CN117089019B - Modified aqueous solution polyacrylamide flocculant and preparation method thereof - Google Patents
Modified aqueous solution polyacrylamide flocculant and preparation method thereof Download PDFInfo
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- CN117089019B CN117089019B CN202311344758.2A CN202311344758A CN117089019B CN 117089019 B CN117089019 B CN 117089019B CN 202311344758 A CN202311344758 A CN 202311344758A CN 117089019 B CN117089019 B CN 117089019B
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- Prior art keywords
- aqueous solution
- polyacrylamide
- modification
- hydrolysis
- monomer
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- 239000007864 aqueous solution Substances 0.000 title claims abstract description 196
- 229920002401 polyacrylamide Polymers 0.000 title claims abstract description 188
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 230000004048 modification Effects 0.000 claims abstract description 127
- 238000012986 modification Methods 0.000 claims abstract description 127
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 88
- 230000007062 hydrolysis Effects 0.000 claims abstract description 85
- 239000000178 monomer Substances 0.000 claims abstract description 76
- 239000000243 solution Substances 0.000 claims abstract description 63
- 239000003999 initiator Substances 0.000 claims abstract description 42
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 38
- 239000003607 modifier Substances 0.000 claims abstract description 38
- 239000003377 acid catalyst Substances 0.000 claims abstract description 34
- 238000005886 esterification reaction Methods 0.000 claims abstract description 34
- 230000032050 esterification Effects 0.000 claims abstract description 33
- 238000005902 aminomethylation reaction Methods 0.000 claims abstract description 31
- 239000007853 buffer solution Substances 0.000 claims abstract description 25
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 25
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 19
- 229910052751 metal Inorganic materials 0.000 claims abstract description 18
- 239000002184 metal Substances 0.000 claims abstract description 18
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims abstract description 16
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000005904 alkaline hydrolysis reaction Methods 0.000 claims abstract description 12
- 239000008139 complexing agent Substances 0.000 claims abstract description 12
- 239000006184 cosolvent Substances 0.000 claims abstract description 12
- 239000002270 dispersing agent Substances 0.000 claims abstract description 12
- 239000012986 chain transfer agent Substances 0.000 claims abstract description 11
- 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 abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 239000011734 sodium Substances 0.000 claims abstract description 8
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 7
- 150000001336 alkenes Chemical class 0.000 claims abstract description 7
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 7
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 4
- 125000000446 sulfanediyl group Chemical group *S* 0.000 claims abstract 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 85
- 238000002156 mixing Methods 0.000 claims description 31
- 150000001412 amines Chemical class 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- 238000006116 polymerization reaction Methods 0.000 claims description 26
- 238000010438 heat treatment Methods 0.000 claims description 22
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 21
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 20
- 239000003085 diluting agent Substances 0.000 claims description 18
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical group O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 15
- XQKRYBXCYCKQLL-UHFFFAOYSA-N dimethylaminomethanol Chemical compound CN(C)CO XQKRYBXCYCKQLL-UHFFFAOYSA-N 0.000 claims description 15
- 238000005502 peroxidation Methods 0.000 claims description 13
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- 150000001299 aldehydes Chemical class 0.000 claims description 12
- 229960000583 acetic acid Drugs 0.000 claims description 10
- 230000000655 anti-hydrolysis Effects 0.000 claims description 10
- 239000012362 glacial acetic acid Substances 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- 230000000977 initiatory effect Effects 0.000 claims description 9
- WVMSIBFANXCZKT-UHFFFAOYSA-N triethyl(hydroxy)silane Chemical compound CC[Si](O)(CC)CC WVMSIBFANXCZKT-UHFFFAOYSA-N 0.000 claims description 9
- CUNWUEBNSZSNRX-RKGWDQTMSA-N (2r,3r,4r,5s)-hexane-1,2,3,4,5,6-hexol;(z)-octadec-9-enoic acid Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO.OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO.CCCCCCCC\C=C/CCCCCCCC(O)=O.CCCCCCCC\C=C/CCCCCCCC(O)=O.CCCCCCCC\C=C/CCCCCCCC(O)=O CUNWUEBNSZSNRX-RKGWDQTMSA-N 0.000 claims description 8
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 8
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 8
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 claims description 8
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 claims description 8
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 8
- 239000003112 inhibitor Substances 0.000 claims description 8
- BWYYYTVSBPRQCN-UHFFFAOYSA-M sodium;ethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=C BWYYYTVSBPRQCN-UHFFFAOYSA-M 0.000 claims description 8
- 229960005078 sorbitan sesquioleate Drugs 0.000 claims description 8
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims description 8
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 claims description 8
- QWUWMCYKGHVNAV-UHFFFAOYSA-N 1,2-dihydrostilbene Chemical group C=1C=CC=CC=1CCC1=CC=CC=C1 QWUWMCYKGHVNAV-UHFFFAOYSA-N 0.000 claims description 7
- FULZLIGZKMKICU-UHFFFAOYSA-N N-phenylthiourea Chemical compound NC(=S)NC1=CC=CC=C1 FULZLIGZKMKICU-UHFFFAOYSA-N 0.000 claims description 7
- ROSDSFDQCJNGOL-UHFFFAOYSA-N protonated dimethyl amine Natural products CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 6
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 6
- VZXOZSQDJJNBRC-UHFFFAOYSA-N 4-chlorobenzenethiol Chemical compound SC1=CC=C(Cl)C=C1 VZXOZSQDJJNBRC-UHFFFAOYSA-N 0.000 claims description 5
- JGHKDVSIFPFNIJ-UHFFFAOYSA-N dodecylsulfanylmethanedithioic acid Chemical group CCCCCCCCCCCCSC(S)=S JGHKDVSIFPFNIJ-UHFFFAOYSA-N 0.000 claims description 5
- 229940078490 n,n-dimethylglycine Drugs 0.000 claims description 5
- GQECANUIPBFPLA-UHFFFAOYSA-N 2-(carboxymethylsulfanylcarbothioylsulfanyl)acetic acid Chemical compound OC(=O)CSC(=S)SCC(O)=O GQECANUIPBFPLA-UHFFFAOYSA-N 0.000 claims description 4
- USJDOLXCPFASNV-UHFFFAOYSA-N 9-bromononan-1-ol Chemical compound OCCCCCCCCCBr USJDOLXCPFASNV-UHFFFAOYSA-N 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- BHATUINFZWUDIX-UHFFFAOYSA-N Zwittergent 3-14 Chemical compound CCCCCCCCCCCCCC[N+](C)(C)CCCS([O-])(=O)=O BHATUINFZWUDIX-UHFFFAOYSA-N 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- SONHXMAHPHADTF-UHFFFAOYSA-M sodium;2-methylprop-2-enoate Chemical compound [Na+].CC(=C)C([O-])=O SONHXMAHPHADTF-UHFFFAOYSA-M 0.000 claims description 4
- ANHSGCWTORACPM-UHFFFAOYSA-N triazanium phosphoric acid phosphate Chemical compound [NH4+].[NH4+].[NH4+].OP(O)(O)=O.[O-]P([O-])([O-])=O ANHSGCWTORACPM-UHFFFAOYSA-N 0.000 claims description 4
- IDBNECMSCRAUNU-UHFFFAOYSA-N 1-ethylpyrrolidin-3-ol Chemical compound CCN1CCC(O)C1 IDBNECMSCRAUNU-UHFFFAOYSA-N 0.000 claims description 3
- RAUHREXYGRKIOJ-UHFFFAOYSA-N 1h-imidazole-5-carbodithioic acid Chemical compound SC(=S)C1=CN=CN1 RAUHREXYGRKIOJ-UHFFFAOYSA-N 0.000 claims description 3
- KYNFOMQIXZUKRK-UHFFFAOYSA-N 2,2'-dithiodiethanol Chemical compound OCCSSCCO KYNFOMQIXZUKRK-UHFFFAOYSA-N 0.000 claims description 3
- ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 2,3-dimethylbutane Chemical group CC(C)C(C)C ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 0.000 claims description 3
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 3
- BIISIZOQPWZPPS-UHFFFAOYSA-N 2-tert-butylperoxypropan-2-ylbenzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=CC=C1 BIISIZOQPWZPPS-UHFFFAOYSA-N 0.000 claims description 3
- RVBUGGBMJDPOST-UHFFFAOYSA-N 2-thiobarbituric acid Chemical compound O=C1CC(=O)NC(=S)N1 RVBUGGBMJDPOST-UHFFFAOYSA-N 0.000 claims description 3
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 claims description 3
- PTVZQOAHCSKAAS-UHFFFAOYSA-N 4-methyl-3-thiosemicarbazide Chemical compound CNC(=S)NN PTVZQOAHCSKAAS-UHFFFAOYSA-N 0.000 claims description 3
- KKIGUVBJOHCXSP-UHFFFAOYSA-N 4-phenylthiosemicarbazide Chemical compound NNC(=S)NC1=CC=CC=C1 KKIGUVBJOHCXSP-UHFFFAOYSA-N 0.000 claims description 3
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 3
- FSVCELGFZIQNCK-UHFFFAOYSA-N N,N-bis(2-hydroxyethyl)glycine Chemical compound OCCN(CCO)CC(O)=O FSVCELGFZIQNCK-UHFFFAOYSA-N 0.000 claims description 3
- 239000004280 Sodium formate Substances 0.000 claims description 3
- 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 claims description 3
- HVUMOYIDDBPOLL-XWVZOOPGSA-N Sorbitan monostearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O HVUMOYIDDBPOLL-XWVZOOPGSA-N 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 3
- 229940090960 diethylenetriamine pentamethylene phosphonic acid Drugs 0.000 claims description 3
- DUYCTCQXNHFCSJ-UHFFFAOYSA-N dtpmp Chemical compound OP(=O)(O)CN(CP(O)(O)=O)CCN(CP(O)(=O)O)CCN(CP(O)(O)=O)CP(O)(O)=O DUYCTCQXNHFCSJ-UHFFFAOYSA-N 0.000 claims description 3
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 claims description 3
- BPCNEKWROYSOLT-UHFFFAOYSA-N n-phenylprop-2-enamide Chemical compound C=CC(=O)NC1=CC=CC=C1 BPCNEKWROYSOLT-UHFFFAOYSA-N 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- BHZOKUMUHVTPBX-UHFFFAOYSA-M sodium acetic acid acetate Chemical compound [Na+].CC(O)=O.CC([O-])=O BHZOKUMUHVTPBX-UHFFFAOYSA-M 0.000 claims description 3
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 claims description 3
- 235000019254 sodium formate Nutrition 0.000 claims description 3
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 3
- ZDQYSKICYIVCPN-UHFFFAOYSA-L sodium succinate (anhydrous) Chemical compound [Na+].[Na+].[O-]C(=O)CCC([O-])=O ZDQYSKICYIVCPN-UHFFFAOYSA-L 0.000 claims description 3
- XFTALRAZSCGSKN-UHFFFAOYSA-M sodium;4-ethenylbenzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=C(C=C)C=C1 XFTALRAZSCGSKN-UHFFFAOYSA-M 0.000 claims description 3
- 235000011071 sorbitan monopalmitate Nutrition 0.000 claims description 3
- 239000001570 sorbitan monopalmitate Substances 0.000 claims description 3
- 229940031953 sorbitan monopalmitate Drugs 0.000 claims description 3
- 239000001587 sorbitan monostearate Substances 0.000 claims description 3
- 235000011076 sorbitan monostearate Nutrition 0.000 claims description 3
- 229940035048 sorbitan monostearate Drugs 0.000 claims description 3
- FGWRMMTYIZKYMA-UHFFFAOYSA-N tert-butyl-hydroxy-dimethylsilane Chemical compound CC(C)(C)[Si](C)(C)O FGWRMMTYIZKYMA-UHFFFAOYSA-N 0.000 claims description 3
- XPFJYKARVSSRHE-UHFFFAOYSA-K trisodium;2-hydroxypropane-1,2,3-tricarboxylate;2-hydroxypropane-1,2,3-tricarboxylic acid Chemical compound [Na+].[Na+].[Na+].OC(=O)CC(O)(C(O)=O)CC(O)=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O XPFJYKARVSSRHE-UHFFFAOYSA-K 0.000 claims description 3
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical group C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 4
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 38
- 238000005189 flocculation Methods 0.000 abstract description 29
- 230000016615 flocculation Effects 0.000 abstract description 29
- 239000010865 sewage Substances 0.000 abstract description 24
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 22
- 150000002500 ions Chemical class 0.000 abstract description 21
- 230000032683 aging Effects 0.000 abstract description 7
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 abstract 1
- 239000000047 product Substances 0.000 description 48
- 238000003756 stirring Methods 0.000 description 43
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 42
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 38
- 239000010949 copper Substances 0.000 description 34
- 238000006243 chemical reaction Methods 0.000 description 31
- 238000001816 cooling Methods 0.000 description 26
- 125000003368 amide group Chemical group 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 22
- 229910052757 nitrogen Inorganic materials 0.000 description 19
- 125000004149 thio group Chemical group *S* 0.000 description 18
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 16
- 229910052717 sulfur Inorganic materials 0.000 description 16
- 239000011593 sulfur Substances 0.000 description 16
- 239000008367 deionised water Substances 0.000 description 12
- 229910021641 deionized water Inorganic materials 0.000 description 12
- 230000011987 methylation Effects 0.000 description 12
- 238000007069 methylation reaction Methods 0.000 description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 11
- 238000007664 blowing Methods 0.000 description 11
- 229910052760 oxygen Inorganic materials 0.000 description 11
- 239000001301 oxygen Substances 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- 239000006228 supernatant Substances 0.000 description 10
- 239000011550 stock solution Substances 0.000 description 9
- 239000002351 wastewater Substances 0.000 description 9
- 238000011084 recovery Methods 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- 238000007789 sealing Methods 0.000 description 7
- 150000004696 coordination complex Chemical group 0.000 description 6
- 230000002349 favourable effect Effects 0.000 description 6
- 230000003301 hydrolyzing effect Effects 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
- XXPIVMBNLKIMFE-UHFFFAOYSA-N [NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O Chemical compound [NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XXPIVMBNLKIMFE-UHFFFAOYSA-N 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 5
- 239000013522 chelant Substances 0.000 description 5
- 230000000536 complexating effect Effects 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000008363 phosphate buffer Substances 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- 239000011574 phosphorus Substances 0.000 description 5
- 230000001105 regulatory effect Effects 0.000 description 5
- 239000005995 Aluminium silicate Substances 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 235000012211 aluminium silicate Nutrition 0.000 description 4
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 4
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 4
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 125000000129 anionic group Chemical group 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 3
- 239000000084 colloidal system Substances 0.000 description 3
- 238000010790 dilution Methods 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 125000004434 sulfur atom Chemical group 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 238000010408 sweeping Methods 0.000 description 3
- AJTVSSFTXWNIRG-UHFFFAOYSA-N 2-[bis(2-hydroxyethyl)amino]ethanesulfonic acid Chemical compound OCC[NH+](CCO)CCS([O-])(=O)=O AJTVSSFTXWNIRG-UHFFFAOYSA-N 0.000 description 2
- 238000006683 Mannich reaction Methods 0.000 description 2
- VLCDUOXHFNUCKK-UHFFFAOYSA-N N,N'-Dimethylthiourea Chemical compound CNC(=S)NC VLCDUOXHFNUCKK-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 150000007942 carboxylates Chemical group 0.000 description 2
- 125000002843 carboxylic acid group Chemical group 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 description 2
- 150000004692 metal hydroxides Chemical class 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 229910052976 metal sulfide Inorganic materials 0.000 description 2
- 238000006011 modification reaction Methods 0.000 description 2
- 239000006174 pH buffer Substances 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- LEVVMZZBTOYKSC-UHFFFAOYSA-N 1-amino-4-hydroxybutane-2-sulfonic acid Chemical compound NCC(S(O)(=O)=O)CCO LEVVMZZBTOYKSC-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- -1 and preferably Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 1
- 229960003237 betaine Drugs 0.000 description 1
- 231100000693 bioaccumulation Toxicity 0.000 description 1
- ICHNIWWYEHETFJ-UHFFFAOYSA-N bis(4-methoxyphenyl)diazene Chemical compound C1=CC(OC)=CC=C1N=NC1=CC=C(OC)C=C1 ICHNIWWYEHETFJ-UHFFFAOYSA-N 0.000 description 1
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000012990 dithiocarbamate Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- DVEKCXOJTLDBFE-UHFFFAOYSA-N n-dodecyl-n,n-dimethylglycinate Chemical compound CCCCCCCCCCCC[N+](C)(C)CC([O-])=O DVEKCXOJTLDBFE-UHFFFAOYSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- SOBHUZYZLFQYFK-UHFFFAOYSA-K trisodium;hydroxy-[[phosphonatomethyl(phosphonomethyl)amino]methyl]phosphinate Chemical compound [Na+].[Na+].[Na+].OP(O)(=O)CN(CP(O)([O-])=O)CP([O-])([O-])=O SOBHUZYZLFQYFK-UHFFFAOYSA-K 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 238000005406 washing 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
- 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
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/56—Acrylamide; Methacrylamide
-
- 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
-
- 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
- C08F8/00—Chemical modification by after-treatment
- C08F8/14—Esterification
-
- 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
- C08F8/00—Chemical modification by after-treatment
- C08F8/42—Introducing metal atoms or metal-containing groups
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Hydrology & Water Resources (AREA)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
Abstract
The invention relates to a modified aqueous solution polyacrylamide flocculant and a preparation method thereof, belonging to the technical field of polymer flocculant synthesis. The method comprises the following steps: polymerizing raw materials comprising acrylamide monomers, pH buffer solution with the pH value of 6.1-6.3, sodium olefin sulfonate monomers, thiourea monomers, a cosolvent, an initiator, a metal complexing agent and a chain transfer agent to obtain aqueous solution polyacrylamide; sequentially carrying out aminomethylation modification and grafting modification on thio monomers on aqueous solution polyacrylamide, and then adding an alkaline hydrolysis agent and a dispersing agent for hydrolysis; and adding an acid catalyst and a hydroxyl-containing modifier solution into the obtained hydrolysis modified aqueous solution polyacrylamide for esterification grafting modification to obtain the modified aqueous solution polyacrylamide flocculant. The flocculant product prepared by the invention is in the shape of an aqueous solution, has good solubility and good ageing resistance, and has the double functions of excellent sewage flocculation effect and heavy metal ion removal effect.
Description
Technical Field
The invention relates to the technical field of synthesis of polymeric flocculant, in particular to a modified aqueous solution polyacrylamide flocculant and a preparation method thereof.
Background
Along with the promotion of industrialization progress, the amount of wastewater discharged by industrial enterprises such as metal ore exploitation, smelting processing and the like is increased year by year, and if the wastewater is not treated, heavy metals such as copper, lead, chromium and the like contained in the wastewater are discharged into the environment, so that the structure of an aquatic ecological system is seriously damaged and water resources are polluted. The heavy metal pollution has the characteristics of nondegradability, bioaccumulation, very large toxicity generated by trace amount, and the like, so that the heavy metal pollution can be extremely harmful to human bodies and natural environments.
For treating heavy metal wastewater, the traditional high-molecular polyacrylamide flocculant can have a good flocculation effect on conventional suspended particles in the wastewater, but can not effectively remove dissolved heavy metal ions, and has a weak flocculation effect on the heavy metal ions. In the prior art (see Yan Yaping. Copper removal response surface optimization and model establishment [ J ] [2023-09-21 ]) by taking traditional Polyacrylamide (PAM) as a matrix, carrying out aminomethylation modification on the PAM to obtain an aminomethylated polyacrylamide APAM, and then introducing dithiocarboxyl groups into the APAM to obtain a final product dithiocarboxylated aminomethylpolyacrylamide, wherein the flocculation effect on suspended matters in sewage is not improved although the removal effect on heavy metal ions is improved, and the obtained dithiocarboxylated aminomethylpolyacrylamide has very low viscosity-average molecular mass and very poor flocculation effect on sewage.
In view of the current situation that heavy metal wastewater is to be treated urgently, it is very necessary to develop a flocculant with excellent sewage flocculation effect and excellent heavy metal ion removal effect, which has great significance in heavy metal sewage treatment.
Disclosure of Invention
In order to solve one or more technical problems in the prior art, the invention provides a modified aqueous solution polyacrylamide flocculant and a preparation method thereof. The modified aqueous solution polyacrylamide flocculant prepared by the invention is in an aqueous solution state, and has the characteristics of no pollution, low cost, good solubility, good ageing resistance, good cationic sewage flocculation effect, low turbidity of the flocculated sewage supernatant, high turbidity removal rate of the supernatant, good stability of complex flocs, difficult secondary pollution, high removal rate of heavy metal ions and the like; the modified aqueous solution polyacrylamide flocculant has the double functions of excellent sewage flocculation effect and excellent heavy metal ion removal effect.
The invention provides a preparation method of a modified aqueous solution polyacrylamide flocculant in a first aspect, which comprises the following steps:
(1) Polymerizing raw materials comprising acrylamide monomers, pH buffer solution with the pH value of 6.1-6.3, diluent, anti-hydrolysis agent, a cosolvent, an initiator, a metal complexing agent and a chain transfer agent to obtain aqueous solution polyacrylamide; the diluent is sodium olefin sulfonate monomer; the anti-hydrolysis agent is thiourea monomer;
(2) Sequentially carrying out aminomethylation modification and grafting modification on thio monomers on aqueous solution polyacrylamide, and then adding an alkaline hydrolysis agent and a dispersing agent for hydrolysis modification to obtain hydrolysis modified aqueous solution polyacrylamide;
(3) Adding an acid catalyst and a hydroxyl-containing modifier solution into the hydrolysis modified aqueous solution polyacrylamide for esterification grafting modification to prepare a modified aqueous solution polyacrylamide flocculant; the hydroxyl-containing modifier in the hydroxyl-containing modifier solution is one or more of triethylsilanol, tert-butyldimethylsilanol, N-ethyl-3-pyrrolidinol, N-undecanol and 9-bromo-1-nonanol.
Preferably, in step (1): the polymerization reaction is carried out in a nitrogen atmosphere; initiating a polymerization reaction at 28-31 ℃, naturally heating the polymerization reaction, wherein the peak temperature of the natural heating is 88-90 ℃, and then preserving heat for 2-2.5 h at the peak temperature; the acrylamide monomer is one or more of acrylamide, methacrylamide, N-dimethylacrylamide and N-phenylacrylamide; the pH buffer solution is one or more of sodium acetate-acetic acid buffer solution, ammonium phosphate-phosphoric acid buffer solution and sodium citrate-citric acid buffer solution; the sodium olefin sulfonate monomer is one or more of sodium vinyl sulfonate, sodium methacrylate sulfonate and sodium p-styrene sulfonate; the thiourea monomer is one or more of 4-phenyl-3-thiosemicarbazide, N-phenylthiourea, N' -dimethylthiourea and 4-methyl thiosemicarbazide; the cosolvent is a monomer containing amino and/or sulfonate, and the monomer containing amino and/or sulfonate is one or more of N-dodecyl-N, N-dimethylglycine, N-tetradecyl-N, N-dimethyl-3-ammonio-1-propanesulfonate, 3- (N, N-dimethyl hexadecyl ammonium) propanesulfonate and 3- (dodecyl dimethyl ammonium) propanesulfonate; the initiator comprises azo initiator and peroxidation initiator, wherein the azo initiator is one or more of dibenzyl azodicarbonate, 4' -azobisanisole, diisopropyl azodicarbonate and azobisisobutylamidine hydrochloride, and the peroxidation initiator is one or more of di-tert-butyl peroxide, benzoyl peroxide, dicumyl peroxide, cumene hydroperoxide and tert-butylcumene peroxide; the metal complexing agent is one or more of ethylenediamine tetramethylene phosphoric acid, diethylenetriamine pentamethylene phosphonic acid and dihydroxyethyl glycine; and/or the chain transfer agent is one or more of sodium hypophosphite, sodium formate, ammonium oxalate and disodium succinate.
Preferably, in step (1): the initiator comprises azo initiator and peroxidation initiator; the mass ratio of the acrylamide monomer, the pH buffer solution, the diluent, the hydrolysis inhibitor, the cosolvent, the azo initiator, the metal complexing agent, the chain transfer agent and the peroxidation initiator is (25.5-27.2): (62.7 to 67.8): (3-5): (2.6 to 3.5): (1.1 to 1.6): (0.012-0.013): (0.0062-0.0068): (0.0078-0.0083): (0.011 to 0.012).
Preferably, in step (3): the acid catalyst is one or more of hydrochloric acid solution, glacial acetic acid and sulfuric acid solution; the hydroxyl-containing modifier solution is formed by mixing a hydroxyl-containing modifier and an organic solvent, wherein the organic solvent is one or more of ethanol, styrene, ethylene glycol and trichloroethylene; the mass ratio of the hydrolysis modified aqueous solution polyacrylamide to the hydroxyl-containing modifier to the organic solvent to the acid catalyst is (94.48-95.11): (2.4 to 2.7): (2.4 to 2.7): (0.09-0.12); the temperature of the esterification grafting modification is 55-58 ℃ and the time is 4-5 h.
Preferably, in step (2): the alkaline hydrolysis agent is one or more of potassium hydroxide, sodium carbonate and ammonia water; the dispersing agent is one or more of sorbitan monostearate, sorbitan sesquioleate and sorbitan monopalmitate; the temperature of the hydrolysis modification is 88-90 ℃ and the time is 6.5-7 h; and/or the mass ratio of the alkaline hydrolysis agent, the dispersant and the product obtained by graft modification of the thio-monomer is (2.8-3.2): (1.1 to 1.5): (95.3-96.1).
Preferably, the viscosity-average molecular weight of the aqueous solution polyacrylamide obtained in the step (1) is 600-800 ten thousand; the hydrolysis degree of the hydrolysis modified aqueous solution polyacrylamide obtained in the step (2) is 23-26%; and/or the viscosity average molecular weight of the modified aqueous solution polyacrylamide flocculant obtained in the step (3) is 1200-1300 ten thousand.
Preferably, in step (2), the aminomethylation modification is to: and (3) uniformly mixing and reacting aldehyde, amine and an acid catalyst with water to obtain a hydroxymethyl dimethylamine aqueous solution, and then adding the hydroxymethyl dimethylamine aqueous solution into the aqueous solution polyacrylamide obtained in the step (1), uniformly mixing and carrying out aminomethylation modification.
Preferably, the aldehyde is one or more of formaldehyde, acetaldehyde, and trioxymethylene; the amine is one or more of dibutylamine, diethylamine, dimethylamine and pyridine; the acid catalyst adopted by the aminomethylation modification is one or more of hydrochloric acid solution, glacial acetic acid and sulfuric acid solution; the temperature of the aminomethylation modification is 55-58 ℃ and the time is 1.5-2 h; and/or the mass ratio of the water, the aldehyde, the amine, the acid catalyst and the aqueous solution polyacrylamide is (17.31-20.75): (1.4 to 1.8): (1.4 to 1.8): (0.05-0.09): (74.46 to 79.04).
Preferably, in step (2): the thio monomer is one or more of 4-chlorthiophenol, 2-thiobarbituric acid, 2- (dodecyl trithiocarbonate group) -2-methylpropionic acid, 2' -dithiodibenzoic acid, 4-imidazole dithiocarboxylic acid, 2-hydroxyethyl disulfide and bis (carboxymethyl) trithiocarbonate; the grafting modification of the thio-monomer is carried out in the presence of an acid catalyst, wherein the acid catalyst is one or more of hydrochloric acid solution, glacial acetic acid and sulfuric acid solution; in the graft modification of the thio-monomer, the mass ratio of the thio-monomer, the acid catalyst and the product obtained by the aminomethylation modification is (5.2-5.8): (0.08-0.11): (94.09-94.72); the grafting modification temperature of the thio-monomer is 55-58 ℃ and the time is 2-2.5 h.
The present invention provides in a second aspect a modified aqueous polyacrylamide flocculant produced by the method of the invention described in the first aspect.
Compared with the prior art, the invention has at least the following beneficial effects:
(1) According to the invention, when the aqueous solution polyacrylamide is prepared, the diluent, the hydrolysis inhibitor and the solvent promoter are added, the diluent is favorable for ensuring that a polymerization system is in an aqueous solution state and does not form colloid, the aqueous solution polyacrylamide with a viscosity-average molecular weight of 600-800 ten thousand can be ensured to be obtained while the subsequent reaction is ensured to be smoothly carried out, the flocculation effect of a final flocculant product is more favorable for the polyacrylamide with a relatively high molecular weight, the addition of the hydrolysis inhibitor can ensure that an amide group is not hydrolyzed into carboxylate groups in a high-temperature section (for example, 70-90 ℃), enough amide groups are provided for the subsequent modification, the subsequent reaction is ensured to be normal, and in the invention, the hydrolysis inhibitor can not only prevent the amide group from being subjected to self-hydrolysis under the influence of high temperature, but also can improve the thermal stability of the product; the solvent has a special amphoteric structure, and can greatly improve the solubility of polyacrylamide.
(2) The aqueous solution polyacrylamide is taken as a basic system, the activity of amide groups contained in the molecular chain is high, and the aqueous solution polyacrylamide is easy to carry out modification reaction with other monomers under various conditions, so that an excellent grafting modification platform is provided for subsequent reactions; the aqueous solution polyacrylamide is modified in multiple steps, so that each functional monomer can be grafted on an amide group according to a preset path, each functional monomer does not conflict, and the purpose of modification is achieved; the basic system adopted by the invention is in an aqueous solution state, and in the preparation process, the aqueous solution state can ensure that all the systems can be fully mixed and contacted and react fully, so that an ideal target product is easier to obtain.
(3) According to the preparation method, part of amide groups on the aqueous solution polyacrylamide are subjected to amine methylation modification through a Mannich reaction, the amide groups are modified into amine methylation amide groups with higher activity, and the amine methylation amide groups can react with sulfur-containing groups (grafting modification of thio monomers) to obtain strong coordination metal complex groups; in the metal indissolvable salts and metal hydroxides of various anions, the solubility product of metal sulfides is minimum, so that the strong coordination metal complexing group containing sulfur atoms can play a good role in complexing metal ions in sewage; according to the invention, part of amide groups are hydrolyzed into carboxylic acid groups through hydrolysis modification, and esterification grafting reaction can be carried out with a hydroxyl-containing modifier; the invention discovers that the proper short branched chain is introduced on the molecular chain of the polyacrylamide, which is favorable for improving the net capturing and rolling sweeping capacity of the polyacrylamide, thereby obviously improving the flocculation capacity and the thermal stability of flocculant products.
(4) The modified aqueous solution polyacrylamide flocculant prepared by the invention has the characteristics of no pollution, low cost, good solubility, good flocculation effect of cationic sewage, good stability of complex flocs, difficult secondary pollution, low turbidity, simple treatment process, high removal rate of heavy metals, especially Cu (II), suitability for the flocculation field of heavy metal sewage, especially sewage containing Cu (II), and the like, and the viscosity-average molecular weight of the modified aqueous solution polyacrylamide flocculant obtained by some preferred embodiments of the invention can reach 1200-1300 ten thousand, and the apparent viscosity is 550-650 mPa.s,Cu 2+ Ion removal rate is more than or equal to 97%, and chelating floc Cu 2+ The ion recovery rate is more than or equal to 85 percent, the turbidity removal rate of the supernatant fluid is more than or equal to 92 percent, and the ageing resistance (thermal stability) is more than or equal to 88 percent; the invention provides the strong coordination grafted polyacrylamide which can chelate and flocculate heavy metal ions and has good sewage flocculation effect, and is very suitable for the field of heavy metal wastewater flocculation.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be clearly and completely described below in connection with the embodiments of the present invention. It will be apparent that the described embodiments are some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides a preparation method of a modified aqueous solution polyacrylamide flocculant in a first aspect, which comprises the following steps:
(1) Polymerizing raw materials comprising acrylamide monomers, pH buffer solution with the pH value of 6.1-6.3, diluent, anti-hydrolysis agent, a cosolvent, an initiator, a metal complexing agent and a chain transfer agent to obtain aqueous solution polyacrylamide; the diluent is sodium olefin sulfonate monomer; the anti-hydrolysis agent is thiourea monomer; according to the invention, the pH buffer solution with the pH value of 6.1-6.3 is adopted to replace water for polymerization reaction, so that the pH of a polymerization system is ensured not to change in the process of blowing nitrogen to remove oxygen, and the polymerization system is maintained at the optimal pH; the aqueous solution polyacrylamide obtained in the step (1) is used as a basic system, the activity of amide groups contained in a molecular chain is high, and the aqueous solution polyacrylamide is easy to carry out modification reaction with other monomers under various conditions, so that an excellent grafting modification platform is provided for subsequent reactions; the aqueous solution polyacrylamide prepared by the method is in an aqueous solution state, and in the preparation process, the aqueous solution state can ensure that all systems can be fully mixed and contacted and react fully, so that an ideal target product is easier to obtain, an aqueous solution flocculant product is beneficial to being obtained, and the flocculant has the advantages of quick dissolution, good solubility, environmental protection, no dust and oil-based pollution and good application effect in practical application;
(2) Sequentially carrying out aminomethylation modification and grafting modification on thio monomers on aqueous solution polyacrylamide, and then adding an alkaline hydrolysis agent and a dispersing agent for hydrolysis modification to obtain hydrolysis modified aqueous solution polyacrylamide; according to the preparation method, part of amide groups in aqueous solution polyacrylamide are subjected to aminomethylation modification through Mannich reaction, amide groups are modified into aminomethylation amide groups with higher activity, and the amide groups can react with sulfur-containing groups (grafting modification of thio monomers) to obtain strong coordination metal complex groups; in metal indissolvable salts and metal hydroxides of various anions, the solubility product of metal sulfide is minimum, so that a strong coordination metal complexing group containing sulfur atoms can play a good role in complexing metal ions in sewage, and the added strong coordination metal complexing group contains sulfur atoms, is typical soft alkaline coordination atoms, has the characteristics of electronegativity, easy oxidation and easy polarization, has a strong chelation effect on both Cd ions and Cu ions, has the best Cu (II) removal effect in practical application, and is Cd (II) secondary;
(3) Adding an acid catalyst and a hydroxyl-containing modifier solution into the hydrolysis modified aqueous solution polyacrylamide for esterification grafting modification to prepare a modified aqueous solution polyacrylamide flocculant; the hydroxyl-containing modifier in the hydroxyl-containing modifier solution is one or more of triethylsilanol, tert-butyldimethylsilanol, N-ethyl-3-pyrrolidinol, N-undecanol and 9-bromo-1-nonanol; in the invention, the hydroxyl-containing modifier is adopted, one end is hydroxyl, the other end is a straight short chain or a plurality of short chains, the hydroxyl groups can ensure the esterification reaction, and the straight short chain or the plurality of short chains can ensure that the grafted polyacrylamide has a branched structure, thereby being beneficial to improving the flocculation effect of the system; in the invention, the modified aqueous solution polyacrylamide flocculant can be simply referred to as flocculant; according to the hydrolysis modification method, part of amide groups can be hydrolyzed into carboxylic acid groups to obtain hydrolysis modification aqueous solution polyacrylamide, so that esterification grafting modification of the step (3) can be performed, esterification grafting reaction can be performed with a hydroxyl-containing modifier, and the net capturing and sweeping capacity of the polyacrylamide can be improved by introducing proper short branched chains on the molecular chain of the polyacrylamide, so that flocculation capacity and thermal stability of a flocculant product can be remarkably improved.
According to the invention, when the aqueous solution polyacrylamide is prepared, a diluent, an anti-hydrolysis agent and a solvent promoter are added, the addition of the diluent can ensure that a polymerization system is in an aqueous solution state and does not form colloid, the subsequent reaction is ensured to be smoothly carried out, meanwhile, the aqueous solution polyacrylamide with a viscosity-average molecular weight of 600-800 ten thousand can be ensured to be obtained, the flocculation effect of a final flocculant product is ensured more favorably than that of the high-molecular-weight polyacrylamide, the addition of the anti-hydrolysis agent can ensure that an amide group is not hydrolyzed into carboxylate groups in a high-temperature section (for example, 70-90 ℃), enough amide groups are provided for subsequent modification, the subsequent reaction is ensured to be normal, and in the invention, the anti-hydrolysis agent can not only prevent the amide group from being subjected to self-hydrolysis under the influence of high temperature, but also can improve the thermal stability of the product; the cosolvent has a special amphoteric structure, and can greatly improve the solubility of the polyacrylamide; according to the invention, through the esterification grafting modification, proper short branched chains are introduced into the polyacrylamide molecular chain, and the effect of resisting aging is obvious, and the hydrolysis resistance agent and the esterification grafting modification are added into the synthetic basic system, so that the prepared modified aqueous solution polyacrylamide flocculant has excellent heat stability.
The modified aqueous solution polyacrylamide flocculant prepared by the invention has the characteristics of no pollution, low cost, good solubility, good flocculation effect of cationic sewage, good stability of complex flocs, difficult secondary pollution, low turbidity, simple treatment process, high removal rate of heavy metals, especially Cu (II), suitability for the flocculation field of heavy metal sewage, especially sewage containing Cu (II), and the like, and the viscosity-average molecular weight of the modified aqueous solution polyacrylamide flocculant obtained by some preferred embodiments of the invention can reach 1200-1300 ten thousand, and the apparent viscosity is 550-550%650mPa·s、Cu 2+ Ion removal rate is more than or equal to 97%, and chelating floc Cu 2+ The ion recovery rate is more than or equal to 85%, the turbidity removal rate of the supernatant is more than or equal to 92%, and the ageing resistance is more than or equal to 88%; the invention provides the strong coordination grafted polyacrylamide which can chelate and flocculate heavy metal ions and has good sewage flocculation effect, and is very suitable for the field of heavy metal wastewater flocculation.
According to some preferred embodiments, in step (1): the polymerization reaction is carried out in a nitrogen atmosphere; initiating a polymerization reaction at 28-31 ℃, naturally heating the polymerization reaction, wherein the peak temperature of the natural heating is 88-90 ℃, and then preserving heat for 2-2.5 h at the peak temperature; the acrylamide monomer is one or more of acrylamide, methacrylamide, N-dimethylacrylamide and N-phenylacrylamide, and preferably the acrylamide monomer is acrylamide; the pH buffer solution is one or more of sodium acetate-acetic acid buffer solution, ammonium phosphate-phosphoric acid buffer solution and sodium citrate-citric acid buffer solution, and preferably, the pH buffer solution is ammonium phosphate-phosphoric acid buffer solution; the sodium olefin sulfonate monomer is one or more of sodium vinyl sulfonate, sodium methacrylate sulfonate and sodium p-styrene sulfonate; the thiourea monomer is one or more of 4-phenyl-3-thiosemicarbazide, N-phenylthiourea, N' -dimethylthiourea and 4-methyl thiosemicarbazide; the cosolvent is a monomer containing amino and/or sulfonate, and the monomer containing amino and/or sulfonate is one or more of N-dodecyl-N, N-dimethylglycine, N-tetradecyl-N, N-dimethyl-3-ammonio-1-propanesulfonate, 3- (N, N-dimethyl hexadecyl ammonium) propanesulfonate and 3- (dodecyl dimethyl ammonium) propanesulfonate; in the invention, N-dodecyl-N, N-dimethyl glycine refers to N, N-dimethyl-N-dodecyl glycine betaine, N-tetradecyl-N, N-dimethyl-3-ammonio-1-propanesulfonate refers to 3- (N, N-dimethyl tetradecyl ammonium) propanesulfonate, and 3- (dodecyl dimethyl ammonium) propanesulfonate refers to 3- (N, N-dimethyl dodecyl ammonium) propanesulfonate; the initiator comprises azo initiator and peroxidation initiator, wherein the azo initiator is one or more of dibenzyl azodicarbonate, 4' -azobisanisole, diisopropyl azodicarbonate and azobisisobutylamidine hydrochloride, and the peroxidation initiator is one or more of di-tert-butyl peroxide, benzoyl peroxide, dicumyl peroxide, cumene hydroperoxide and tert-butylcumene peroxide; in the invention, the azo initiator is used as a high-temperature initiator, and the peroxide initiator is used as a medium-temperature initiator; the metal complexing agent is one or more of ethylenediamine tetramethylene phosphoric acid, diethylenetriamine pentamethylene phosphonic acid and dihydroxyethyl glycine; and/or the chain transfer agent is one or more of sodium hypophosphite, sodium formate, ammonium oxalate and disodium succinate.
According to some preferred embodiments, in step (1): the initiator comprises azo initiator and peroxidation initiator; the mass ratio of the acrylamide monomer, the pH buffer solution, the diluent, the hydrolysis inhibitor, the cosolvent, the azo initiator, the metal complexing agent, the chain transfer agent and the peroxidation initiator is (25.5-27.2): (62.7 to 67.8): (3-5): (2.6 to 3.5): (1.1 to 1.6): (0.012-0.013): (0.0062-0.0068): (0.0078-0.0083): (0.011 to 0.012); the preparation of the pH buffer solution is not particularly limited, and the pH of the pH buffer solution can be 6.1-6.3; in the present invention, the pH buffer is prepared by dissolving a weak acid and a conjugate acid salt in water, and when the pH buffer is prepared, the mass percentages of the raw material components may be, for example: 12.4-14.2% of weak acid, 24.1-26.3% of conjugate acid salt and 59.5-63.5% of water (such as deionized water).
In the step (1) of the invention, the diluent, the hydrolysis inhibitor and the dissolution promoter are added, the dosage proportion of each component in the raw materials is controlled, the aqueous solution polyacrylamide with quick dissolution, good solubility, good aging resistance, viscosity average molecular weight of 600-800 ten thousand and apparent viscosity of 300-400 mPa.s is more favorably obtained, the important effect is played for the subsequent obtaining of the modified aqueous solution polyacrylamide flocculant with proper viscosity average molecular weight (1200-1300 ten thousand) and still in the aqueous solution state and high-efficiency flocculation effect, the invention discovers that if the viscosity average molecular weight of the aqueous solution polyacrylamide obtained in the step (1) is too low, the viscosity average molecular weight of the finally obtained modified aqueous solution polyacrylamide flocculant is too low, the molecular weight of the aqueous solution polyacrylamide is insufficient to effectively adsorb and coagulate micro particles or suspended matters in sewage into large floccules, which results in poor flocculation effect, while if the viscosity-average molecular weight of the aqueous solution polyacrylamide obtained in the step (1) is too high, the viscosity-average molecular weight of the finally obtained flocculant product is too high, if the viscosity-average molecular weight is too high, the flocculant product molecules are large and very long, the macromolecular chains interweave with each other in water, the diffusion and movement capacity of the macromolecular chains in the water are limited, the dispersibility of the macromolecular chains in the sewage is poor, the solubility is poor, the interaction with the suspended matters and the floccules are difficult to effectively form, the flocculant efficiency is reduced, and moreover, the flocculant product with too high molecular weight can make the solution too viscous, the uniform distribution and the mixing property of the flocculant are reduced, which is disadvantageous to the practical sewage treatment operation, affecting the application effect.
According to some specific embodiments, step (1) is: adding an acrylamide monomer, a pH buffer solution with a pH value of 6.1-6.3, a diluent, an anti-hydrolysis agent and a cosolvent into a reaction kettle, starting stirring, fully dissolving, blowing nitrogen to remove oxygen for 35-37 min (for example 36 min), and raising the temperature of the system to 28-31 ℃; then sequentially adding a high-temperature initiator (azo initiator), a metal complexing agent, a chain transfer agent and a medium-temperature initiator (peroxidation initiator) into the system, continuously blowing nitrogen to remove oxygen for 10-12 min (for example, 11 min), then initiating polymerization under the condition of nitrogen protection and stirring at 28-31 ℃, naturally heating the polymerization, wherein the natural heating peak temperature is 88-90 ℃, the natural heating time is generally 3-4 h, then preserving heat for 2-2.5 h at the peak temperature, and changing the system into a transparent aqueous solution state at the moment, so as to obtain the aqueous solution nonionic polyacrylamide, and cooling the system to 23-25 ℃ for later use; testing that the viscosity-average molecular weight of the aqueous solution polyacrylamide is 600-800 ten thousand and the apparent viscosity is 300-400 mPa.s at normal temperature; the invention can prepare the aqueous solution polyacrylamide with the viscosity-average molecular weight of 600-800 ten thousand, adopts the aqueous solution polyacrylamide with the proper viscosity-average molecular weight as a basic system for subsequent multi-step modification, and can ensure that the modified aqueous solution polyacrylamide flocculant with the viscosity-average molecular weight of moderate (1200-1300 ten thousand) is obtained, thereby effectively ensuring the sewage flocculation effect of flocculant products.
According to some preferred embodiments, in step (3): the acid catalyst is one or more of hydrochloric acid solution, glacial acetic acid and sulfuric acid solution, and is preferably hydrochloric acid solution; in the invention, under the condition that no special description exists, the hydrochloric acid solution is 36-38% hydrochloric acid aqueous solution (concentrated hydrochloric acid) by mass fraction, the purity of glacial acetic acid is not less than 99%, and the sulfuric acid solution is not less than 98% concentrated sulfuric acid aqueous solution by mass fraction; the hydroxyl-containing modifier solution is formed by mixing a hydroxyl-containing modifier and an organic solvent, wherein the organic solvent is one or more of ethanol, styrene, ethylene glycol and trichloroethylene; the mass ratio of the hydrolysis modified aqueous solution polyacrylamide to the hydroxyl-containing modifier to the organic solvent to the acid catalyst is (94.48-95.11): (2.4 to 2.7): (2.4 to 2.7): (0.09-0.12); in the present invention, it is preferable that the pH of the system is 7 to 7.05 when the esterification grafting reaction is performed.
According to some preferred embodiments, in step (3): the temperature of the esterification grafting modification is 55-58 ℃ and the time is 4-5 h.
In the present invention, preferably, the mass ratio of the hydroxyl group-containing modifier to the hydrolysis-modified aqueous solution polyacrylamide is (2.4 to 2.7): (94.48-95.11), the temperature of the esterification grafting modification is 55-58 ℃ and the time is 4-5 h, so that the finally prepared modified aqueous solution polyacrylamide flocculant has proper modification degree, thereby being beneficial to ensuring that the prepared flocculant product has better salt resistance and sewage flocculation effect, the invention discovers that the mass ratio of the hydroxyl-containing modifier to the hydrolysis modified aqueous solution polyacrylamide is too low, the modification time is too short and/or the modifier temperature is too low, the hydrolysis modified aqueous solution polyacrylamide is not sufficiently modified, enough carboxyl on a molecular chain cannot be subjected to esterification grafting reaction, the net scanning capacity of the flocculant product cannot be effectively improved, and the salt resistance and the heat stability of the product are poor due to the fact that too many carboxyl groups are reserved on the molecular chain of the flocculant, and if the mass ratio of the hydroxyl-containing modifier to the hydrolysis modified aqueous solution polyacrylamide is too high, the modification time and/or the modifier temperature is too high, the hydroxyl-containing modifier is easy to react, the crosslinking property of the flocculant is not influenced by the fact that the crosslinking agent is too long, and the cross-linked product can not be produced; when the modified aqueous solution polyacrylamide flocculant is prepared, the temperature of esterification grafting modification, the modification time and the dosage of the hydroxyl-containing modifier are precisely controlled, so that the final flocculant product has proper modification degree, and the modified aqueous solution polyacrylamide flocculant is favorable for exhibiting excellent salt resistance and sewage flocculation effect.
According to some specific embodiments, step (3) is: adding an acid catalyst and a hydroxyl-containing modifier solution into the hydrolysis modified aqueous solution polyacrylamide obtained in the step (2), stirring and mixing uniformly, simultaneously raising the temperature to 55-58 ℃ under the condition that the pH value of a system is 7.0-7.05, carrying out esterification grafting modification for 4-5 hours, and cooling the system to 23-25 ℃ to obtain the modified aqueous solution polyacrylamide flocculant; the apparent viscosity of the modified aqueous solution polyacrylamide flocculant obtained by the test is 550-650 mPa.s at normal temperature, and the viscosity-to-average molecular weight is 1200-1300 ten thousand; the hydroxyl-containing modifier solution is obtained by dissolving the hydroxyl-containing modifier in an organic solvent.
According to some preferred embodiments, in step (2): the alkaline hydrolysis agent is one or more of potassium hydroxide, sodium carbonate and ammonia water, preferably sodium hydroxide; the dispersing agent is one or more of sorbitan monostearate, sorbitan sesquioleate and sorbitan monopalmitate; the temperature of the hydrolysis modification is 88-90 ℃ and the time is 6.5-7 h; the mass ratio of the alkaline hydrolysis agent to the dispersant to the product obtained by graft modification of the thio monomer is (2.8-3.2): (1.1 to 1.5): (95.3-96.1).
According to some specific embodiments, in step (2), the hydrolytic modification is: adding an alkaline hydrolysis agent and a dispersing agent into the sulfur-containing strong coordination aqueous solution amine methylated polyacrylamide obtained by grafting modification of a thio-group monomer, starting stirring and mixing uniformly, raising the system pH value to be 11.2-11.4 at the same time, sealing a reaction kettle, continuing to keep the temperature for hydrolysis for 6.5-7 h at the temperature to obtain hydrolysis modified aqueous solution polyacrylamide, and cooling the system to 23-25 ℃ for later use; and testing that the hydrolysis degree of the hydrolysis modified aqueous solution polyacrylamide is 23-26% at normal temperature.
In the invention, the hydrolysis modification temperature is controlled to be 88-90 ℃ and the time is controlled to be 6.5-7 hours, and the mass ratio of the alkaline hydrolysis agent to the product obtained by grafting modification of the dispersant and the thio monomer is (2.8-3.2): (1.1 to 1.5): (95.3-96.1), which is favorable for ensuring that the hydrolysis modified aqueous solution polyacrylamide with the hydrolysis degree of 23-26% is prepared, and the hydrolysis modified aqueous solution polyacrylamide with the hydrolysis degree is adopted for esterification grafting reaction, so that a proper amount of short branched chains can be ensured to be introduced into a flocculant molecular chain, the net capturing and rolling sweeping capacity of a product can be improved, and the flocculation capacity of the product can be further improved; the invention discovers that if the hydrolysis modification aqueous solution polyacrylamide with too small hydrolysis degree is adopted for esterification grafting modification, enough short branched chains cannot be introduced into a flocculant molecular chain, which is not beneficial to effectively improving the net capturing and rolling capability of a product, and if the hydrolysis modification aqueous solution polyacrylamide with too high hydrolysis degree is adopted for esterification grafting modification, too many carboxyl groups still remain on the flocculant molecular chain after esterification grafting modification, and the flocculation effect and the thermal stability of the flocculant product are also affected.
According to some preferred embodiments, the viscosity-average molecular weight of the aqueous solution polyacrylamide obtained in the step (1) is 600-800 ten thousand; the hydrolysis degree of the hydrolysis modified aqueous solution polyacrylamide obtained in the step (2) is 23-26%; and/or the viscosity average molecular weight of the modified aqueous solution polyacrylamide flocculant obtained in the step (3) is 1200-1300 ten thousand.
According to some preferred embodiments, in step (2), the aminomethylation modification is to: uniformly mixing and reacting aldehyde, amine and an acid catalyst with water to obtain a hydroxymethyl dimethylamine aqueous solution, and then adding the hydroxymethyl dimethylamine aqueous solution into the aqueous solution polyacrylamide obtained in the step (1), uniformly mixing and carrying out aminomethylation modification; preferably, the aldehyde, the amine and the acid catalyst are uniformly mixed by water and react for 1 to 1.5 hours at the temperature of 35 to 38 ℃ at the pH of 2.3 to 2.5, so as to obtain the hydroxymethyl dimethylamine aqueous solution.
According to some preferred embodiments, the aldehyde is one or more of formaldehyde, acetaldehyde, trioxymethylene, preferably formaldehyde; the amine is one or more of dibutylamine, diethylamine, dimethylamine and pyridine; the acid catalyst adopted by the aminomethylation modification is one or more of hydrochloric acid solution, glacial acetic acid and sulfuric acid solution, and is preferably hydrochloric acid solution; the temperature of the aminomethylation modification is 55-58 ℃ and the time is 1.5-2 h; and/or the mass ratio of the water, the aldehyde, the amine, the acid catalyst and the aqueous solution polyacrylamide is (17.31-20.75): (1.4 to 1.8): (1.4 to 1.8): (0.05-0.09): (74.46 to 79.04).
According to some preferred embodiments, the aminomethylation modification is performed under the condition that the pH of the system is 6.4-6.6, and an alkaline pH regulator is adopted for regulating, wherein the alkaline pH regulator is one or more of sodium hydroxide, potassium hydroxide, ammonia water and sodium carbonate; the dosage of the alkaline pH regulator is not particularly limited, and the pH of the system can reach the target range.
According to some specific embodiments, the aminomethylation modification is: adding deionized water, aldehyde and amine into a reaction kettle, starting stirring, uniformly mixing, adding an acid catalyst, wherein the pH value of the system is 2.3-2.5, raising the temperature of the system to 35-38 ℃ at the same time, and reacting for 1-1.5 h to obtain a hydroxymethyl dimethylamine aqueous solution; adding the aqueous solution polyacrylamide prepared in the step (1) into a hydroxymethyl dimethylamine aqueous solution system, stirring and mixing uniformly, regulating the pH of the system to 6.4-6.6 by using an alkaline pH regulator, raising the temperature to 55-58 ℃, carrying out aminomethylation modification for 1.5-2 h at the temperature to obtain the aqueous solution amine-methylated polyacrylamide, and cooling the system to 23-25 ℃ for later use.
According to some preferred embodiments, in step (2): the thio monomer is thio monomer which can react with amide groups, and the thio monomer is one or more of 4-chlorthiophenol, 2-thiobarbituric acid, 2- (dodecyl trithiocarbonate group) -2-methylpropionic acid, 2' -dithiodibenzoic acid, 4-imidazole dithiocarboxylic acid, 2-hydroxyethyl disulfide and bis (carboxymethyl) trithiocarbonate; in the present invention, the 4-chlorothiophenol means 4-chlorothiophenol; of course, in the present invention, the thio-based monomer may be a strong coordination metal complex group such as a dithiocarbamate and its Derivative (DTC), a trisodium trimercaptan (TMT), sodium Trimercaptan (STC), a dimercapto, a dithiophosphate or thioglycollic acid (TGA) which can react with an amide group; the grafting modification of the thio-monomer is carried out in the presence of an acid catalyst, wherein the acid catalyst is one or more of hydrochloric acid solution, glacial acetic acid and sulfuric acid solution, and is preferably hydrochloric acid solution; in the graft modification of the thio-monomer, the mass ratio of the thio-monomer, the acid catalyst and the product obtained by the aminomethylation modification is (5.2-5.8): (0.08-0.11): (94.09-94.72); the grafting modification temperature of the thio-monomer is 55-58 ℃ and the time is 2-2.5 h.
In the present invention, it is preferable that the mass ratio of the water, the aldehyde, the amine, the acid catalyst, and the aqueous solution-based polyacrylamide in the step (2) is controlled to be (17.31 to 20.75): (1.4 to 1.8): (1.4 to 1.8): (0.05-0.09): (74.46-79.04), and when a grafting reaction of a thio monomer is carried out, the mass ratio of the thio monomer, the acid catalyst and a product obtained by amine methylation modification is (5.2-5.8): (0.08-0.11): (94.09-94.72), by controlling the addition of each raw material in the amine methylation process and the addition of the thio-monomer in the grafting process of the thio-monomer, the amine methylation modification and the grafting process of the thio-monomer can be effectively controlled, and if the degree of grafting of the amine methylation modification and the thio-monomer is too low, the heavy metal complexation effect is poor; if the degree of grafting of the amine methylation modification and thio monomers is too high, amide groups are less during hydrolysis, the degree of hydrolysis is reduced, and the flocculation effect is deteriorated.
According to some specific embodiments, in step (2), the grafting modification of the thio-based monomer is: adding a thio-monomer into an aqueous solution amine-methylated polyacrylamide obtained through amine methylation modification, starting stirring and mixing uniformly, adding an acid catalyst, raising the pH value of a system to 3.1-3.3, raising the temperature to 55-58 ℃, performing grafting modification on the thio-monomer at the temperature for 2-2.5 h, and obtaining the sulfur-containing strong coordination aqueous solution amine-methylated polyacrylamide, and cooling the system to 23-25 ℃ for later use.
Under the condition that the invention is not particularly described, the adopted raw material substances can be directly purchased products on the market or synthesized by the existing method; in the present invention, the occurrence of "and/or" between a plurality of technical features means that the technical features are connected in "and/or" relation, and that any one of the technical features may be represented, or a combination of any two or more of the technical features may be represented; in the invention, when each reaction is carried out, the stirrer is always started, and the rotation speed of the stirrer can be 260-280 r/min, preferably 275r/min; in the present invention, the normal temperature state may be, for example, a state of 23 to 25 ℃ at normal temperature.
The present invention provides in a second aspect a modified aqueous polyacrylamide flocculant produced by the method of the invention described in the first aspect.
The invention will be further illustrated by way of example, but the scope of the invention is not limited to these examples.
Example 1
(1) Preparing aqueous solution polyacrylamide:
adding 263g of acrylamide, 654g of ammonium phosphate-phosphate buffer with the pH value of 6.23, 41g of sodium vinylsulfonate, 29g of N-phenylthiourea and 13g of 3- (N, N-dimethyl hexadecyl ammonium) propanesulfonate into a reaction kettle, starting stirring, setting the rotating speed to 275r/min, fully dissolving the system, blowing nitrogen to remove oxygen for 36min, and raising the temperature of the system to 30 ℃; then adding 0.125g of dibenzyl azodicarbonate, 0.065g of ethylenediamine tetramethylene phosphorus, 0.079g of ammonium oxalate and 0.113g of benzoyl peroxide into the system in turn, continuously blowing nitrogen to remove oxygen for 11min, then protecting nitrogen, keeping the stirring state (the rotating speed is set to 275 r/min), initiating the polymerization reaction under the condition of 30 ℃, naturally heating the polymerization reaction, naturally heating the system to 89 ℃ at the peak temperature, naturally heating the system to the peak temperature for 3.6h, then preserving the temperature for 2.3h at the peak temperature, changing the system into a transparent aqueous solution state at the moment, obtaining aqueous solution polyacrylamide, and cooling the system to 25 ℃ for later use; the viscosity-average molecular weight of the aqueous solution polyacrylamide at 25℃was 710 ten thousand, and the apparent viscosity was 362 mPa.s.
(2) Amine methylation modification:
adding 18.581g of deionized water, 1.6g of formaldehyde and 1.6g of diethylamine into a reaction kettle, starting stirring, setting the rotating speed to 275r/min, uniformly mixing the system, adding 0.063g of hydrochloric acid solution (concentrated hydrochloric acid with the mass fraction of 37 percent), wherein the pH value of the system is 2.36, and simultaneously raising the temperature of the system to 37 ℃ to react for 1.2 hours to obtain a hydroxymethyl dimethylamine aqueous solution; adding 77g of the aqueous solution polyacrylamide obtained in the step (1) into a hydroxymethyl dimethylamine aqueous solution system, stirring and mixing uniformly, regulating the pH value of the system to 6.51 by using sodium hydroxide, simultaneously raising the temperature to 56 ℃, carrying out aminomethylation modification for 1.7h at the temperature to obtain a product obtained by aminomethylation modification, namely the aqueous solution amine methylated polyacrylamide, and cooling the system to 25 ℃ for later use.
(3) Graft modification of thio-monomers (strong coordination complex groups):
adding 5.4g of 2- (dodecyl trithiocarbonate group) -2-methylpropanoic acid into 94.51g of the aqueous solution amine-methylated polyacrylamide system obtained in the step (2), starting stirring, setting the stirring rotation speed to 275r/min, adding 0.09g of hydrochloric acid solution (concentrated hydrochloric acid with the mass fraction of 37%) after the system is uniformly mixed, at the moment, raising the pH value of the system to 3.15, and simultaneously raising the temperature to 56 ℃, and carrying out graft modification on the thio-monomer for 2.2h at the temperature to obtain a product obtained through graft modification of the thio-monomer, namely the sulfur-containing strong coordination aqueous solution amine-methylated polyacrylamide, and cooling the system to 25 ℃ for later use.
(4) Hydrolysis modification:
adding 3g of sodium hydroxide and 1.3g of sorbitan sesquioleate into 95.7g of the sulfur-containing strong coordination aqueous solution amine-type polyacrylamide system obtained in the step (3), starting stirring, setting the rotating speed to 275r/min, uniformly mixing, wherein the pH value of the system is 11.25, simultaneously raising the temperature of the system to 89 ℃, sealing a reaction kettle, continuously preserving heat and hydrolyzing for 6.7h at the temperature to obtain hydrolysis modified aqueous solution polyacrylamide (also called as anionic sulfur-containing strong coordination aqueous solution amine-type polyacrylamide), and cooling the system to 25 ℃ for later use; the hydrolysis degree of the hydrolysis modified aqueous solution polyacrylamide at the normal temperature of 25 ℃ is 24 percent.
(5) Esterification grafting modification:
adding 0.093g of hydrochloric acid solution (concentrated hydrochloric acid with the mass fraction of 37%) and 5g of hydroxyl-containing modifier solution (obtained by dissolving 2.5g of triethylsilanol with 2.5g of trichloroethylene) into 94.907g of hydrolysis modified aqueous solution polyacrylamide system obtained in the step (4), starting stirring, setting the rotating speed to 275r/min, uniformly mixing, wherein the pH value of the system is 7.03, and simultaneously raising the temperature to 56 ℃ for esterification grafting modification for 4.6 hours, and cooling the system to 25 ℃ to obtain the modified aqueous solution polyacrylamide flocculant; the apparent viscosity of the modified aqueous solution polyacrylamide flocculant at the normal temperature of 25 ℃ is 600 mPas, and the viscosity average molecular weight is 1262 ten thousand.
Example 2
(1) Preparing aqueous solution polyacrylamide:
255g of acrylamide, 678g of ammonium phosphate-phosphate buffer with the pH of 6.1, 30g of sodium methacrylate, 26g of N, N' -dimethylthiourea and 11g of 3- (N, N-dimethyl hexadecyl ammonium) propanesulfonate are added into a reaction kettle, stirring is started, the rotating speed is set to be 260r/min, after the system is fully dissolved, nitrogen is blown for deoxidization for 35min, and the temperature of the system is increased to 30 ℃; then adding 0.12g of 4,4' -azo-bis-anisole, 0.062g of ethylenediamine tetra-methylene phosphorus, 0.078g of ammonium oxalate and 0.11g of benzoyl peroxide into the system in turn, continuously blowing nitrogen to remove oxygen for 10min, then protecting nitrogen, keeping the stirring state (the rotating speed is set to 260 r/min), initiating polymerization under the condition of 30 ℃, naturally heating the polymerization, naturally heating the system to 89 ℃, naturally heating the system to the peak temperature for 3h, then keeping the temperature for 2h at the peak temperature, changing the system into a transparent aqueous solution state to obtain aqueous solution polyacrylamide, and cooling the system to 25 ℃ for later use; the measured viscosity-average molecular weight of the aqueous solution polyacrylamide at 25 ℃ at normal temperature was 680 ten thousand, and apparent viscosity was 356 mPa.s.
(2) Amine methylation modification:
adding 17.31g of deionized water, 1.8g of formaldehyde and 1.7g of dimethylamine into a reaction kettle, starting stirring, setting the rotating speed to 260r/min, uniformly mixing the system, adding 0.05g of hydrochloric acid solution (concentrated hydrochloric acid with the mass fraction of 37 percent), wherein the pH value of the system is 2.3, and simultaneously raising the temperature of the system to 37 ℃ to react for 1.2 hours to obtain a hydroxymethyl dimethylamine aqueous solution; adding 78.34g of aqueous solution polyacrylamide obtained in the step (1) into a hydroxymethyl dimethylamine aqueous solution system, stirring and mixing uniformly, regulating the pH value of the system to 6.4 by using sodium hydroxide, simultaneously raising the temperature to 56 ℃, carrying out aminomethylation modification for 1.7h at the temperature to obtain an aminomethylation modified product, namely the aqueous solution amine methylated polyacrylamide, and cooling the system to 25 ℃ for later use.
(3) Graft modification of thio-monomers (strong coordination complex groups):
adding 5.8g of 2- (dodecyl trithiocarbonate group) -2-methylpropanoic acid into 94.118g of the aqueous solution amine-methylated polyacrylamide system obtained in the step (2), starting stirring, setting the stirring rotation speed to 260r/min, adding 0.082g of hydrochloric acid solution (concentrated hydrochloric acid with the mass fraction of 37%) after the system is uniformly mixed, at the moment, increasing the pH value of the system to 3.1, and simultaneously raising the temperature to 56 ℃, and carrying out graft modification on the thio-monomer for 2.2h at the temperature to obtain a product obtained through graft modification of the thio-monomer, namely the sulfur-containing strong coordination aqueous solution amine-methylated polyacrylamide, and cooling the system to 25 ℃ for later use.
(4) Hydrolysis modification:
adding 3.2g of sodium hydroxide and 1.1g of sorbitan sesquioleate into 95.7g of the sulfur-containing strong coordination aqueous solution amine-type polyacrylamide system obtained in the step (3), starting stirring, setting the rotating speed to 260r/min, uniformly mixing, wherein the pH value of the system is 11.2, simultaneously raising the temperature of the system to 89 ℃, sealing a reaction kettle, continuously preserving heat and hydrolyzing for 6.7h at the temperature to obtain hydrolysis modified aqueous solution polyacrylamide (also called as anionic sulfur-containing strong coordination aqueous solution amine-type polyacrylamide), and cooling the system to 25 ℃ for later use; the hydrolysis degree of the hydrolysis modified aqueous solution polyacrylamide at the normal temperature of 25 ℃ is 24 percent.
(5) Esterification grafting modification:
adding 0.12g of hydrochloric acid solution (concentrated hydrochloric acid with the mass fraction of 37%) and 5.02g of hydroxyl-containing modifier solution (obtained by dissolving 2.57g of 9-bromo-1-nonanol with 2.45g of trichloroethylene) into 94.86g of hydrolysis modified aqueous solution polyacrylamide system obtained in the step (4), starting stirring, setting the rotating speed to 260r/min, uniformly mixing, then, setting the pH value of the system to 7.0, simultaneously raising the temperature to 56 ℃ for esterification grafting modification for 4.6h, and cooling the system to 25 ℃ to obtain the modified aqueous solution polyacrylamide flocculant; the apparent viscosity of the modified aqueous solution polyacrylamide flocculant at the normal temperature of 25 ℃ is 552 mPas, and the viscosity-average molecular weight is 1205 ten thousand.
Example 3
(1) Preparing aqueous solution polyacrylamide:
272g of acrylamide, 627g of ammonium phosphate-phosphate buffer with the pH value of 6.23, 50g of sodium vinylsulfonate, 35g of N, N' -dimethylthiourea and 16g of N-dodecyl-N, N-dimethylglycine are added into a reaction kettle, stirring is started, the rotating speed is set to 275r/min, after the system is fully dissolved, nitrogen is blown for deoxidization for 36min, and the temperature of the system is increased to 28 ℃; then adding 0.13g of dibenzyl azodicarbonate, 0.068g of ethylenediamine tetramethylene phosphorus, 0.083g of ammonium oxalate and 0.12g of benzoyl peroxide into the system in turn, continuously blowing nitrogen to remove oxygen for 11min, then protecting nitrogen, keeping the stirring state (the rotating speed is set to 275 r/min), initiating the polymerization reaction under the condition of 28 ℃, naturally heating the polymerization reaction, naturally heating the system to the peak temperature at 88 ℃, naturally heating the system to the peak temperature for 3.6h, then preserving the temperature for 2.3h at the peak temperature, changing the system into a transparent aqueous solution state at the moment, obtaining aqueous solution polyacrylamide, and cooling the system to 25 ℃ for later use; the measured viscosity-average molecular weight of the aqueous solution polyacrylamide at 25 ℃ at normal temperature was 716 ten thousand, and apparent viscosity was 370 mPa.s.
(2) Amine methylation modification:
adding 17.8g of deionized water, 1.7g of formaldehyde and 1.75g of diethylamine into a reaction kettle, starting stirring, setting the rotating speed to 275r/min, uniformly mixing the system, adding 0.09g of hydrochloric acid solution (concentrated hydrochloric acid with the mass fraction of 37 percent), wherein the pH value of the system is 2.36, simultaneously raising the temperature of the system to 35 ℃, and reacting for 1h to obtain a hydroxymethyl dimethylamine aqueous solution; adding 77.66g of the aqueous solution polyacrylamide obtained in the step (1) into a hydroxymethyl dimethylamine aqueous solution system, stirring and mixing uniformly, regulating the pH value of the system to 6.51 by using sodium hydroxide, simultaneously raising the temperature to 55 ℃, carrying out aminomethylation modification for 1.5h to obtain an aminomethylation modified product, namely the aqueous solution amine methylated polyacrylamide, and cooling the system to 25 ℃ for later use.
(3) Graft modification of thio-monomers (strong coordination complex groups):
adding 5.2g of bis (carboxymethyl) trithiocarbonate into 94.69g of the aqueous solution amine-methylated polyacrylamide system obtained in the step (2), starting stirring, setting the stirring rotation speed to 275r/min, adding 0.11g of hydrochloric acid solution (concentrated hydrochloric acid with the mass fraction of 37 percent) after the system is uniformly mixed, at the moment, raising the pH value of the system to 3.15, raising the temperature to 55 ℃, and carrying out grafting modification on the thio monomer at the temperature for 2h to obtain a product obtained through grafting modification of the thio monomer, namely the sulfur-containing strong coordination aqueous solution amine-methylated polyacrylamide, and cooling the system to 25 ℃ for later use.
(4) Hydrolysis modification:
adding 3.15g of sodium hydroxide and 1.5g of sorbitan sesquioleate into 95.35g of the sulfur-containing strong coordination aqueous solution amine-type polyacrylamide system obtained in the step (3), starting stirring, setting the rotating speed to 275r/min, uniformly mixing, wherein the pH value of the system is 11.25, simultaneously raising the temperature of the system to 88 ℃, sealing a reaction kettle, continuously preserving heat and hydrolyzing for 6.5h at the temperature to obtain hydrolysis modified aqueous solution polyacrylamide (also called as anionic sulfur-containing strong coordination aqueous solution amine-type polyacrylamide), and cooling the system to 25 ℃ for later use; the hydrolysis degree of the hydrolysis modified aqueous solution polyacrylamide at the normal temperature of 25 ℃ is 24.5 percent.
(5) Esterification grafting modification:
adding 0.11g of hydrochloric acid solution (concentrated hydrochloric acid with the mass fraction of 37%) and 5.11g of hydroxyl-containing modifier solution (obtained by dissolving 2.48g of triethylsilanol with 2.63g of trichloroethylene) into 94.78g of the hydrolysis modified aqueous solution polyacrylamide system obtained in the step (4), starting stirring, setting the rotating speed to 275r/min, uniformly mixing, then setting the pH value of the system to 7.03, simultaneously raising the temperature to 55 ℃ for esterification grafting modification for 4 hours, and cooling the system to 25 ℃ to obtain the modified aqueous solution polyacrylamide flocculant; the apparent viscosity of the modified aqueous solution polyacrylamide flocculant at the normal temperature of 25 ℃ is 626 mPas, and the viscosity average molecular weight is 1293 ten thousand.
Example 4
Example 4 is substantially the same as example 1 except that:
(4) hydrolysis modification:
adding 2g of sodium hydroxide and 0.87g of sorbitan sesquioleate into 95.7g of the sulfur-containing strong coordination aqueous solution amine-type polyacrylamide system obtained in the step (3), starting stirring, setting the rotating speed to 275r/min, uniformly mixing, simultaneously raising the temperature of the system to 70 ℃, sealing the reaction kettle, continuously preserving heat and hydrolyzing for 5 hours at the temperature to obtain hydrolysis modified aqueous solution-type polyacrylamide, and cooling the system to 25 ℃ for later use; the hydrolysis degree of the hydrolysis modified aqueous solution polyacrylamide at the normal temperature of 25 ℃ is 10 percent.
Example 5
Example 5 is substantially the same as example 1 except that:
(4) hydrolysis modification:
adding 4g of sodium hydroxide and 1.74g of sorbitan sesquioleate into 95.7g of the sulfur-containing strong coordination aqueous solution amine-type polyacrylamide system obtained in the step (3), starting stirring, setting the rotating speed to 275r/min, uniformly mixing, simultaneously raising the temperature of the system to 89 ℃, sealing the reaction kettle, continuously preserving heat and hydrolyzing for 8 hours at the temperature to obtain hydrolysis modified aqueous solution-type polyacrylamide, and cooling the system to 25 ℃ for later use; the hydrolysis degree of the hydrolysis modified aqueous solution polyacrylamide at the normal temperature of 25 ℃ is measured to be 45%.
Example 6
Example 6 is substantially the same as example 1 except that:
(1) preparing aqueous solution polyacrylamide:
adding 263g of acrylamide, 654g of ammonium phosphate-phosphate buffer with the pH value of 6.23, 41g of sodium vinylsulfonate, 29g of N-phenylthiourea and 13g of 3- (N, N-dimethyl hexadecyl ammonium) propanesulfonate into a reaction kettle, starting stirring, setting the rotating speed to 275r/min, fully dissolving the system, blowing nitrogen to remove oxygen for 36min, and raising the temperature of the system to 30 ℃; then adding 0.125g of dibenzyl azodicarbonate, 0.065g of ethylenediamine tetramethylene phosphorus, 0.2g of ammonium oxalate and 0.113g of benzoyl peroxide into the system in turn, continuously blowing nitrogen to remove oxygen for 11min, then protecting nitrogen, keeping the stirring state (the rotating speed is set to 275 r/min), initiating the polymerization under the condition of 30 ℃, naturally heating the polymerization, naturally heating the system to 89 ℃ at the peak temperature for 3.6h, then preserving heat for 2.3h at the peak temperature, changing the system into a transparent aqueous solution state at the moment, obtaining aqueous solution polyacrylamide, and cooling the system to 25 ℃ for later use; the measured viscosity-average molecular weight of the aqueous solution polyacrylamide at 25 ℃ at normal temperature was 200 ten thousand, and the apparent viscosity was 95 mPa.s.
Example 7
Example 7 is substantially the same as example 1 except that:
(1) preparing aqueous solution polyacrylamide:
adding 263g of acrylamide, 654g of ammonium phosphate-phosphate buffer with the pH value of 6.23, 41g of sodium vinylsulfonate, 29g of N-phenylthiourea and 13g of 3- (N, N-dimethyl hexadecyl ammonium) propanesulfonate into a reaction kettle, starting stirring, setting the rotating speed to 275r/min, fully dissolving the system, blowing nitrogen to remove oxygen for 36min, and raising the temperature of the system to 30 ℃; then adding 0.125g of dibenzyl azodicarbonate, 0.065g of ethylenediamine tetramethylene phosphorus, 0.02g of ammonium oxalate and 0.113g of benzoyl peroxide into the system in turn, continuously blowing nitrogen to remove oxygen for 11min, then protecting nitrogen, keeping the stirring state (the rotating speed is set to 275 r/min), initiating the polymerization under the condition of 30 ℃, naturally heating the polymerization, naturally heating the system to 89 ℃ at the peak temperature for 3.6h, then preserving heat for 2.3h at the peak temperature, changing the system into a transparent aqueous solution state at the moment, obtaining aqueous solution polyacrylamide, and cooling the system to 25 ℃ for later use; the measured viscosity-average molecular weight of the aqueous solution polyacrylamide at the normal temperature of 25 ℃ is 1000 ten thousand, and the apparent viscosity is 500 mPa.s.
The modified polyacrylamide flocculant obtained in the step (5) of the embodiment has excessively high viscosity-to-phase molecular mass, so that the system is in a viscous state, the obtained viscous modified polyacrylamide flocculant has poor product solubility and poor application effect.
Example 8
Example 8 is substantially the same as example 1 except that:
(5) esterification grafting modification:
adding 0.093g of hydrochloric acid solution (concentrated hydrochloric acid with the mass fraction of 37%) and 4g of hydroxyl-containing modifier solution (obtained by dissolving 2g of triethylsilanol with 2g of trichloroethylene) into 94.907g of hydrolysis modified aqueous solution polyacrylamide system obtained in the step (4), starting stirring, setting the rotating speed to 275r/min, uniformly mixing, raising the temperature to 48 ℃ for esterification grafting modification for 3.5h, and cooling the system to 25 ℃ to obtain the modified aqueous solution polyacrylamide flocculant.
Example 9
Example 9 is substantially the same as example 1 except that:
(5) esterification grafting modification:
adding 0.093g of hydrochloric acid solution (concentrated hydrochloric acid with the mass fraction of 37%) and 7g of hydroxyl-containing modifier solution (obtained by dissolving 3.5g of triethylsilanol with 3.5g of trichloroethylene) into 94.907g of hydrolysis modified aqueous solution polyacrylamide system obtained in the step (4), starting stirring, setting the rotating speed to 275r/min, uniformly mixing, raising the temperature to 65 ℃ for esterification grafting modification for 6 hours, and cooling the system to 25 ℃ to obtain the modified aqueous solution polyacrylamide flocculant.
In this example, too much amount of the hydroxyl group-containing modifier is liable to cause intermolecular and intramolecular crosslinking, resulting in poor product solubility, and thus a soluble modified aqueous solution type polyacrylamide flocculant cannot be obtained.
Comparative example 1
Comparative example 1 is substantially the same as example 1 except that:
in the comparative example, the diluent sodium vinylsulfonate was not added in the preparation of the aqueous polyacrylamide in the step (1).
In the preparation process of comparative example 1, the aqueous solution polyacrylamide system obtained in step (1) is in a colloid state, and subsequent steps (2) to (5) cannot be performed.
Comparative example 2
Comparative example 2 is substantially the same as example 1 except that:
in the comparative example, the hydrolysis inhibitor N-phenylthiourea was not added in the preparation of the aqueous polyacrylamide in the step (1).
The viscosity-average molecular weight of the aqueous solution polyacrylamide prepared in the step (1) of the comparative example is 463 ten thousand, the hydrolysis degree of the hydrolysis modified aqueous solution polyacrylamide prepared in the step (4) is 56%, the viscosity-average molecular weight of the flocculant prepared in the step (5) is 1058 ten thousand, the viscosity-average molecular weight of the flocculant product is slightly reduced, probably because the hydrolysis resisting agent is favorable for ensuring the stability of the system in a high-temperature state in the reaction process, the hydrolysis resisting agent is not added, amide groups can be hydrolyzed at high temperature, viscosity reduction phenomenon occurs, the viscosity-average molecular weight of a basic system and the flocculant product is slightly reduced, and the amide groups used for subsequent modification are obviously reduced due to self-hydrolysis of the basic system, so that the overall performance of the flocculant product is obviously deteriorated.
Comparative example 3
Comparative example 3 is substantially the same as example 1 except that:
in the comparative example, the modification was carried out in step (3) using the common metal complexing agent ethylenediamine tetraacetic acid instead of 2- (dodecyltrithiocarbonate) -2-methylpropanoic acid.
Comparative example 4
Comparative example 4 is substantially the same as example 1 except that:
the comparative example does not comprise the step (4) and does not comprise the step (5), and the sulfur-containing strong coordination aqueous solution amine methylated polyacrylamide obtained in the step (3) is used as a flocculant product.
Comparative example 5
Comparative example 5 is substantially the same as example 1 except that:
the comparative example does not comprise the step (5), and the hydrolysis modified aqueous solution polyacrylamide obtained in the step (4) is used as a flocculant product.
Comparative example 6
Comparative example 6 is substantially the same as example 1 except that:
in the comparative example, in the step (5), N-bis (2-hydroxyethyl) -2-aminoethanesulfonic acid is adopted to replace triethylsilanol for esterification grafting modification.
The comparative example adopts N, N-bis (2-hydroxyethyl) -2-aminoethanesulfonic acid to replace triethylsilanol for esterification grafting modification, and can not obtain soluble modified aqueous solution polyacrylamide flocculant, probably because the N, N-bis (2-hydroxyethyl) -2-aminoethanesulfonic acid is adopted to easily cause the product to crosslink.
The flocculant products finally prepared in examples 1-8 and comparative examples 2-5 were subjected to performance evaluation, and the results are shown in Table 1.
Cu 2+ The method for testing the ion removal rate comprises the following steps:
(a) Preparation of stock solution:
weigh 1.5625g CuSO 4 ·5H 2 O, dissolving the mixture to a volume of 1000mL by deionized water to obtain Cu with a concentration of 1000mg/L 2+ A stock solution; 40.0g of NaOH is weighed, and dissolved by deionized water to reach 1000mL of constant volume to obtain NaOH stock solution with the concentration of 1 mol/L; weighing 36.5g of HCl, and dissolving the HCl with deionized water to a volume of 1000mL to obtain a HCl stock solution with a concentration of 1 mol/L; in the subsequent test, various stock solutions are diluted to a certain concentration by deionized water according to the requirement for standby.
(b) Cu is added with 2+ Stock solution is diluted to Cu 2+ Concentration ofs 0 20mg/L to give Cu 2+ Storing the diluted solution and removing Cu 2+ Stock diluentV 0 500mL into a beaker. Cu was adjusted with HCl stock dilution to 0.1mol/L or NaOH stock dilution to 0.1mol/L 2+ Storing the pH value of the diluent to 6.5, placing the water sample under a six-link stirrer (ZH 7098, zhonghui Tiancheng technology Co., ltd.), adjusting the rotating speed to 150r/min, adding a flocculant sample according to the concentration of 2 per mill by mass, stirring at 150r/min for 25 seconds, reducing the rotating speed to 50r/min, continuing stirring for 60 seconds, standing for 5 minutes, and taking the supernatant by a pipette V 1 For Cu in atomic absorption spectrometer (PerkinElmer, pinAAcle T) 2+ Concentration was measured to determine residual Cu 2+ Concentration ofs 1 The flocculated precipitate was used as a chelate floc and the removal rate CQ was calculated according to the following formula (1), as followsCalculating Cu in the chelate floc according to the formula (2) 2+ Quality of (2)W 1 The method comprises the steps of carrying out a first treatment on the surface of the Wherein Cu is 2+ The concentration is measured by a Perkinelmer PinAAcle 900T atomic absorption spectrometer, a standard curve method is used, the measuring range is 0.1-20 mg/L, an air-acetylene flame is adopted, the flow rate of fuel gas (acetylene) is 1.6L/min, the flow rate of combustion-supporting gas (air) is 12.0L/min, and the set wavelength of the copper hollow cathode lamp is 324.75nm.
（1）
（2）
Chelating floc Cu 2+ The ion recovery rate test method comprises the following steps:
Cu 2+ preparing an ion recovery liquid: weighing 36.5g of HCl, dissolving with deionized water to 1000mL to obtain hydrochloric acid solution with concentration of 1mol/L as Cu 2+ The ion recovery liquid is used, and copper ions can be replaced by a replacement reaction.
The mass obtained isW 1 After washing and drying the chelate flocs with deionized water, 100mL of 1mol/L Cu was used 2+ Soaking in ion recovery solution for 20min, transferring 60mL of soaking solution with a pipette, and performing atomic absorption spectrometry (PerkinElmer, pinAAcle T) on Cu 2+ Measuring the concentration, and calculating Cu in the soaking solution 2+ Quality of (2)W 2 Chelating floc Cu 2+ Ion recovery E was calculated according to equation (3).
（3）/>
The test method of the turbidity removal rate of the supernatant fluid comprises the following steps:
preparation of a kaolin suspension: 10g of kaolin is weighed, dissolved with deionized water to a volume of 1000mL to obtain a kaolin suspension with a concentration of 10 g/L.
Turbidity removal rate of supernatantCN 0 Is determined by the test of (a): cu is added with 2+ Stock solution is diluted to Cu 2+ The concentration is 20mg/L, and Cu is obtained 2+ Storing the diluted solution and removing Cu 2+ 200mL of stock dilution was added to a beaker, and 200mL of a 10g/L kaolin suspension was added to prepare an initial turbidityN 1 Adjusting pH of 100NTU waste water to 6.5 with 0.1mol/L HCl stock solution or 0.1mol/L NaOH stock solution, placing water sample under six-connected stirrer (ZHI TIANCHONG technology Co., ltd., ZH 7098), adjusting rotation speed to 150r/min, adding flocculant sample at a concentration of 2%o by mass, stirring at 150r/min for 25 s, reducing rotation speed to 50r/min, continuing stirring for 60 s, standing for 5 min, taking supernatant with pipette, and testing turbidity with turbidimeter (2100P type, U.S. Hash Co.) to obtain supernatantN 2 Turbidity removal rate of supernatantCN 0 Calculated according to formula (4).
（4）
The test for thermal stability (resistance to aging) was: and (3) placing the water solution flocculant product in a sealing tank, deoxidizing, and placing at 80 ℃ for 5 days to measure the apparent viscosity change rate of the flocculant product, namely the thermal stability.
Specifically, the invention relates to a test of viscosity-average molecular weight and degree of hydrolysis (i.e., degree of anions): tested according to GB/T17514-2017 standard; apparent viscosity test: the test is carried out by a BROOKFIELD viscometer (DV 2T, shanghai micro-Sichuan precision instruments Co., ltd.) at 23-25deg.C, with the rotation speed set at 30r/min and the rotor selected from 63#.
TABLE 1
The invention is not described in detail in a manner known to those skilled in the art.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. The preparation method of the modified aqueous solution polyacrylamide flocculant is characterized by comprising the following steps of:
(1) Polymerizing raw materials comprising acrylamide monomers, pH buffer solution with the pH value of 6.1-6.3, diluent, anti-hydrolysis agent, a cosolvent, an initiator, a metal complexing agent and a chain transfer agent to obtain aqueous solution polyacrylamide; the diluent is sodium olefin sulfonate monomer; the anti-hydrolysis agent is thiourea monomer; the thiourea monomer is one or more of 4-phenyl-3-thiosemicarbazide, N-phenylthiourea, N' -dimethylthiourea and 4-methyl thiosemicarbazide;
(2) Sequentially carrying out aminomethylation modification and grafting modification on thio monomers on aqueous solution polyacrylamide, and then adding an alkaline hydrolysis agent and a dispersing agent for hydrolysis modification to obtain hydrolysis modified aqueous solution polyacrylamide; the thio monomer is one or more of 4-chlorthiophenol, 2-thiobarbituric acid, 2- (dodecyl trithiocarbonate group) -2-methylpropionic acid, 2' -dithiodibenzoic acid, 4-imidazole dithiocarboxylic acid, 2-hydroxyethyl disulfide and bis (carboxymethyl) trithiocarbonate;
(3) Adding an acid catalyst and a hydroxyl-containing modifier solution into the hydrolysis modified aqueous solution polyacrylamide for esterification grafting modification to prepare a modified aqueous solution polyacrylamide flocculant; the hydroxyl-containing modifier in the hydroxyl-containing modifier solution is one or more of triethylsilanol, tert-butyldimethylsilanol, N-ethyl-3-pyrrolidinol, N-undecanol and 9-bromo-1-nonanol.
2. The method of claim 1, wherein in step (1):
the polymerization reaction is carried out in a nitrogen atmosphere;
initiating a polymerization reaction at 28-31 ℃, naturally heating the polymerization reaction, wherein the peak temperature of the natural heating is 88-90 ℃, and then preserving heat for 2-2.5 h at the peak temperature;
the acrylamide monomer is one or more of acrylamide, methacrylamide, N-dimethylacrylamide and N-phenylacrylamide;
the pH buffer solution is one or more of sodium acetate-acetic acid buffer solution, ammonium phosphate-phosphoric acid buffer solution and sodium citrate-citric acid buffer solution;
the sodium olefin sulfonate monomer is one or more of sodium vinyl sulfonate, sodium methacrylate sulfonate and sodium p-styrene sulfonate;
the cosolvent is a monomer containing amino and/or sulfonate, and the monomer containing amino and/or sulfonate is one or more of N-dodecyl-N, N-dimethylglycine, N-tetradecyl-N, N-dimethyl-3-ammonio-1-propanesulfonate, 3- (N, N-dimethyl hexadecyl ammonium) propanesulfonate and 3- (dodecyl dimethyl ammonium) propanesulfonate;
the initiator comprises azo initiator and peroxidation initiator, wherein the azo initiator is one or more of dibenzyl azodicarbonate, 4' -azobisanisole, diisopropyl azodicarbonate and azobisisobutylamidine hydrochloride, and the peroxidation initiator is one or more of di-tert-butyl peroxide, benzoyl peroxide, dicumyl peroxide, cumene hydroperoxide and tert-butylcumene peroxide;
The metal complexing agent is one or more of ethylenediamine tetramethylene phosphoric acid, diethylenetriamine pentamethylene phosphonic acid and dihydroxyethyl glycine; and/or
The chain transfer agent is one or more of sodium hypophosphite, sodium formate, ammonium oxalate and disodium succinate.
3. The method of claim 1, wherein in step (1):
the initiator comprises azo initiator and peroxidation initiator;
the mass ratio of the acrylamide monomer, the pH buffer solution, the diluent, the hydrolysis inhibitor, the cosolvent, the azo initiator, the metal complexing agent, the chain transfer agent and the peroxidation initiator is (25.5-27.2): (62.7 to 67.8): (3-5): (2.6 to 3.5): (1.1 to 1.6): (0.012-0.013): (0.0062-0.0068): (0.0078-0.0083): (0.011 to 0.012).
4. The method of claim 1, wherein in step (3):
the acid catalyst is one or more of hydrochloric acid solution, glacial acetic acid and sulfuric acid solution;
the hydroxyl-containing modifier solution is formed by mixing a hydroxyl-containing modifier and an organic solvent, wherein the organic solvent is one or more of ethanol, styrene, ethylene glycol and trichloroethylene;
The mass ratio of the hydrolysis modified aqueous solution polyacrylamide to the hydroxyl-containing modifier to the organic solvent to the acid catalyst is (94.48-95.11): (2.4 to 2.7): (2.4 to 2.7): (0.09-0.12);
the temperature of the esterification grafting modification is 55-58 ℃ and the time is 4-5 h.
5. The method of claim 1, wherein in step (2):
the alkaline hydrolysis agent is one or more of potassium hydroxide, sodium carbonate and ammonia water;
the dispersing agent is one or more of sorbitan monostearate, sorbitan sesquioleate and sorbitan monopalmitate;
the temperature of the hydrolysis modification is 88-90 ℃ and the time is 6.5-7 h; and/or
The mass ratio of the alkaline hydrolysis agent to the dispersant to the product obtained by graft modification of the thio monomer is (2.8-3.2): (1.1 to 1.5): (95.3-96.1).
6. The method of manufacturing according to claim 1, characterized in that:
the viscosity-average molecular weight of the aqueous solution polyacrylamide obtained in the step (1) is 600-800 ten thousand;
the hydrolysis degree of the hydrolysis modified aqueous solution polyacrylamide obtained in the step (2) is 23-26%; and/or
The viscosity-average molecular weight of the modified aqueous solution polyacrylamide flocculant obtained in the step (3) is 1200-1300 ten thousand.
7. The method according to any one of claims 1 to 6, wherein in step (2), the aminomethylation modification is:
and (3) uniformly mixing and reacting aldehyde, amine and an acid catalyst with water to obtain a hydroxymethyl dimethylamine aqueous solution, and then adding the hydroxymethyl dimethylamine aqueous solution into the aqueous solution polyacrylamide obtained in the step (1), uniformly mixing and carrying out aminomethylation modification.
8. The method of manufacturing according to claim 7, wherein:
the aldehyde is formaldehyde and/or trioxymethylene;
the amine is dimethylamine;
the acid catalyst adopted by the aminomethylation modification is one or more of hydrochloric acid solution, glacial acetic acid and sulfuric acid solution;
the temperature of the aminomethylation modification is 55-58 ℃ and the time is 1.5-2 h; and/or
The mass ratio of the water, the aldehyde, the amine, the acid catalyst and the aqueous solution polyacrylamide is (17.31-20.75): (1.4 to 1.8): (1.4 to 1.8): (0.05-0.09): (74.46 to 79.04).
9. The production method according to any one of claims 1 to 6, wherein in step (2):
The grafting modification of the thio-monomer is carried out in the presence of an acid catalyst, wherein the acid catalyst is one or more of hydrochloric acid solution, glacial acetic acid and sulfuric acid solution;
in the graft modification of the thio-monomer, the mass ratio of the thio-monomer, the acid catalyst and the product obtained by the aminomethylation modification is (5.2-5.8): (0.08-0.11): (94.09-94.72);
the grafting modification temperature of the thio-monomer is 55-58 ℃ and the time is 2-2.5 h.
10. A modified aqueous solution-based polyacrylamide flocculant produced by the production method of any one of claims 1 to 9.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4744893A (en) * | 1985-08-28 | 1988-05-17 | American Cyanamid Company | Polymeric sulfide mineral depressants |
| CN102060965A (en) * | 2009-11-11 | 2011-05-18 | 中国科学院理化技术研究所 | Preparation method of partially hydrolyzed polyacrylamide with improved temperature resistance and salt resistance |
| CN103788295A (en) * | 2012-10-30 | 2014-05-14 | 中国石油化工股份有限公司 | Two-step preparation method of acrylamide copolymer |
| CN106977631A (en) * | 2017-03-20 | 2017-07-25 | 浙江工商大学 | A kind of modified polyacrylamide and its preparation method and application |
| CN111285966A (en) * | 2020-03-13 | 2020-06-16 | 爱森（中国）絮凝剂有限公司 | Modified strong anionic polymer flocculant and preparation method thereof |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4744893A (en) * | 1985-08-28 | 1988-05-17 | American Cyanamid Company | Polymeric sulfide mineral depressants |
| CN102060965A (en) * | 2009-11-11 | 2011-05-18 | 中国科学院理化技术研究所 | Preparation method of partially hydrolyzed polyacrylamide with improved temperature resistance and salt resistance |
| CN103788295A (en) * | 2012-10-30 | 2014-05-14 | 中国石油化工股份有限公司 | Two-step preparation method of acrylamide copolymer |
| CN106977631A (en) * | 2017-03-20 | 2017-07-25 | 浙江工商大学 | A kind of modified polyacrylamide and its preparation method and application |
| CN111285966A (en) * | 2020-03-13 | 2020-06-16 | 爱森（中国）絮凝剂有限公司 | Modified strong anionic polymer flocculant and preparation method thereof |
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