composition as shown in table 6.
TABLE 6 feed composition of cationic flocculants
The preparation method of the cationic flocculant comprises the following steps:
adding 120mL of kerosene, 5.5g of span85, 4.5g of span40 and 100mL of deionized water into a three-neck flask, then emulsifying for 45min at a high speed on an emulsifying machine after all polymerized monomers (hydrophobic monomers, water-soluble monomers and cationic monomers) are added, and introducing nitrogen for protection; and then heating the three-neck flask to 60 ℃, preserving heat for 15min, adding 0.2g of azodiisobutyl amidine hydrochloride, 0.1g of potassium persulfate and 0.06g of sodium bisulfite into the three-neck flask, reacting for 6h at the constant temperature of 60 ℃, cooling to finish polymerization reaction, centrifuging to separate oil from water, and removing an oil phase to obtain the cationic flocculant.
And (3) testing the flocculation effect of the cationic flocculant:
the test method comprises the following steps: preparing reactive red dye Evercion Red-E3B, reactive blue dye Evercion blue ED-G, fluorescent brightener MST and fluorescent brightener BBT with different concentrations respectively to simulate printing and dyeing wastewater, then respectively putting the cationic flocculant and the commercial cationic flocculant KW178 (manufactured by the company of Anson (SNFFLOERGER)) provided in examples 1-6 into the simulated wastewater solution for flocculation and decoloration treatment, and measuring the absorbance of the wastewater solution before and after flocculation and precipitation of the flocculant by using ultraviolet visible absorption spectroscopy (wherein the wastewater containing the fluorescent brightener is measured and calculated according to the national standard GB/T21883-2008), and the calculation formula is shown as formula I:
formula I
In the formula I, A0Absorbance of the waste water solution before flocculation, A1The absorbance of the wastewater solution after flocculation precipitation filtration; and (3) testing and comparing the decolorizing and fluorescence removing effects of various cationic flocculants on the printing and dyeing wastewater.
1) Solutions of red reactive dyes (evercion red h-E3B) were prepared at different concentrations, and then the cationic flocculants provided in examples 1 to 6 and commercial flocculants (KW178, 59%) were used to perform the flocculation precipitation test (after adding the cationic flocculants provided in examples 1 to 6 and commercial cationic flocculants, 120mg/L of aluminum sulfate was added to assist precipitation), and the results are shown in table 7.
TABLE 7 flocculation Effect of different flocculants on Evercion RedH-E3B
As can be seen from Table 7, the cationic flocculant provided by the invention has good decolorizing effect on reactive dyes, and the decolorizing is more prominent along with the reduction of the dye concentration; compared with commercial cationic flocculants, the cationic flocculant provided by the invention has stronger flocculation capacity on low-concentration reactive dye solution (10mg/L), and the dye solution is almost colorless after flocculation and decoloration, so that the requirement of water quality in part of printing and dyeing processes is met.
2) Blue reactive dye (EvercionBlue ED-G) solutions with different concentrations were prepared, and then flocculating precipitation was performed by using the cationic flocculant and the commercial flocculant (KW178, solid content 59%) provided in examples 1-6, respectively (after adding the cationic flocculant and the commercial cationic flocculant provided in examples 1-6, 120mg/L aluminum sulfate was added to assist precipitation, respectively), and the results are shown in Table 8.
TABLE 8 flocculation Effect of different flocculants on Evercion BlueED-GB
As can be seen from Table 8, the cationic flocculant provided by the invention has good decolorizing effect on reactive dyes, and the decolorizing effect is more prominent with the reduction of the dye concentration.
When the concentration of EvercionBlueED-G is 20mg/L, the decoloring rate of the commercial cationic flocculant is still lower than that of the flocculant provided by example 3 even if the addition amount of the commercial cationic flocculant is doubled compared with that of the flocculant provided by example 3; when the dye concentration is respectively 20mg/L and 50mg/L, the residual concentration of the dye after flocculation by the commercial cationic flocculant is basically consistent, so that the decolorization rate is reduced to some extent when the decolorization rate is 20mg/L compared with 50mg/L, which shows that the decolorization effect of the commercial cationic flocculant on low-concentration dye wastewater is not good;
after the cationic flocculant provided by the embodiment 3 is used for flocculating and decoloring Evercion blue ED-G solutions with the concentrations of 20mg/L and 10mg/L respectively, wastewater is colorless, the water quality requirement of a part of printing and dyeing process is met, the defect that commercial flocculants are not completely decolored is overcome, and particularly when the concentration of the Evercion blue ED-G solution is 10mg/L, a good decoloring effect can be achieved by using a very small amount of the cationic flocculant provided by the embodiment 3;
examples 1-6 all provided cationic flocculants that exhibited better decolorizing performance than commercial flocculants at dye concentrations below 20 mg/L.
3) Fluorescent brightener solutions (BBT, MST as fluorescent brightener used) were prepared in different concentrations and subjected to the flocculation precipitation test using the cationic flocculant and commercial flocculant (KW178, 59% solids) provided in examples 1 and 3, respectively, and the results are shown in Table 9.
TABLE 9 flocculation Effect of different flocculants on fluorescent whitening agents MST and BBT
As can be seen from Table 9, the cationic flocculant prepared by the invention has better flocculation effect on the fluorescent whitening agent, particularly, the removal rate is close to 100% at lower concentration (less than or equal to 50mg/L), and compared with the corresponding commercial flocculant, the flocculation precipitation effect is obviously improved and the flocculant can be directly reused in part of processes, as can be seen from comparative examples (commercial flocculant KW178) and 3.
In conclusion, the cationic flocculant provided by the invention has good flocculation capacity for dyeing wastewater with low content of active dyes and/or fluorescent whitening agents (the content of the fluorescent whitening agents and/or the active dyes is lower than 50mg/L), and wastewater after flocculation and decoloration can be directly reused in part of printing and dyeing processes, so that the cationic flocculant has good application prospect.
Claims (10)
1. A cationic flocculant, which is obtained by carrying out polymerization reaction on reaction monomers under the action of a free radical initiator; the reaction monomer comprises 30-80 parts of cationic monomer and 20-50 parts of hydrophobic monomer, and 0.1-2 parts of free radical initiator; wherein,
the cationic monomer comprises one or more of acryloxyethyl alkyl quaternary ammonium salt and/or allyl alkyl quaternary ammonium salt;
the hydrophobic monomer comprises one or a combination of more of styrene, acrylonitrile, vinyl acetate, vinyl trimethoxy silane, vinyl triethoxy silane and acrylate;
the free radical initiator comprises one or a combination of a plurality of azodiisobutyronitrile, azodiisoheptonitrile, azodiisobutyl amidine hydrochloride, cyclohexanone peroxide, benzoyl peroxide and persulfate.
2. The cationic flocculant of claim 1, wherein: the acryloyloxyethyl alkyl quaternary ammonium salt comprises one or a combination of more of acryloyloxyethyl trimethyl ammonium chloride, acryloyloxyethyl trimethyl ammonium bromide, methacryloyloxyethyl trimethyl ammonium chloride and methacryloyloxyethyl trimethyl ammonium bromide.
3. The cationic flocculant of claim 1 or 2, wherein: the allyl alkyl quaternary ammonium salt comprises one or a combination of more of allyl trimethyl ammonium chloride, allyl trimethyl ammonium bromide, dimethyl diallyl ammonium chloride, dimethyl diallyl ammonium bromide, dodecyl dimethyl allyl ammonium chloride, dodecyl dimethyl allyl ammonium bromide, tetradecyl dimethyl allyl ammonium chloride, tetradecyl dimethyl allyl ammonium bromide, hexadecyl dimethyl allyl ammonium chloride, hexadecyl dimethyl allyl ammonium bromide, octadecyl dimethyl allyl ammonium chloride and octadecyl dimethyl allyl ammonium bromide.
4. The cationic flocculant of any one of claims 1-3, wherein: the acrylate comprises one or more of methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, octyl acrylate, octyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, pentaerythritol triacrylate and diethylene glycol acrylate.
5. The cationic flocculant of any one of claims 1-4, wherein: the reactive monomers further include water soluble monomers;
preferably, the water-soluble monomer comprises one or a combination of more of acrylamide, acrylic acid, methacrylic acid, maleic anhydride and N, N-methylene-bisacrylamide;
more preferably, the water-soluble monomer is added in an amount of not more than 20 parts by mass.
6. A method for preparing the cationic flocculant according to any one of claims 1 to 5, which comprises a step of polymerizing reaction monomers by a radical initiator; wherein, the reaction temperature is 40-90 ℃ and the reaction time is 4-12h when the polymerization reaction is carried out.
7. The production method according to claim 6, wherein: when the polymerization reaction is carried out, the polymerization manner includes solution polymerization, emulsion polymerization or inverse emulsion polymerization.
8. The production method according to claim 7, wherein: the solution polymerization comprises the following steps:
step one, adding an organic solvent and a reaction monomer into a reaction container, stirring and heating to 60-90 ℃;
step two, adding a free radical initiator into the reaction vessel in batches for reaction to obtain a cationic flocculant;
preferably, the total adding amount of the organic solvent is 50-200 parts by mass;
more preferably, the organic solvent comprises one or more of methanol, ethanol, propanol, isopropanol, N-butanol, tetrahydrofuran, ethyl acetate, butyl acetate, acetone, 1, 4-dioxane, N-dimethylformamide, N-dimethylacetamide and dimethyl sulfoxide.
9. The production method according to claim 7 or 8, wherein: the emulsion polymerization comprises the following steps:
step one, adding water and partial reaction monomers into a reaction container, stirring and heating to 60-85 ℃;
and step two, adding part of the free radical initiator and the rest of the reaction monomers into the reaction vessel, completing the addition within 1-3h, then supplementing the rest of the free radical initiator, and reacting for 4-7h at 70-90 ℃ to obtain the cationic flocculant.
10. The production method according to any one of claims 7 to 9, wherein: the inverse emulsion polymerization comprises the following steps:
step one, adding water, a disperse phase medium and an emulsifier into a reaction vessel, and shearing at a high speed to form an emulsion;
adding a reaction monomer into a reaction container, introducing nitrogen into the reaction container, heating the reaction container to 45-80 ℃, adding a free radical initiator into the reaction container, performing demulsification and removing a dispersed phase medium after reacting for 3-8 hours to obtain a cationic flocculant; wherein,
the disperse phase medium comprises one or a combination of more of C6-C18 alkane, petroleum ether, kerosene, liquid paraffin, toluene and xylene;
the emulsifier is a nonionic surfactant, and the nonionic surfactant comprises one or a combination of more of Span series, Tween series and/or OP series.
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